JPH06345885A - Method for treating cyclic olefinic resin - Google Patents

Abstract

PURPOSE:To provide a method for treating an olefinic resin, capable of obtaining the olefinic resin improved in various physical properties such as heat resistance, water resistance and chemical resistance and having sufficient elasticity and flexibility. CONSTITUTION:One or more cyclic olefinic resins having glass transition temperatures (Tg) of <= 50 deg.C and selected from an alphaolefin-cyclic olefin addition copolymer [a], a polymer produced by ring-opening polymerization of a cyclic olefin [b], its ring-opened copolymer [c], and their hydrogenated products [a'], [b'] and [c'] are treated with electron rays or radiation rays.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating a cyclic olein-based resin. More specifically, it relates to a method for treating a cyclic olefin resin, which can provide a cyclic olefin resin that is preferably used in the medical field such as an infusion bag, the packaging field, the food field, and the like.

[0002]

2. Description of the Related Art The present applicant has previously proposed a cyclic olefin resin which is excellent in flexibility and elastic recovery property and can be used as a film, a sheet and the like in various fields such as medical, packaging and food products fields. (Japanese Patent Application No. 4-90261). However, depending on the application in which the cyclic olefin resin is used, for example, in the case of medical and waterproof sheet applications, thermal stability, water resistance, chemical resistance, elasticity, etc. are required. As it is, it is not always satisfactory, and it was necessary to modify it.

Further, a method of crosslinking a cyclic olefin copolymer with sulfur or the like has been disclosed (Japanese Patent Laid-Open No. 62-62-62).
34924). However, the cyclic olefin-based copolymer disclosed herein has a glass transition temperature (Tg) of 60 ° C. or higher and lacks flexibility, and thus in a field requiring a film or sheet having elasticity or flexibility. It was not always completely satisfactory.

Further, in the medical field, a method of sterilizing a material used for an infusion bag or the like by γ-ray is used, but a conventional sheet using soft vinyl chloride or L-LDPE is yellowed by γ-ray. There was a problem of doing.
In addition, in the method of crosslinking using sulfur or organic peroxide,
There are problems that additives are released from the resin and decomposition products are generated.

[0005]

The present invention has been made in view of the above problems and is excellent in various physical properties such as heat resistance, water resistance, chemical resistance and the like, and has sufficient elasticity and flexibility. An object of the present invention is to provide a method for treating an olefin resin, which is also capable of obtaining an olefin resin.

[0006]

According to the present invention, a copolymer [a] formed by addition-polymerizing an α-olefin and a cyclic olefin, a polymer [b] formed by ring-opening polymerization of a cyclic olefin, A glass transition temperature (Tg) selected from the group consisting of the ring-opening copolymer [c] and hydrogenated products [a ′], [b ′] and [c ′] thereof is 50 ° C. or lower. There is provided a method for treating a cyclic olefin resin, which comprises treating the above cyclic olefin resin with an electron beam or radiation.

Further, the cyclic olefin resin before the treatment is in a mol% of the α-olefin and the cyclic olefins.
Is 80:20 to 99.9: 0.1, and a method for treating a cyclic olefin resin is provided.

Further, a cross-linked cyclic olefin resin obtained by the above treatment method is provided.

Further, melt index [MI] (19
0 ° C., 2.16 kg) is less than 0.1 g / 10 min, the tensile elastic modulus is 50 to 3,000 kg / cm ² , and the elastic recovery rate is 20 to 100%. The body is provided.

The present invention will be described in detail below. 1. Cyclic olefin-based resin The cyclic olefin-based resin used in the present invention is a copolymer obtained by addition-polymerizing an α-olefin and a cyclic olefin as described above, a polymer obtained by ring-opening polymerization of a cyclic olefin, One or more is selected from the group consisting of the copolymer and hydrogenated products thereof. α-Olefin The α-olefin used in the production of the cyclic olefin-based resin used in the present invention is not particularly limited, and includes, for example, the following general formula [X]

[Chemical 1] (In the formula [X], Ra represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms).

In the repeating unit of the α-olefin represented by the general formula [X], R ^a represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms as described above.
Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, isopropyl group, isobutyl group, n-butyl group, n-hexyl group, octyl group and octadecyl group. be able to. Further, specific examples of the α-olefin that gives the repeating unit of the α-olefin represented by the general formula [X] include, for example, ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1. -Pentene, 1-hexene, 1-octene, decene, eicosene and the like can be mentioned.
Of these, ethylene or propylene, or ethylene and propylene are preferable. Cyclic olefins The cyclic olefins used in the present invention include cyclic olefins and cyclic dienes. -1 Cyclic Olefin The cyclic olefin used in the present invention is not particularly limited, and examples thereof include those giving a repeating unit represented by the following general formula [Y].

[Chemical 2] (In the formula [Y], R ^{b to} R ^m each represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a substituent containing a halogen atom, an oxygen atom or a nitrogen atom, and n represents an integer of 0 or more. R ^j or R ^k and R ^l or R ^m may form a ring with each other, and R ^{b to} R ^m may be the same or different from each other.)

In the repeating unit represented by the above general formula [Y], R ^{b to} R ^m are each a hydrogen atom or a carbon number 1
~ 20 hydrocarbon groups, or a substituent containing a halogen atom, an oxygen atom or a nitrogen atom. Here, as the hydrocarbon group having 1 to 20 carbon atoms, specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group,
C1-C20 alkyl group such as n-butyl group, isobutyl group, t-butyl group, hexyl group, etc., C6-C20 aryl group such as phenyl group, tolyl group, benzyl group, alkylaryl group or aryl 1 to 20 carbon atoms such as alkyl group, methylidene group, ethylidene group, propylidene group
2 to 2 carbon atoms such as alkylidene group, vinyl group and allyl group
There may be mentioned 20 alkenyl groups and the like. However, R
^b , R ^c , R ^f , and R ^{g do not} include an alkylidene group. In addition,
When any of R ^d , R ^e and R ^{h to} R ^m is an alkylidene group, the carbon atom to which it is attached has no other substituent.

Specific examples of the substituent containing a halogen atom include halogen groups such as fluorine, chlorine, bromine and iodine, and halogen substitution having 1 to 20 carbon atoms such as chloromethyl group, bromomethyl group and chloroethyl group. An alkyl group etc. can be mentioned. Specific examples of the substituent containing an oxygen atom include, for example, an alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a phenoxy group, and a 1 to 20 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group. And an alkoxycarbonyl group. Specifically as a substituent containing a nitrogen atom,
For example, a C1-C20 alkylamino group, such as a dimethylamino group and a diethylamino group, a cyano group, etc. can be mentioned.

Specific examples of the cyclic olefin giving the repeating unit represented by the general formula [Y] include, for example, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1 -Methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene, 5
-Phenyl norbornene, 5-benzyl norbornene,
5-ethylidene norbornene, 5-vinyl norbornene, 1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2,3-
Dimethyl-1,4,5,8-dimethano-1,2,3
4,4a, 5,8,8a-octahydronaphthalene, 2
-Hexyl-1,4,5,8-dimethano-1,2,3,3
4,4a, 5,8,8a-octahydronaphthalene, 2
-Ethylidene-1,4,5,8-dimethano-1,2,
3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,
2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Octahydronaphthalene, 2,3-dichloro-1,4,5,8-
Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8
-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,2-dihydrodicyclopentadiene, 5-chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5 , 5, 6
-Trifluoro-6-trifluoromethyl norbornene, 5-chloromethyl norbornene, 5-methoxy norbornene, 5,6-dicarboxyl norbornene anhydrate, 5-dimethylamino norbornene, 5-cyanonorbornene and the like can be mentioned.

Further, it may give a repeating unit represented by the following formula [Z].

[0016]

[Chemical 3] (In the formula, l is an integer of 0 or 1, and m and n are
0, 1 or 2, R ^{1 to} R ¹⁵ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, and R ⁵ (or R ⁶ ).
And R ⁹ (or R ⁷ ) may be bonded to each other through an alkylene group having 1 to 3 carbon atoms, or may be directly bonded to each other without any group. )

Specific examples of the cyclic olefin giving the repeating unit represented by the above formula [Z] include 5-methyl-
5-Phenyl-bicyclo [2.2.1] hept-2-ene, 5-tolyl-bicyclo [2.2.1] hept-2-
Ene, 5- (ethylphenyl) -bicyclo [2.2.
1] hept-2-ene, 5- (isopropylphenyl)
-Bicyclo [2.2.1] hept-2-ene, 1,4-
Methano-1,1a, 4,4a-tetrahydrofluorene, 1,4-methano-1,4,4a, 5,10,10a
-Hexahydroanthracene, cyclopentadiene-acenaphthylene adduct, 5- (α-naphthyl) -bicyclo [2.2.1] hept-2-ene, 5- (anthracenyl) -bicyclo [2.2.1] hept- 2-ene can be mentioned.

-2 Cyclic Diene The cyclic diene used in the present invention is not particularly limited, but for example, 1,3-cyclopentadiene, 1,3-
Cyclohexadiene, 1,4-cyclohexadiene, 5
-Ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,4-cycloheptadiene, 1,3
-Cyclooctadiene, 1,4-cyclooctadiene,
1,5-cyclooctadiene, 5-methylene-2-norbornene, dicyclopentadiene, dimethyldicyclopentadiene, and

[Chemical 4] Etc. can be mentioned. Among these, norbornene, norbornene derivatives, 5-ethylidene-2-norbornene, 5-vinylnorbornene and dicyclopentadiene are particularly preferable. The cyclic diene may have at least two double bonds, and includes, for example, cyclic triene and the like.

Copolymer of α-Olefin and Cyclic Olefin [a] α-Olefin of a copolymer obtained by addition-polymerizing an α-olefin used in a cyclic olefin resin,
The composition ratio of olefin (for example, one having a repeating unit represented by the general formula [X]) and cyclic olefin (for example, one having a repeating unit represented by the general formula [Y]) is mol%. Then, from 80:20
99.9: 0.1 is preferable. When the content of α-olefin is less than 80 mol%, Tg and elastic modulus increase, and the elastic recovery property and flexibility of the obtained film or sheet decrease. Further, when the content of cyclic olefins is less than 0.1 mol%, the crystallinity of the copolymer becomes high, and the effect of introducing the cyclic olefin becomes insufficient in terms of elastic recovery and the like. More preferably, it is 90:10 to 99.5: 0.5 in terms of mol%, and most preferably 85:15 to 98: 2 in terms of mol%.

In addition to ethylene as the α-olefin, the following general formula [R]

[Chemical 5] (R ^p is a hydrocarbon group having 1 to 20 carbon atoms, preferably propylene, 1-butene, 4-methyl-1-butene, 1-
It is octene. When two kinds of the α-olefin represented by (4) are used, the composition ratio thereof is ethylene 5 to 99.
8 mol% and α-olefin of the general formula [R] 75-
It is preferably 0.1 mol% and 20 to 0.1 mol% of cyclic olefins. More preferably, ethylene is 32 to 99 mol%, and α-olefin [R] 50 to.
0.5 mol% and cyclic olefins 18 to 0.5 mol%. Among them, 55 to 98 mol% of ethylene, 30 to 1 mol% of α-olefin [R], and 15 to 1 mol% of cyclic olefins are most preferable. In this case, ethylene and α-olefin [R] are preferably 80 to 99.9 mol% of the whole copolymer.

The method of addition polymerizing the α-olefin and the cyclic olefins is not particularly limited, and any catalyst system of an ion complex catalyst, an aluminoxane catalyst and a soluble vanadium catalyst may be used. Among these, ion complex catalysts are preferable because of their high polymerizability. Hereinafter, as specific examples of the ion complex catalyst, the following (A) and (B)
A catalyst containing as the main component or a catalyst system containing the following compounds (A), (B) and (C) as the main components will be described. (A) Transition metal compound (B) Transition metal compound (A) or compound capable of forming an ionic complex from its derivative (C) Organoaluminum compound

In this case, the transition metal compound (A) includes IVB group, VB group, VIB group, VIIB group and VI of the periodic table.
Transition metal compounds including transition metals belonging to Group II can be used. As the transition metal, specifically, titanium, zirconium, hafnium, chromium, manganese, nickel, palladium, platinum and the like are preferable, and among them, zirconium, hafnium, titanium, nickel and palladium are particularly preferable.

As the transition metal compound (A), various compounds can be mentioned, particularly IVB group,
A compound containing a transition metal of VB group, VI group or VIII group, especially a transition metal selected from IVB group of the periodic table, that is, a compound containing titanium (Ti), zirconium (Zr) or hafnium (Hf) is preferable. A cyclopentadienyl compound represented by the following general formula (I), (II) or (III) or a derivative thereof or a compound represented by the following general formula (IV) or a derivative thereof is particularly preferable. Is. ^{_{CpM 1 R 1 a R 2 b}} R 3 c ... (I) Cp 2 M 1 R 1 a R 2 b ... (II) (Cp-A e -Cp) M 1 R 1 a R 2 b ... (III) M ¹ R ¹ _a R ² _b R ³ _c R ⁴ _d (IV)

[In the formulas (I) to (IV), M ¹ is Ti, Zr.
Or Hf atom, Cp is a cyclopentadienyl group,
A cyclic unsaturated hydrocarbon group or a chain unsaturated hydrocarbon group such as a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group is shown. R ¹ , R ² , R ³ and R ⁴ are each σ
A binding ligand, a chelating ligand, a Lewis base, or other ligand is shown. Specific examples of the σ binding ligand include a hydrogen atom, an oxygen atom, a halogen atom, and a carbon number of 1 to 1. 20 alkyl groups, C 1-20 alkoxy groups, C 6-
Examples include 20 aryl groups, alkylaryl groups or arylalkyl groups, acyloxy groups having 1 to 20 carbon atoms, allyl groups, substituted allyl groups, substituents containing a silicon atom, and the like. Examples thereof include an acetylacetonate group and a substituted acetylacetonate group. A indicates crosslinking by covalent bond. a, b, c and d
Are integers of 0 to 4, respectively, and e is an integer of 0 to 6. R
Two or more of ¹ , R ² , R ³ and R ⁴ may combine with each other to form a ring. When the Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms. In the formulas (II) and (III), the two Cp's may be the same or different from each other. ]

Examples of the substituted cyclopentadienyl group in the above formulas (I) to (III) include a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an isopropylcyclopentadienyl group, 1,2-dimethyl. Cyclopentadienyl group, tetramethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,
2,3-trimethylcyclopentadienyl group, 1,2,
4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group and the like can be mentioned. Further, specific examples of R ^{1 to} R ⁴ in the above formulas (I) to (IV) include:
For example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom as a halogen atom; a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an octyl group as an alkyl group having 1 to 20 carbon atoms, 2-Ethylhexyl group; methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group as alkoxy group having 1 to 20 carbon atoms; phenyl group, tolyl group as aryl group, alkylaryl group or arylalkyl group having 6 to 20 carbon atoms Group, xylyl group, benzyl group; heptadecylcarbonyloxy group as an acyloxy group having 1 to 20 carbon atoms; trimethylsilyl group as a substituent containing a silicon atom, (trimethylsilyl) methyl group: dimethyl ether, diethyl ether, tetrahydrofuran etc. as a Lewis base Ethers, Tetra Thioethers such as dorothiophene, esters such as ethylbenzoate, nitriles such as acetonitrile and benzonitrile, amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 2,2′-bipyridine, phenanthroline , Triethylphosphine,
Phosphines such as triphenylphosphine; ethylene, butadiene, 1-pentene, as chain unsaturated hydrocarbon
Isoprene, pentadiene, 1-hexene and their derivatives; examples of cyclic unsaturated hydrocarbons include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and their derivatives. . Examples of the cross-linking by the covalent bond of A in the formula (III) include, for example, methylene cross-link, dimethyl methylene cross-link, ethylene cross-link, 1,1′-cyclohexylene cross-link, dimethyl silylene cross-link, dimethyl germylene cross-link, dimethyl stannylene cross-link. Etc. can be mentioned.

Examples of such compounds include the following and compounds in which zirconium of these compounds is replaced with titanium or hafnium. Compound of formula (I) (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl) tribenzylzirconium, (pentamethylcyclopentadienyl) trichloro Zirconium, (pentamethylcyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium, (cyclopentadienyl) tribenzylzirconium, (cyclopentadienyl) trichloro Zirconium, (cyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) dimethyl (methoxy) zirconium, (methylcyclopentadienyl) trimethyldi Ruconium, (methylcyclopentadienyl) triphenylzirconium, (methylcyclopentadienyl) tribenzylzirconium, (methylcyclopentadienyl) trichlorozirconium, (methylcyclopentadienyl) dimethyl (methoxy) zirconium,
(Dimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium, (trimethylsilylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium,

A compound of formula (II) bis (cyclopentadienyl) dimethyl zirconium,
Bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) diethylzirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium , Bis (cyclopentadienyl) dihydride zirconium, bis (cyclopentadienyl) monochloromonohydrido zirconium, bis (methylcyclopentadienyl) dimethylzirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclo Pentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) dimethylzirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, Scan (pentamethylcyclopentadienyl) dibenzyl zirconium, bis (pentamethylcyclopentadienyl) chloromethyl zirconium,
Bis (pentamethylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl) (pentamethylcyclopentadienyl) dichlorozirconium,

Compounds of the formula (III) ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) dichlorozirconium, ethylenebis (tetrahydroindenyl) dimethylzirconium, ethylenebis (tetrahydroindenyl) dichlorozirconium, dimethylsilylenebis (cyclo) Pentadienyl) dimethyl zirconium, dimethylsilylene bis (cyclopentadienyl) dichlorozirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dichlorozirconium , [Phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, diphenylmethylene (cyclopen Tadienyl)
(9-fluorenyl) dimethylzirconium, ethylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclohexylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium,
Cyclopentylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclobutylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium,
Dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dimethylzirconium, dimethylsilylenebis (indenyl) dichlorozirconium

Examples of the compounds other than the cyclopentadienyl compounds represented by the above general formulas (I), (II) and (III) include the compounds of the above formula (IV). Examples thereof include zirconium compounds having one or more kinds of alkyl groups, alkoxy groups and halogen atoms such as compounds in which zirconium is replaced with hafnium or titanium, hafnium compounds and titanium compounds. Tetramethylzirconium, tetrabenzylzirconium, tetramethoxyzirconium,
Tetraethoxyzirconium, tetrabutoxyzirconium, tetraphenoxyzirconium, tetra (2-ethylhexyloxy) zirconium, tetrachlorozirconium, tetrabromozirconium, butoxytrichlorozirconium, dibutoxydichlorozirconium, bis (2,6-di-t-butyl). Phenoxy) dimethyl zirconium, bis (2,6-di-t-butylphenoxy)
Dichlorozirconium, zirconium tetrakis (acetylacetonate),

The transition metal compound containing a VB to VIII group transition metal is not particularly limited, and specific examples of the chromium compound include tetramethylchromium and tetra (t).
-Butoxy) chromium, bis (cyclopentadienyl) chromium, hydridotricarbonyl (cyclopentadienyl) chromium, hexacarbonyl (cyclopentadienyl) chromium, bis (benzene) chromium, tricarbonyltris (triphenylphosphonate) Examples thereof include chromium, tris (allyl) chromium, triphenyltris (tetrahydrofuran) chromium, chromium tris (acetylacetonate), and the like.

Specific examples of manganese compounds include tricarbonyl (cyclopentadienyl) manganese, pentacarbonylmethylmanganese, bis (cyclopentadienyl) manganese, manganese bis (acetylacetonate) and the like. .

Specific examples of the nickel compound include, for example, dicarbonylbis (triphenylphosphine) nickel, dibromobis (triphenylphosphine) nickel, dinitrogen bis (bis (tricyclohexylphosphine) nickel), and chlorohydridobis (tricyclohexyl). Phosphine) nickel, chloro (phenyl) bis (triphenylphosphine) nickel, dimethylbis (trimethylphosphine) nickel, diethyl (2,
2'-bipyridyl) nickel, bis (allyl) nickel, bis (cyclopentadienyl) nickel, bis (methylcyclopentadienyl) nickel, bis (pentamethylcyclopentadienyl) nickel, allyl (cyclopentadienyl) Nickel, (cyclopentadienyl)
(Cyclooctadiene) nickel tetrafluoroborate, bis (cyclooctadiene) nickel, nickel bis (acetylacetonate), allyl nickel chloride, tetrakis (triphenylphosphine) nickel, nickel chloride, (C ₆ H ₅ ) Ni {OC (C ₆ H ₅ ) CH = P (C ₆ H ₅ ) ₂ } {P
_{(C 6 H 5) 3}} , (C 6 H 5) Ni {OC (C 6 H 5) C (SO 3 Na) = P (C 6 H 5) 2} {P (C 6
H ₅ ) ₃ } and the like can be mentioned.

Specific examples of the palladium compound include dichlorobis (benzonitrile) palladium, carbonyltris (triphenylphosphine) palladium,
Dichlorobis (triethylphosphine) palladium, bis (t-butylisocyanide) palladium, palladium bis (acetylacetonate), dichloro (tetraphenylcyclobutadiene) palladium, dichloro (1,5
-Cyclooctadiene) palladium, allyl (cyclopentadienyl) palladium, bis (allyl) palladium, allyl (1,5-cyclooctadiene) palladium tetrafluoroborate, (acetylacetonate)
Examples include (1,5-cyclooctadiene) palladium tetrafluoroborate, tetrakis (acetonitrile) palladium ditetrafluoroborate, and the like.

Further, examples of the transition metal compound include those represented by the following general formula [W].

[Chemical 6] Wherein, R ^q is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, Y ^a is -O -, - S -, - NR s -, - PR
^s −, or a neutral two-atom donor ligand selected from OR ^s , SR ^s , NR ^s ₂ , and PR ^s ₂ , M ¹ is an element selected from Group IVB of the periodic table, Z ^a is Si
R ^s ₂ , CR ^s ₂ , SiR ^s ₂ —SiR ^s ₂ , CR ^s ₂ —CR ^s ₂ ,
CR ^s = CR ^s , or GeR ^s ₂ , BR ^s , BR ^s ₂ . R ^s is a moiety selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a substituent containing an oxygen or nitrogen or silicon atom, and a combination thereof having up to 20 non-hydrogen atoms. Or Y ^a , Z ^a
Or two or more R ^s from both Y ^a and Z ^a
The groups form fused rings. ]

The compound (B) is not necessarily limited, but any compound that can form a cation species from the transition metal compound (A) or a derivative thereof can be used. For example, an ionic compound (B-1) capable of forming an ionic complex from a transition metal compound (A) or a derivative thereof, specifically, a compound comprising a cation and an anion in which a plurality of groups are bound to an element, particularly A coordination complex compound composed of a cation and an anion in which a plurality of groups are bound to an element can be preferably used. As a compound composed of such a cation and an anion in which a plurality of groups are bound to an element, a compound represented by the following formula (V) or (VI) can be preferably used. ([L ¹ −R ⁷ ] ^{k +} ) _p ([M ³ Z ¹ Z ² … Z ⁿ ] ^(nm)- ) _q … (V) ([L ² ] ^{k +} ) _p ([M ⁴ Z ¹ Z ² …. Z ⁿ ] ^(nm)- ) _q (VI) (where L ² is M ⁵ , R ⁸ R ⁹ M ⁶ , R ¹⁰ ₃ C or R ¹¹ M ⁶ )

[In the formulas (V) and (VI), L ¹ is a Lewis base, M ³ and M ⁴ are VB group, VIB group and V of the periodic table, respectively.
IIB, VIII, IB, IIB, IIIA, IVA and
Elements selected from Group VA, preferably elements selected from Group IIIA, Group IVA and Group VA, M ⁵ and M ⁶ are Group IIIB, Group IVB, Group VB, Group VIB, Group V of the periodic table, respectively.
An element selected from Group III, Group IA, Group IB, Group IIA, Group IIB, and Group VIIA, Z ^{1 to} Z ⁿ are each a hydrogen atom, a dialkylamino group, an alkoxy group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms. Aryloxy group, C1-C20 alkyl group, C6-C20 aryl group, alkylaryl group, arylalkyl group, C1-C20 halogen-substituted hydrocarbon group, C1-C20 acyloxy It represents a group, an organic metalloid group or a halogen atom, and two or more of Z ^{1 to} Z ⁿ may be bonded to each other to form a ring. R ⁷
Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon number of 6 to
20 represents an aryl group, an alkylaryl group or an arylalkyl group, R ⁸ and R ⁹ are each a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ¹⁰ is a C 1-20 carbon atom. An alkyl group, an aryl group, an alkylaryl group or an arylalkyl group is shown. R ¹¹ is tetraphenylporphyrin,
A macrocyclic ligand such as phthalocyanine is shown. m is M ³ , M
^With an atomic valence of ⁴ , an integer of 1 to 7, n is an integer of 2 to 8, k is an integer of 1 to 7 with an ionic valence of [L ¹ -R ⁷ ], [L ² ],
p is an integer of 1 or more, and q = (p × k) / (nm). ]

Specific examples of the Lewis base include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amine such as trimethylamine, triethylamine, tri-n-butylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p-promo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine Phosphines such as fin, triphenylphosphine and diphenylphosphine,
Examples thereof include ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane, thioethers such as diethyl thioether and tetrahydrothiophene, and esters such as ethyl benzoate.
Specific examples of M ³ and M ⁴ include B, Al, Si, P and A.
s, Sb, etc., preferably B or P, specific examples of M ⁵ are Li, Na, Ag, Cu, Br, I, I _3, etc., and specific examples of M ⁶ are Mn, Fe, Co, Ni, Zn. Etc. can be mentioned.

Specific examples of Z ^{1 to} Z ⁿ include, for example, a dimethylamino group and a diethylamino group as a dialkylamino group; a methoxy group, an ethoxy group, an n-butoxy group as an alkoxy group having 1 to 20 carbon atoms; and a carbon number of 6 A phenoxy group, a 2,6-dimethylphenoxy group, a naphthyloxy group as an aryloxy group having 20 to 20; a methyl group, an ethyl group, an n-propyl group having an alkyl group having 1 to 20 carbon atoms,
iso-propyl group, n-butyl group, n-octyl group,
2-ethylhexyl group; aryl group having 6 to 20 carbon atoms,
As an alkylaryl group or an arylalkyl group, a phenyl group, a p-tolyl group, a benzyl group, a 4-tert-butylphenyl group, a 2,6-dimethylphenyl group,
3,5-dimethylphenyl group, 2,4-dimethylphenyl group, 2,3-dimethylphenyl group; p-fluorophenyl group, 3,5-difluorophenyl group as a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, Pentachlorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-di (trifluoromethyl) phenyl group; F, Cl, Br as halogen atoms,
I: Examples of the organic metalloid group include a pentamethylantimony group, a trimethylsilyl group, a trimethylgermyl group, a diphenylarsine group, a dicyclohexylantimony group, and a diphenylboron group. Specific examples of R ⁷ and R ¹⁰ are the same as those listed above. Specific examples of the substituted cyclopentadienyl group for R ⁸ and R ⁹ include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Here, the alkyl group usually has 1 to 6 carbon atoms, and the number of substituted alkyl groups can be selected as an integer of 1 to 5. Among the compounds of formulas (V) and (VI), M ³ ,
It is preferred that M ⁴ is boron.

Among the compounds of the formulas (V) and (VI), the following can be used particularly preferably. Compound of formula (V) triphenylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyltri (n-butyl) ammonium tetraphenylborate, benzyltriphenylphenylborate (N-Butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyl tetraphenylborate (2-cyanopyridinium) ), Trimethylsulfonium tetraphenylborate, benzyldimethylsulfonium tetraphenylborate ,

Triethylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl)
Tetrabutylammonium borate, tetrakis (pentafluorophenyl) borate (tetraethylammonium),
Tetrakis (pentafluorophenyl) borate (methyltri (n-butyl) ammonium), tetrakis (pentafluorophenyl) borate (benzyltri (n-butyl))
Ammonium), methyldiphenylammonium tetrakis (pentafluorophenyl) borate, methyltriphenylammonium tetrakis (pentafluorophenyl) borate, dimethyldiphenylammonium tetrakis (pentafluorophenyl) borate, anilinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluoro) (Phenyl) methylanilinium borate,
Dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, dimethyl (m-nitroanilinium) tetrakis (pentafluorophenyl) borate, dimethyl tetrakis (pentafluorophenyl) borate (p-bromo) Anilinium),

Pyridinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (p-cyanopyridinium), tetrakis (pentafluorophenyl) borate (N-methylpyridinium), tetrakis (pentafluorophenyl) borate (N
-Benzylpyridinium), tetrakis (pentafluorophenyl) borate (O-cyano-N-methylpyridinium), tetrakis (pentafluorophenyl) borate (p
-Cyano-N-methylpyridinium), tetrakis (pentafluorophenyl) borate (p-cyano-N-benzylpyridinium), tetrakis (pentafluorophenyl) borate trimethylsulfonium, tetrakis (pentafluorophenyl) borate benzyldimethylsulfonium, tetrakis ( Pentafluorophenyl) borate tetraphenylphosphonium, tetrakis (pentafluorophenyl) borate triphenylphosphonium, tetrakis (3,5-ditrifluoromethylphenyl) borate dimethylanilinium, hexafluoroarsenate triethylammonium,

Compound of Formula (VI) Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylborate (tetraphenylporphyrin manganese), ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (1,1'-
Dimethylferrocenium), tetrakis (pentafluorophenyl) borate decamethylferrocenium, tetrakis (pentafluorophenyl) borate acetylferrocenium, tetrakis (pentafluorophenyl) borate formylferrocenium, tetrakis (pentafluorophenyl) borate Cyanoferrocenium, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (tetra Phenylporphyrin manganese), tetrakis (pentafluorophenyl) boric acid (tetraphenylporphyrin iron chloride), tetrakis (pentafluoro) Phenyl) borate (tetraphenylporphyrin zinc), silver tetrafluoroborate, hexafluoroarsenate, silver hexafluoroantimonate, silver

Compounds other than those represented by formulas (V) and (VI), such as tris (pentafluorophenyl) boron, tris (3,5-di (trifluoromethyl) phenyl) boron,
Triphenyl boron or the like can also be used. Moreover, aluminoxane (B-2) can also be used as a compound (B). Specific examples of the aluminoxanes include:

[0044]

[Chemical 7] (R ¹⁶ represents a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group, or an arylalkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, a hydrogen atom, and a halogen atom, which are independently the same. But it can be different.
s represents the degree of polymerization, and is usually 3 to 50, preferably 7 to 40.
Is. ) A chain aluminoxane represented by.

[0045]

[Chemical 8] (R ¹⁶ is the same as that of formula (VII), s is the degree of polymerization, and the number of repeating units is preferably 3 to 50, preferably 7 to 40.) Aluminoxane. Among the compounds of the formulas (VII) to (VIII), methylaluminoxane, ethylaluminoxane and isobutylaluminoxane having a degree of polymerization of 7 or more are preferable. Further, the aluminoxane may be a modified aluminoxane insoluble in a general solvent, which is obtained by modifying aluminoxane with a compound having active hydrogen such as water.

Examples of the method for producing the aluminoxane include a method in which an alkylaluminum and a condensing agent such as water are brought into contact with each other, but the means therefor is not particularly limited.
The reaction may be performed according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and then brought into contact with water, a method in which an organoaluminum compound is initially added at the time of polymerization, and water is added later, water of crystallization contained in a metal salt, etc. There are a method of reacting water adsorbed on an inorganic substance or an organic substance with an organoaluminum compound, a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and further reacting with water.

Further, a Lewis acid may be used as the compound (B). The Lewis acid (B-3) is not particularly limited and may be an organic substance or a solid inorganic substance. A boron compound and an aluminum compound are preferably used as the organic substance, and a magnesium compound and an aluminum compound are suitably used as the inorganic substance. Examples of the aluminum compound include bis (2,6-di-t-butyl-4-methylphenoxy) aluminum methyl and (1,1′-bi-2-naphthoxy).
Aluminum methyl and magnesium compounds include magnesium chloride and diethoxymagnesium, aluminum compounds include aluminum oxide and aluminum chloride, and boron compounds include triphenylboron, tris (pentafluorophenyl) boron, and tris [3,5-bis (3,5-bis) bis (trifluoro)). (Trifluoromethyl) phenyl] boron, tris [(4-fluoromethyl) phenyl] boron, trimethylboron, triethylboron, tri (n-butyl) boron, tris (fluoromethyl) boron, tris (pentafluoroethyl) boron, Tris (nonafluorobutyl) boron, tris (2,4,6-trifluorophenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, tris (3,5-difluorophenyl) boron, bis (Pentafluorophenyl Fluoro boron, diphenyl fluoro boron, bis (pentafluorophenyl) chloro boron, dimethyl fluoro boron, diethyl fluoro boron,
Di (n-butyl) fluoroboron, (pentafluorophenyl) difluoroboron, phenyldifluoroboron, (pentafluorophenyl) difluoroboron, phenyldifluoroboron, (pentafluorophenyl) dichloroboron, methyldifluoroboron, ethyldifluoroboron,
Mention may be made of (n-butyl) difluoroboron.

Here, the mixing ratio (molar ratio) of the compound (A) and the compound (B) is the same as that of the compound (B).
-1) is used, 10: 1 to 1: 100, preferably 2: 1 to 1:10, and compound (B-2) is used, 1: 1 to 1: 100,000, preferably 1 : 10
It is 1: 10,000.

The mixing ratio (molar ratio) of the compound (A) and the compound (B-3) is 1: 0.1 to 1: 2,000, preferably 1: 0.2 to 1: 1,000, and particularly Preferably 1:
It is 0.5 to 1: 500. Further, as the compound (B), (B-1), (B-2), (B-3) and the like can be used alone, or two or more kinds of them can be used in combination.

Examples of the organoaluminum compound which is the component (C) include compounds represented by the following general formula (IX). R ¹⁷ _r AlQ _3-r (IX) (R ¹⁷ is an alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, Q is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 20 carbon atoms or 6 carbon atoms. ~ 20 aryl groups are shown.
r is an integer of 0-3. ) As a compound of formula (IX),
Specifically, trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride, ethyl aluminum Examples include sesquichloride.

The amount of the component (C) used is usually 0 to 2,000 mol, preferably 5 to 1 mol, per 1 mol of the component (A).
The amount is 1,000 mol, particularly preferably 10 to 500 mol. When the component (C) is used, the polymerization activity can be improved, but if it is too much, a large amount of the organoaluminum compound remains in the polymer, which is not preferable.

The mode of use of the catalyst component is not limited, and for example, the components (A) and (B) may be contacted in advance, or the contact product may be separated and washed before use. You may use it by making a contact. Further, the component (C) may be used by being brought into contact with a contact product of the component (A), the component (B) or the component (A) and the component (B) in advance.
The contact may be made in advance or in the polymerization system. Furthermore, the catalyst component can be added to the monomer or the polymerization solvent in advance, or can be added to the polymerization system. The catalyst component can be used by supporting it on an inorganic or organic carrier, if necessary.

The ratio of the catalyst used to the reaction raw material is 1 to 10 ^{9 of} the raw material monomer / the above-mentioned component (A) (molar ratio) or the raw material monomer / the above-mentioned (B) component (molar ratio), particularly 1
It is preferably from 00 to 10 ⁷ .

Polymerization methods include bulk polymerization, solution polymerization,
Any method such as suspension polymerization or gas phase polymerization may be used.
Further, a batch method or a continuous method may be used. A non-aromatic solvent is used as the polymerization solvent. For example, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane and cyclooctane, aliphatic hydrocarbons such as hexane, octane, decane and dodecane, halogenated hydrocarbons such as chloroform and dichloromethane are used. be able to. These solvents may be used alone or in combination of two or more.
Further, a monomer such as α-olefin may be used as a solvent.

Regarding the polymerization conditions, the polymerization temperature is 50 to 250.
C. is preferable, more preferably 70 to 220.degree. C., and most preferably 80 to 200.degree. The polymerization time is usually 1 minute to 10 hours, and the reaction pressure is atmospheric pressure to 100 kg /
cm ² G, preferably atmospheric pressure to 50 kg / cm ² G.
The method for adjusting the molecular weight of the copolymer can be selected by the amount of each catalyst component used, the polymerization temperature, and the polymerization reaction in the presence of hydrogen. The concentration of the obtained copolymer is preferably 5 to 500 g / liter, and 10 to 40
More preferably 0 grams / liter.

As the soluble vanadium-based catalyst, a catalyst composed of a vanadium compound soluble in a hydrocarbon solvent used as a reaction solvent and an organoaluminum compound can be mentioned. Examples of the vanadium compound used as the catalyst include compounds represented by the formula VO (OR) _a V _b or the formula V (OR) _c X _d . However, in the above formula, R is a hydrocarbon group, and 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦
3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ c + d ≦ 4.

Further, the vanadium compound may be an electron donor adduct of the vanadium compound represented by the above formula. Examples of these vanadium compounds include VO
Cl ₃ , VO (OC ₂ H ₅ ) Cl ₂ , VO (OC ₂ H
₅ ) ₂ Cl, VO (O-iso-C ₃ H ₇ ) Cl ₂ , V
_{O (O-n-C 4} H 9) Cl 2, VO (OC 2 H
₅ ) ₃ , VOBr ₂ , VCl ₄ , VOCl ₂ , VO (O
-N-C ₄ H _{9) 3} and _{VCl 3 · 2 (OC 8 H} 17 O
Examples thereof include vanadium compounds such as H). These vanadium compounds can be used alone or in combination.

Examples of the electron donor that forms an adduct with the vanadium compound include alcohols having 1 to 18 carbon atoms and phenols having 6 to 20 carbon atoms (these phenols have a lower alkyl group). , Carbon number 3 to 1
5 ketones, 2 to 15 carbon aldehydes, 2 carbon atoms
To 30 carboxylic acids, esters of organic or inorganic acids, C2 to C15 acid halides, C2 to C20 ethers, acid amides, acid anhydrides, alkoxysilane, and other oxygen-containing electron donors And nitrogen-containing electron donors such as ammonia, amines, nitriles and isocyanates. These electron donors can be used alone or in combination. As the organoaluminum compound used here, a compound having at least one Al-carbon bond in the molecule can be used.

In the cyclic olefin-based resin of the present invention, a hydrogenated product [a] obtained by hydrogenating at least a part of the double bonds present in the above-mentioned addition copolymer of ethylene and cyclic olefins. '] Can also be used.

The method for hydrogenating (hydrogenating) this cyclic olefin copolymer is usually carried out in an organic solvent solution of the polymer. As the solvent, a hydrocarbon solvent such as cyclohexane, methylcyclohexane, benzene, toluene or xylene is used. Although the concentration of the cyclic olefin-based copolymer solution can be appropriately determined, hydrogenation is usually carried out at a concentration of 0.1 to 30% by weight, preferably 1 to 20% by weight. The hydrogenation catalyst used in the method of the present invention can be any catalyst that is commonly used in the hydrogenation of olefin compounds, and is not particularly limited, and examples thereof include the following. .

As the heterogeneous catalyst, a solid catalyst in which nickel, palladium, platinum or a metal thereof is supported on a carrier such as carbon, silica, diatomaceous earth, alumina or titanium oxide, for example, nickel / silica, nickel / diatomaceous earth. , Palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina and the like. Examples of the nickel-based catalyst include Raney nickel catalyst, and examples of the platinum-based catalyst include platinum oxide catalyst and platinum black. As a homogeneous catalyst, those based on a metal of Group VIII of the periodic table, for example, cobalt naphthenate / triethylaluminum, cobalt octenoate / n-butyllithium, nickel acetylacetonate / triethylaluminum, etc.
Examples of the compound include an o compound and an organometallic compound of a metal selected from the groups IA, IIA, and IIIB of the periodic table, and a Rh compound. Further, the Ziegler-based hydrogenation catalyst disclosed by MS Saloan et al. (J. Am. Chem. Soc., 85,
4014 (1983)) can also be used effectively. Examples of these catalysts include the following. _{Ti (O-iC 3 H 7} ) 4 - (iC 4 H 9) 3 Al, Ti (O-iC 3 H 7) 4 - (C 2 H 5) 3 Al, (C 2 H 5) 2 TiCl 2 - _{(C 2 H 5) 3 Al} , Cr (acac) 3 - (C 2 H 5) 3 Al, Ni (acac) 3 - (iC 4 H 9) 3 Al, Mn (acac) 3 - (C 2 H 5 _{) 3 Al, Fe (acac)} 3 - (C 2 H 5) 3 Al, Ca (acac) 2 - (C 2 H 5) 3 Al, (C 2 H 5 COO) 3 Co- (C 2 H 5) ₃ Al, hydrogenation (hydrogenation) reaction is a homogeneous or heterogeneous system depending on the type of catalyst, hydrogen pressure of 1 to 150 atm, 0 to 18
It is carried out at a reaction temperature of 0 ° C, preferably 20-120 ° C. The hydrogenation rate can be arbitrarily adjusted within the range of 0 to 100% by changing the reaction conditions such as hydrogen pressure, reaction temperature, reaction time, catalyst concentration, and the like. The above-mentioned hydrogenated cyclic olefin copolymer In order to exhibit excellent thermal stability, it is preferable that 30% or more of the unsaturated bonds in the copolymer be hydrogenated, more preferably 50% or more, still more preferably 80% or more. Is. As post-processing,
After the hydrogenation reaction, the catalyst is removed by centrifugation, filtration, or in the case of Ziegler type catalyst, by deactivating the catalyst with an acid, etc.
Next, the reaction product is precipitated in a large amount of a polar solvent such as acetone or alcohol, and then the solvent is removed and dried to form a hydride [a '] of the olefin copolymer.
Can be obtained.

Ring-Opening (Co) Polymer ([b], [c]) of Cyclic Olefin The ring-opening (co) polymer ([b], [c]) of the present invention comprises the above-mentioned cyclic olefins. , A catalyst comprising a metal halide such as ruthenium, rhodium, palladium, osmium, indium or platinum, a nitrate or an acetylacetone compound and a reducing agent: a metal halide such as titanium, palladium, zirconium or molybdenum or an acetylacetone compound It can be produced by (co) polymerizing while ring-opening in the presence of a catalyst composed of organoaluminum.

In this ring-opening polymer of cyclic olefins, at least a part of the cyclic olefin represented by the above formula [Y] has a structure represented by the following formula [S]. It is believed that

[0064]

[Chemical 9] For example, 1,4,5,8-dimethano-1,2,3,4
Examples thereof include those copolymerized with 4a, 5,8,8a-octahydronaphthalene, or those copolymerized with norbornene (bicyclo [2.2.1] hept-2-ene). it can. Further, the ring-opened (co) polymer ([b], [c]) is reduced with hydrogen in the presence of a hydrogenation catalyst to obtain a hydrogenated product ([b '],
[C ′]) can also be used in the present invention. in this case,
For example, at least a part of the cyclic olefins having the repeating unit represented by the above formula [Y] is represented by the following formula [T]
It is considered to have a repeating structure represented by.

[0065]

[Chemical 10]

Various Properties of Cyclic Olefin Resin The glass transition temperature (Tg) of the cycloolefin resin used in the present invention must be 50 ° C. or lower.
By using such a resin, there is an effect that it is possible to obtain a film or sheet which is soft at a temperature of the glass transition temperature (Tg) or higher and has an excellent elastic recovery property. More preferable glass transition temperature (Tg) is -30 to 4
5 ° C, and most preferably -30 to 40 ° C. The glass transition temperature (Tg) can be arbitrarily changed by changing the kind and composition of the monomer of the polymer or copolymer according to the intended use and the required physical properties.

The cyclic olefin resin used in the present invention preferably has an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.01 to 20 dl / g. If the intrinsic viscosity [η] is less than 0.01 dl / g, the strength of the film or sheet may decrease, and if it exceeds 20 dl / g, the formability of the film or sheet may deteriorate. More preferable intrinsic viscosity [η] is 0.05 to 10 dl
/ G.

The molecular weight of the cyclic olefin resin used in the present invention is not particularly limited, but the weight average molecular weight Mw measured by gel permeation chromatography (GPC) is 1,000 to 2,000.
50,000, particularly 5,000 to 1,000,000, a number average molecular weight Mn of 500 to 1,000,000, particularly 2,000 to 800,000, and a molecular weight distribution (Mw
/ Mn) is preferably 1.3 to 3, and particularly preferably 1.4 to 2.5. When the molecular weight distribution (Mw / Mn) is greater than 3, the content of low molecular weight substances increases, which may cause stickiness when formed into a film or sheet.

The cycloolefin resin used in the present invention has a crystallinity of 0 to 4 as measured by the X-ray diffraction method.
It is preferably 0%. When the crystallinity exceeds 40%, the elastic recovery property and transparency of the film or sheet may be deteriorated. A more preferable crystallinity is 0 to 30%, especially 0 to 25%.

The cyclic olefin resin used in the present invention has a broad melting peak by DSC of 90 ° C.
It is preferably less than. A resin having a sharp melting peak at 90 ° C. or higher by DSC may have insufficient randomness of the arrangement of the polymerization components, and may have insufficient elasticity when formed into a film or sheet. In addition, D
The broad melting peak by SC is more preferably in the range of 10 to 85 ° C. In the DSC measurement, the melting point (melting) peak of the cyclic olefin-based resin used in the present invention is not seen sharply, and particularly in the case of low crystallinity, it is almost a peak at the ordinary polyethylene measurement condition level. But not.

The cyclic olefin resin used in the present invention has a tensile modulus of 3,000.
It is preferably less than Kg / cm ² . When the tensile modulus is 3,000 Kg / cm ² or more, the impact resistance may be insufficient when used in a film or sheet.
A more preferable tensile elastic modulus is 50 to 2,000 Kg / cm.
^{Is 2} .

Further, the cyclic olefin resin used in the present invention preferably has an elastic recovery rate of 20% or more, more preferably 30% or more, and especially 4
Most preferably, it is 0% or more. If it is less than 20%, for example, when used in a medical infusion bag, the shape of the infusion bag will be deformed due to external force, or the film thickness will be partially reduced, resulting in a decrease in strength.

The cyclic olefin-based resin used in the present invention may be a resin having only the physical properties in the above range, or a resin containing the physical properties outside the above range in part. It may be. In the former case, it may be a mixture of resins having different Tg's having a glass transition temperature (Tg) of 50 ° C. or lower. In the latter case, all physical property values may be included in the above range.

2. Treatment with Electron Beam or Radiation The cycloolefin resin obtained by the above method or a molded product thereof is subjected to irradiation treatment with electron beam or radiation. By this treatment, a crosslinked structure can be imparted to the resin and the resin can be sterilized. In carrying out the cross-linking, diallyl sepacate, triallyl cyanurate, N, N′-hexamethylene bismethacrylamide or the like may be added in order to increase the cross-linking efficiency. The irradiation dose of the electron beam is preferably 10 to 50 Mrad, but even if it is out of this range, there is no particular problem as long as the properties of the cyclic olefin resin are not out of the target range.

Types of Electron Beam or Radiation The electron beam or radiation used in the present invention is not particularly limited, but, for example, α emitted from a radioactive isotope.
Rays, beta rays and gamma rays can be mentioned. Also, Van de Clark type electron accelerator, Cockcroft-Walton type electron accelerator, insulation transformer type electron accelerator, transformer type gas (oil) insulation type electron accelerator, cold cathode impact voltage type electron accelerator, linear filament type electron An electron beam or radiation from an accelerator or the like can be used. Furthermore, X-rays can be mentioned.

Irradiation Method The irradiation method is not particularly limited, but for example, injection molding, extrusion molding, compression molding or the like may be used to previously give the resin a predetermined shape and then irradiation. Also, a so-called in-line method in which irradiation is performed at the same time as molding may be used. In the case of medical radiation sterilization, it is preferable to give a predetermined shape in advance and perform irradiation in a completely sealed state.

By thus irradiating the cyclic olefin resin with an electron beam or radiation to crosslink the resin, for example, the tensile modulus of elasticity is 50 to 3,000.
It is possible to obtain a cyclic olefin resin having excellent heat resistance, water resistance, and chemical resistance while maintaining kg / cm ² and an elastic recovery rate of 20 to 100%.

The cyclic olefin resin treated in the present invention has a melt index (MI) [190 ° C., load 2.16 kg, JIS-K7210] of 0.1 g / 1.
It is preferably less than 0 minutes. If it is 0.1 g / 10 minutes or more, the treatment effect is insufficient and the effect of improving heat resistance, water resistance and chemical resistance may be low. More preferably, 0.
0001 to 0.08 g / 10 minutes, 0.00
Most preferably 1 to 0.05 g / 10 minutes.

In the present invention, a composition comprising the above-mentioned cyclic olefin resin and another thermoplastic resin can also be used. The thermoplastic resin is not particularly limited, but specifically, polyethylene such as high-density polyethylene, low-density polyethylene, linear low-density polyethylene, ethylene / 1-butene copolymer, ethylene-4-ethylene etc.
Methyl-1-pentene copolymer, ethylene / 1-hexene copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer and its metal salts, polypropylene, ethylene / propylene copolymer, propylene / 1 −
Examples thereof include butene copolymer, poly 1-butene, 1-butene-4-methyl-1 pentene copolymer, poly 4-methyl-1-pentene and poly 3-methyl-1-butene. In addition, as the thermoplastic resin, polystyrene, ABS resin, AS resin, polyvinyl alcohol, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, fluororesin (polytetrafluoroethylene, etc.), polycarbonate, polyarylate , Polyethylene terephthalate, polybutylene terephthalate,
Polyphenylene sulfide, polyether sulfone,
Polyamide, polyimide, polyphenylene oxide,
Polyacetal or the like can be used. Particularly preferred as the thermoplastic resin are HDPE, LDPE, L-
LDPE, polypropylene, ethylene / propylene copolymer, polystyrene, polyvinyl chloride and the like. In addition,
Two or more kinds of thermoplastic resins can be used in combination, if necessary. By using the composition containing such a thermoplastic resin, the heat resistance and adhesiveness of the film or sheet can be improved. The orientation ratio of the thermoplastic resin is not particularly limited, and depends on the physical properties of the cycloolefin resin which is another component, but is 0.1 to 99.
It is preferably 9% by weight, particularly 0.5 to 90% by weight. Further, in the present invention, if necessary, other resins, elastomers and the like may be blended in addition to the thermoplastic resin. For example, the addition of a polar group-containing polymer can impart dyeing properties, antistatic properties, and hydrophilic properties, and various additives such as fillers and stabilizers can be added. Specific examples of the additive that can be blended include the following.

The cyclic olefin resin used in the present invention may optionally contain additives such as dispersants, fillers, softeners, plasticizers, tackifiers, colorants, foaming agents, foaming aids, A lubricant, an antiaging agent, a stabilizer, a slip agent, an anti-glocking agent and the like can be used in combination. As fillers, inorganic fillers such as carbon black, white carbon (silicate compound), calcium carbonate, talc, clay, etc .; high styrene resin, coumarone indene resin, phenol resin, lignin, modified melamine resin, petroleum resin, etc. Mention may be made of organic fillers. Of these, an inorganic filler is particularly preferably used. Examples of the softening agent include petroleum-based softening agents such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and petrolatum; coal tar-based softening agents such as coal tar and cortar pitch; castor oil, linseed oil, rapeseed oil, palm. Fat oil softeners such as oils; tall oils; sub; waxes such as beeswax, carnauba wax, lanolin; fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, barium stearate, calcium stearate, zinc laurate; petroleum resins Synthetic polymer substances such as; As a plasticizer, a phthalic acid ester type, an adipic acid ester type, a sebacic acid ester type, a phosphoric acid type, etc., and as a tackifier, a coumarone indene resin, a terbene / phenol resin, a xylene / formalin resin, etc. Is
Foaming agents such as inorganic and organic pigments include sodium bicarbonate, ammonium carbonate, N, N′-dinitrosopentamethylenetetramine, azocarbonamide, azobisisobutyronitrile, benzenesulfonylhydrazide,
As a foaming aid such as toluenesulfonyl hydrazide, calcium amide, paratoluenesulfonyl azide,
Salicylic acid, phthalic acid, etc. can be used.
In addition, a known method using an oven roll mill, a Banbury mixer, a kneader, a calendar roll, a single-screw or twin-screw extruder, etc. can be adopted for the production of the blend.

[0081]

EXAMPLES The present invention will be described in more detail below with reference to examples. Reference Example 1 (Copolymerization of Ethylene and 2-Norbornene) Under a nitrogen atmosphere, at room temperature, 15 liters of toluene, 23 mmol of triisobutylaluminum (TIBA), 38 micromoles of tetrabutoxyzirconium, and tetra (pentafluoro) were added to a 30 liter autoclave. 60 micromoles of phenyl) anilinium borate were added in this order, and then 2.9 liters of a toluene solution containing 70% by weight of 2-norbornene (19 mols of 2-norbornene) was added. After the temperature was raised to 80 ° C., the reaction was carried out for 110 minutes while continuously introducing ethylene so that the ethylene partial pressure became 7.5 kg / cm ² . After completion of the reaction, the polymer solution was poured into 15 liters of methanol to precipitate the polymer. This polymer was collected by filtration and dried to obtain a cyclic olefin-based copolymer (a1). The yield of the cyclic olefin-based copolymer (a1) is 3.21 kg.
Met. The polymerization activity was 928 kg / gZr.

The obtained cyclic olefin-based copolymer (a
The physical properties of 1) were as follows: ¹³ C-NMR 30p
The sum of the ethylene-based peak appearing near pm and the methylene-based peaks at the 5th and 6th positions of norbornene and 3
The norbornene content calculated from the ratio with the peak based on the methylene group at the 7-position of norbornene appearing around 2.5 ppm was 10.1 mol%. The intrinsic viscosity [η] measured in decalin at 135 ° C. was 1.03 dl / g, and the crystallinity determined by the X-ray diffraction method was 2.0%. Piperon 11-EA manufactured by Toyo Boulding Co. as a measuring device
Using a mold, a measuring piece with a width of 4 mm, a length of 40 mm and a thickness of 0.1 mm was measured at a temperature rising rate of 3 ° C./min and a frequency of 3.5 Hz. When the transition temperature (Tg) was determined, the Tg was 4 ° C.
Waters ALC / GPC150 as a measuring device
C, 1,2,4-trichlorobenzene solvent, 13
When the weight average molecular weight Mw, the number average molecular weight Mn, and the molecular weight distribution (Mw / Mn) were calculated at 5 ° C. in terms of polyethylene, Mw was 62,300, Mn was 33,900, Mw /
It was Mn = 1.84. -50 at a temperature rising rate of 10 ° C./min by a 7 series DSC manufactured by Perkin Elmer.
When the melting point (Tm) was measured in the range of 150 ° C to 150 ° C,
Tm was 78 ° C. (broad peak).

Reference Example 2 At room temperature under a nitrogen atmosphere, 15 liters of toluene, 19 mmol of methylaluminoxane, and 38 micromoles of tetrabutoxyzirconium were placed in this order in a 30 liter autoclave, followed by addition of 2-norbornene to 7 parts.
1.14 liters of a toluene solution containing 0% by weight (2-
7.5 mol) was added as norbornene. After the temperature was raised to 90 ° C., the reaction was performed for 110 minutes while continuously introducing ethylene so that the ethylene partial pressure became 6 kg / cm ² . After completion of the reaction, the polymer solution was put into methanol to precipitate a polymer, which was collected by filtration and dried to obtain a cyclic olefin copolymer (a2). The yield of (a2) is 2.7.
It was 5 kg. The polymerization activity was 793 kg / gZr. Further, the norbornene content determined in the same manner as in Reference Example 1 was 5.6 mol%, and the intrinsic viscosity [η] was 1.20 dl /
g, crystallinity 4.3%, Tg 1 ° C., Mw 73.5.
00, Mn is 36,800, Mw / Mn is 2,000, T
m was 90 ° C. (broad peak).

Examples 1 and 2 and Comparative Examples 1 and 2 Using the cyclic olefin copolymers a1 and a2 obtained in Reference Example and linear low density polyethylene, 30 mmφ, L
A sheet having a width of 300 mm and a thickness of 100 μm was obtained by performing T die casting using a single screw extruder with / D = 25.
Next, using a1, a2, a linear low-density polyethylene sheet and a soft Birni chloride sheet (100 μm manufactured by Asahi Kasei Corp.), this was irradiated with 1 Mrad / hour of γ-rays for 5 hours, and the physical properties before and after γ-ray irradiation were compared. did. The results are shown in Table 1. From this table, the sheet formed using the cyclic olefin-based copolymer obtained in the present invention has MI of 0.1 g / 10.
It can be seen that the amount is less than the minute and the yellowing is small. The physical properties were measured as follows. Tensile elastic modulus (kg / cm ² ) was measured according to JIS-K7113 using an autograph. Tensile breaking strength (kg / cm ² ) Autograph was performed according to JIS-K7113. Elastic recovery rate (%) Using autograph, pulling speed 62mm / min, width 6m
m, 50 mm (L ₀ ) between the clamps is stretched and stretched by 150% and kept for 5 minutes, then suddenly contracted without being repelled, and after 1 minute, the sheet length between the clamps (L ₁ ) was measured and calculated by the following formula. Elastic recovery rate (%) = [1- {L ₁ −L ₀ } / L ₀ ] × 1
00 melt index (MI) The measurement was performed according to JIS-K7210 under the conditions of 190 ° C. and 2.16 kg. Total light transmittance (%), haze (%) Digital haze computer (DIGITAL HAZE COMPU
TER) (manufactured by Suga Test Instruments Co., Ltd.) using JIS-K7
The hue of the 105 yellowing sample was measured and the yellowness (YI) was calculated. Yellowness (Y) of the sample before and after irradiation with electron beam or radiation
The difference in I) was defined as the degree of yellowing.

[0085]

[Table 1]

[0086]

As described above, according to the method for treating a cyclic olefin resin of the present invention, various properties such as water resistance and chemical resistance are excellent, and also sufficient elasticity and flexibility are provided. It is possible to obtain a cyclic olefin resin.

Claims (4)

[Claims] 1. A copolymer [a] obtained by addition-polymerizing an α-olefin and a cyclic olefin, a polymer [b] obtained by ring-opening polymerization of a cyclic olefin, and a ring-opening copolymer [c] thereof. ], And these hydrogenated products [a '], [b']
And a cycloolefin resin having a glass transition temperature (Tg) of 50 ° C. or lower selected from the group consisting of [c ′] and an electron beam or radiation. Processing method. 2. The cyclic olefin-based resin before the treatment is a mol% of α-olefin and cyclic olefins.
Is 80:20 to 99.9: 0.1, The method for treating a cyclic olefin resin according to claim 1, wherein 3. A crosslinked cyclic olefin resin obtained by the treatment method according to claim 1. 4. A melt index [MI] (190 ° C.,
2.16 kg) is less than 0.1 g / 10 minutes, the tensile elastic modulus is 50 to 3,000 kg / cm ² , and the elastic recovery rate is 20.
It is -100%, The cyclic olefin resin crosslinked body of Claim 3 characterized by the above-mentioned.