JPH05271356A - Modified cyclic olefin copolymer - Google Patents

Abstract

PURPOSE:To provide a modified cyclic olefin copolymer which has excellent elastic recovery, high compatibility with other resins and high adhesion. CONSTITUTION:The objective modified cyclic olefin copolymer is obtained by graft-copolymerizing a monomer having at least one unsaturated group with a cyclic olefin copolymer which contains the recurring units from an alpha- olefin and the recurring units from a cyclic olefin, and has a glass transition temperature (Tg) lower than 30 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is excellent in elastic recovery, compatibility with other resins, adhesiveness, etc., and is a molding material for industrial products, automobile parts, household appliances parts, multilayer materials, etc. The present invention relates to a modified cyclic olefin-based copolymer that can be suitably used as a substance, a resin compatibilizer, and the like.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
As the polyolefin resin, high density polyethylene,
Resins such as low density polyethylene and polypropylene are widely used in both industrial and household fields. However, many of these polyolefin-based resins have high crystallinity, and although they have excellent mechanical properties, solvent resistance, electrical properties, etc., they do not have the elastic recovery properties that soft polyvinyl chloride resins have. When subjected to tensile stress, necking occurred and permanent set remained.

On the other hand, our group is
It was previously found that a molded article made of a copolymer obtained by copolymerizing an olefin and a specific cyclic olefin has excellent elastic recovery (Japanese Patent Application No. 3-99839). This copolymer has excellent adhesiveness with other thermoplastic resins,
Although it can be effectively used as a resin forming a layer of a multi-layer material, it has a problem that sufficient adhesive strength cannot be obtained depending on the resin of the other party because of its low polarity. In addition, JP-A-6
JP-A 2-27412 discloses a modified cyclic olefin-based copolymer obtained by graft-copolymerizing a copolymer of ethylene and a cyclic olefin with an α, β-unsaturated carboxylic acid or the like. However, this copolymer has a high glass transition temperature, and no example of a copolymer having a temperature of 60 ° C. or lower even after being graft-modified is disclosed. Therefore, although it was excellent in heat resistance, it did not have flexibility and elastic recovery at room temperature, and its properties at low temperature were insufficient.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a modified cyclic olefin-based copolymer having excellent low-temperature characteristics, elastic recovery, compatibility with other resins, adhesiveness, and the like. To aim.

[0005]

As a result of intensive studies, the present inventors have found that a cyclic olefin copolymer having a specific structure having a specific glass transition temperature (Tg) is provided with an unsaturated group-containing monomer. The inventors have found that a modified cyclic olefin-based copolymer satisfying the above requirements can be obtained by graft copolymerization, and completed the present invention.

That is, the present invention provides a cyclic olefin copolymer having a repeating unit derived from an α-olefin and a repeating unit derived from a cyclic olefin and having a glass transition temperature (Tg) of 30 ° C. or lower. Provided is a modified cyclic olefin-based copolymer, which is obtained by graft-copolymerizing an unsaturated group-containing monomer having at least one saturated group.

The present invention will be described in more detail below.
First, the cyclic olefin-based copolymer will be described in detail. As the cyclic olefin-based copolymer, one having a repeating unit derived from α-olefin and a repeating unit derived from cyclic diene and having a glass transition temperature (Tg) of 30 ° C. or lower is used. Here, the above α-olefin is not necessarily limited, but for example, the following general formula [X]

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

In the repeating unit represented by the above general formula [X], R ^a represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Here, as the hydrocarbon group having 1 to 20 carbon atoms, specifically, for example, methyl group, ethyl group, isopropyl group, n-propyl group, isobutyl group, n-butyl group, n-hexyl group, n-octyl group. Group, n-octadecyl group and the like. In addition, the general formula [X]
Specific examples of the α-olefin giving the repeating unit represented by are, for example, ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, Examples thereof include 1-decene and 1-eicosene.

Further, the cyclic olefin is not necessarily limited, but for example, the following general formula [Y]

[Chemical 2] (In the formula [Y], R ^{b to} R ^m are each a hydrogen atom or a carbon number 1
~ 20 represents a hydrocarbon group 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 ¹ or R ^m may form a ring with each other. R ^{b to} R ^m may be the same or different from each other. ) And those which give a repeating unit.

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
To 20 hydrocarbon groups or substituents 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, n
-Butyl group, isobutyl group, t-butyl group, hexyl group and other alkyl groups having 1 to 20 carbon atoms, phenyl group, tolyl group, aryl group having 6 to 20 carbon atoms such as benzyl group, alkylaryl group or arylalkyl Group, methylidene group, ethylidene group, propylidene group, etc., having 1 to 2 carbon atoms
0 alkylidene group, vinyl group, allyl group, etc. with 2 carbon atoms
To 20 alkenyl groups and the like. However,
R ^b , R ^c , R ^f and R ^g exclude alkylidene groups. In addition, R
^{When any of d} , R ^e and R ^{h to} R ^m is an alkylidene group,
The carbon atom to which it is attached has no other substituents.

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 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 carbon number 1 to 20 such as a methoxycarbonyl group and an ethoxycarbonyl group. Alkoxycarbonyl group and the like can be mentioned. 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 providing 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-
Phenylnorbornene, 5-benzylnorbornene, 5
-Ethylidene norbornene, 5-vinyl norbornene,
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-methyl-
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-ethyl-
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4
a, 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-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene,
Examples thereof include 5,6-dicarboxyl norbornene anhydrate, 5-dimethylamino norbornene, and 5-cyanonorbornene. Among these, norbornene or its derivative is particularly preferable.

The cyclic olefin copolymer used in the present invention is basically a copolymer of the above-mentioned α-olefin and a cyclic olefin, but it is within the range not impairing the object of the present invention. So, in addition to these two essential components,
If necessary, other copolymerizable unsaturated monomer components may be used. As such an unsaturated monomer which may be optionally copolymerized, specifically, among the above α-olefin components, those not previously used, among the above cyclic olefin components, Examples thereof include those not used, cyclic dienes such as dicyclopentadiene and norbornadiene, chain dienes such as butadiene, isoprene and 1,5-hexadiene, and monocyclic olefins such as cyclopentene and cycloheptene.

The cyclic olefin-based copolymer used in the present invention has an α-olefin unit content [x] and a cyclic olefin unit content [y] of [x] of 80 to 99.9 mol%. [Y] is 20 to 0.1 mol%, particularly [x] is 82 to 99.5 mol%, [y] is 18 to 0.5 mol%, and in particular [x] is 85 to 98 mol%. [Y] is 1
It is preferably from 5 to 2 mol%. When the content [x] of α-olefin units is less than 80 mol%, the glass transition temperature (Tg) and tensile elastic modulus of the copolymer are increased, and the elastic recovery of the obtained film or sheet and molding of the molded product are increased. The impact resistance and elasticity of the product may become insufficient. On the other hand, when the content [y] of the cyclic olefin unit is less than 0.1 mol%, the crystallinity of the copolymer becomes high and the effect of introducing the cyclic olefin component such as elastic recovery becomes insufficient.

The cyclic olefin copolymer used in the present invention is a substantially linear copolymer in which α-olefin units and cyclic olefin units are linearly arranged, and does not have a gel-like crosslinked structure. It is preferably one. It can be confirmed that the copolymer does not have a gel-like crosslinked structure by completely dissolving the copolymer in decalin at 135 ° C.

The cyclic olefin copolymer 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 may be significantly reduced, and if it exceeds 20 dl / g, the moldability may be significantly deteriorated. A more preferable intrinsic viscosity [η] is 0.05 to 10 dl / g.

The molecular weight of the cyclic olefin copolymer used in the present invention is not particularly limited, but the weight average molecular weight Mw measured by gel permeation chromatography (GPC) [polyethylene conversion] is 1,0.
00 to 2,000,000, especially 5,000 to 100
50,000, the number average molecular weight Mn is 500 to 1,000,
000, particularly 2,000 to 800,000, and a molecular weight distribution (Mw / Mn) of 1.3 to 4, particularly 1.4 to 3. When the molecular weight distribution (Mw / Mn) is greater than 4, the content of low molecular weight substances increases, which may cause stickiness of the molded product.

The cyclic olefin copolymer used in the present invention is required to have a glass transition temperature (Tg) of less than 30 ° C. By using such a copolymer, a film, a sheet, a molded article or the like which can be suitably used at low temperature can be obtained. More preferable glass transition temperature (Tg)
Is -30 to 20 ° C, especially -30 to 15 ° C. In this case, the glass transition temperature (Tg) of the cyclic olefin-based copolymer used in the present invention can be arbitrarily controlled by changing the type and composition of the monomer, and the intended use and use can be achieved. Glass transition temperature (Tg) depending on temperature
Can be changed arbitrarily.

The cyclic olefin copolymer used in the present invention has a crystallinity of 0 to 4 as measured by X-ray diffractometry.
It is preferably 0%. When the crystallinity exceeds 40%, elastic recovery and transparency may be deteriorated. More preferable crystallinity is 0 to 30%, especially 0 to 25%.

The cyclic olefin copolymer used in the present invention preferably has a tensile elastic modulus of less than 3,000 Kg / cm ² . If the tensile modulus is 3,000 Kg / cm ² or more, the impact resistance may be insufficient. A more preferable tensile elastic modulus is 50 to 2,000 Kg / cm ² .

The cyclic olefin-based copolymer used in the present invention preferably has a broad melting peak by DSC (temperature rise measurement) of less than 90 ° C. DSC (temperature rise measurement)
The copolymer having a sharp melting peak at 90 ° C. or higher has a broad composition distribution of the copolymer of cyclic olefin and α-olefin, and the elastic recovery of the molded product may be insufficient. The broad melting peak by DSC (temperature rise measurement) is more preferably in the range of 10 to 85 ° C. In DSC (temperature rise measurement), the melting point (melting peak) of the olefin-based copolymer is not sharply seen, and particularly in the case of low crystallinity, almost no peak appears at the level of ordinary polyethylene measurement conditions. Does not appear.

The cyclic olefin-based copolymer used in the present invention preferably has one or more relatively small sub-peaks on the high temperature side of the main peak in the crystallization peak by DSC (cooling measurement). .. Due to the characteristics of the thermal properties described above, the physical properties of the molded product can be obtained, and the molded product can be stably molded, for example, by widening the molding temperature range.

The cyclic olefin-based copolymer used in the present invention may be a copolymer having only the physical properties in the above range, and may partially include the copolymer having the physical properties outside the above range. It may be one that has been. In the latter case, all physical property values may be included in the above range.

The method for producing the cyclic olefin-based copolymer used in the present invention is not limited, but a catalyst containing the following compounds (A) and (B) as main components or the following compound (A),
It can be efficiently produced by copolymerizing the α-olefin and the cyclic olefin using a catalyst containing (B) and (C) as a main component. (A) Transition metal compound (B) Compound which reacts with transition metal compound to form an ionic complex (C) Organoaluminum compound

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

Examples of such a transition metal compound (A) include various compounds, but in particular, a compound containing a transition metal of IVB 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) can be preferably used, and particularly, a compound represented by the following general formula (I),
A cyclopentadienyl compound represented by (II) or (III) or a derivative thereof, or a compound represented by the following general formula (IV) or a derivative thereof is preferable. ^{_{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 another 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, 1-20 carbon alkoxy groups, 6 carbon atoms
Examples include 20 aryl groups, alkylaryl groups or arylalkyl groups, acyloxy groups having 1 to 20 carbon atoms, allyl groups, substituted allyl groups, and substituents containing a silicon atom, and examples of chelating ligands include 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 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 methylcyclopentadienyl group, ethylcyclopentadienyl group, 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. In addition, (I) ~ (I
Specific examples of R ^{1 to} R ^{4 in} the formula V) include, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom as a halogen atom; a methyl group, an ethyl group and n-propyl as an alkyl group having 1 to 20 carbon atoms. Group, iso-propyl group,
n-butyl group, octyl group, 2-ethylhexyl group; methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group as alkoxy group having 1 to 20 carbon atoms; aryl group having 6 to 20 carbon atoms, alkylaryl group or Phenyl group, tolyl group, xylyl group, benzyl group as an arylalkyl 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: Lewis base As dimethyl ether,
Ethers such as diethyl ether and tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as acetonitrile and benzonitrile, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 2, Amines such as 2'-bipyridine and phenanthroline; phosphines such as triethylphosphine and triphenylphosphine; ethylene, butadiene, 1-pentene, isoprene, pentadiene, 1-hexene and their derivatives as chain unsaturated hydrocarbons;
Examples of the cyclic unsaturated hydrocarbon include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and derivatives thereof. Examples of the cross-linking by the covalent bond of A in the formula (III) include methylene cross-link, dimethyl methylene cross-link, ethylene cross-link, 1,1′-
Examples thereof include cyclohexylene crosslinks, dimethylsilylene crosslinks, dimethylgermylene crosslinks, and dimethylstannylene crosslinks.

Examples of such compounds include the following compounds and compounds obtained by substituting zirconium of these compounds 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) monochloromonohydride 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,

Compound of 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 a zirconium compound, a hafnium compound, and a titanium compound having one or more of an alkyl group, an alkoxy group, and a halogen atom, such as a compound in which zirconium is replaced with hafnium or titanium. Tetramethylzirconium, tetrabenzylzirconium, tetramethoxyzirconium, tetraethoxyzirconium, tetrabutoxyzirconium, tetrachlorozirconium, tetrabromozirconium, butoxytrichlorozirconium, dibutoxydichlorozirconium, bis (2,5-di-t-butylphenoxy) Dimethyl zirconium, bis (2,5-di-t-butylphenoxy) dichlorozirconium, zirconium bis (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, tricarbonyl tris (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 nickel compounds 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 bisacetylacetonate, 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.

Specific examples of the palladium compound include dichlorobis (benzonitrile) palladium, carbonyltris (triphenylphosphine) palladium,
Dichlorobis (triethylphosphine) palladium, bis (t-butyl isocyanide) 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.

Any compound can be used as the compound (B) as long as it reacts with the transition metal compound (A) to form an ionic complex. A compound composed of a bound anion, particularly a coordination complex compound composed of a cation and an anion in which a plurality of groups are bonded to an element can be preferably used. The compound consisting of such a cation and an anion in which a plurality of groups are bound to an element is represented by the following formula (V) or (VI)
The compound represented by 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 VIB 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 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 6 to 6 carbon atoms
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 group. 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
^{4 has} an valence of 1 to 7, n is an integer of 2 to 8, k is an ionic number of [L ¹ -R ⁷ ] and [L ² ] and is an integer of 1 to 7,
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, As and Sb.
Etc., preferably B or P, and specific examples of M ⁵ are Li,
Specific examples of Na, Ag, Cu, Br, I, I _3, etc. and M ⁶ include Mn, Fe, Co, Ni, Zn and the like.

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 carbon atoms, a methyl group, an ethyl group, an n-propyl 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 pentamethylantimony group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group and diphenylboron group. Specific examples of R ⁷ and R ¹⁰ include:
Examples are the same as those listed above. R ⁸ and R ⁹
Specific examples of the substituted cyclopentadienyl group 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 by an integer of 1 to 5. (V), (V
Among the compounds of formula I), those in which M ³ and M ⁴ are boron are preferred.

Among the compounds of the formulas (V) and (VI), the following can be used particularly preferably. Compound of formula (V) triethylammonium 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) tetraphenylphosphonium borate, tetrakis (pentafluorophenyl) triphenylphosphonium borate, tetrakis (3,5-ditrifluoromethylphenyl) dimethylanilinium borate, triethylammonium hexafluoroarsenate,

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 tri (pentafluorophenyl) boron, tri (3,3)
5-di (trifluoromethyl) phenyl) boron, triphenylboron and the like can also be used.

Examples of the organoaluminum compound as the component (C) include those represented by the following general formula (VII), (VIII) or (IX). R ¹² _r AlQ _3-r (VII) (R ¹² is 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, Q is a hydrogen atom, It represents an alkoxy group having 1 to 20 carbon atoms or a halogen atom, and r is in the range of 1 ≦ r ≦ 3. Examples of the compound of the formula (VII) include trimethylaluminum, triethylaluminum and 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 sesquichloride and the like can be mentioned.

[0047]

[Chemical 3] (R < ¹² > shows the same thing as a formula (VII). S shows a polymerization degree and is 3-50 normally, Preferably it is 7-40.) The chain | strand-shaped aluminoxane shown by these.

[0048]

[Chemical 4] (R ¹² represents the same as in formula (VII), s represents the degree of polymerization, and the preferred number of repeating units is 3 to 50, preferably 7 to 40.) Cyclic alkyl having a repeating unit Aluminoxane. Among the compounds represented by the formulas (VII) to (IX), an alkyl group-containing aluminum compound or aluminoxane having at least one alkyl group having 3 or more carbon atoms, and particularly having at least one branched alkyl group is preferable. Particularly preferred is triisobutylaluminum or aluminoxane having a degree of polymerization of 7 or more. When this triisobutylaluminum, aluminoxane having a degree of polymerization of 7 or more, or a mixture thereof is used, high activity can be obtained. Further, a modified aluminoxane which is insoluble in a general solvent obtained by modifying the aluminoxane represented by the formulas (VIII) to (IX) with a compound having active hydrogen such as water is also preferably used.

As a method for producing the aluminoxane, there may be mentioned 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, and the reaction may be carried out according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and 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 water to obtain a solvent-insoluble aluminoxane.

The catalyst used in the production of the olefinic copolymer of the present invention comprises the above-mentioned components (A) and (B) or (A),
The components (B) and (C) are the main components. In this case, the use conditions of the component (A) and the component (B) are not limited, but the ratio (molar ratio) of the component (A) to the component (B) is 1:
It is preferably 0.01 to 1: 100, particularly 1: 0.5 to 1:10, and particularly preferably 1: 1 to 1: 5. The operating temperature is preferably in the range of -100 to 250 ° C, and the pressure and time can be set arbitrarily.

The amount of the component (C) used is usually 0 to 2,000 mol, preferably 5 to 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 the 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. Further, 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 to the reaction raw material is 1 to 10 ^{9 of} raw material monomer / component (A) (molar ratio) or raw material monomer / component (B) (molar ratio), especially 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. When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane,
Aliphatic hydrocarbons such as pentane, hexane, heptane and octane, halogenated hydrocarbons such as chloroform and dichloromethane can be used. 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 -100 to 2
The temperature is preferably 50 ° C, particularly preferably -50 to 200 ° C.
The polymerization time is usually 1 minute to 10 hours, and the reaction pressure is atmospheric pressure to 10
0 Kg / cm ² G, preferably normal pressure to 50 Kg / cm ² G
Is. The method for controlling 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 modified cyclic olefin copolymer of the present invention is obtained by graft-copolymerizing the above-mentioned cyclic olefin copolymer with an unsaturated group-containing monomer having at least one unsaturated group. Here, the type of unsaturated group-containing monomer is not limited, but, for example, unsaturated carboxylic acid or its derivative, unsaturated epoxy compound, styrene-based hydrocarbon,
Organic silicon compounds and the like can be preferably used.

Specific examples of the unsaturated carboxylic acid include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and α-ethylacrylic acid, maleic acid and fumaric acid.
Itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid, methyl-endocis-bicyclo [2.2.1] Examples thereof include unsaturated dicarboxylic acids such as hept-5-ene-2,3-dicarboxylic acid. Examples of the unsaturated carboxylic acid derivative include acid halides, amides, imides, acid anhydrides and esters of the above unsaturated carboxylic acids, and specific examples include maleenyl chloride, maleimide, maleic anhydride,
Examples include chloromaleic anhydride, butenyl succinic anhydride, tetrahydrophthalic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate. Among these, unsaturated dicarboxylic acids or acid anhydrides thereof, particularly maleic anhydride, fumaric acid, and itaconic acid are particularly preferable.

Examples of unsaturated epoxy compounds include unsaturated glycidyl esters, unsaturated glycidyl ethers, and epoxy alkenes. Specifically, glycidyl acrylate, glycidyl methacrylate, vinyl glycidyl ether, hydroxyalkyl (meth) acrylate glycidyl ether, polyalkylene glycol (meth) acrylate glycidyl ether, itaconic acid mono- and diglycidyl esters,
Mono- and diglycidyl esters of butenetricarboxylic acid, mono- and diglycidyl esters of citraconic acid, endocis-bicyclo [2.2.1] hept-5-ene-
Mono and diglycidyl esters of 2,3-dicarboxylic acid, mono- and diglycidyl esters of methyl-endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid, mono and di of allyl succinic acid Glycidyl ester, glycidyl ester of p-styrenecarboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl- Examples thereof include 1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene and vinylcyclohexene monoxide. Of these, glycidyl methacrylate and glycidyl acrylate are particularly preferable.

As the styrene-based hydrocarbon, specifically,
For example, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, m-
Examples thereof include ethyl styrene, p-ethyl styrene, o-isopropyl styrene, m-isopropyl styrene and p-isopropyl styrene. Of these, styrene and p-methylstyrene are particularly preferable.

As the organic silicon compound, those having an olefinically unsaturated bond and a hydrolyzable group can be preferably used. Specific examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (methoxyethoxy) silane, vinylmethyldiethoxysilane, and vinylphenyldimethoxysilane. Of these, vinyltrimethoxysilane is particularly preferable.

The modified cyclic olefin-based copolymer of the present invention can be produced by a conventional method for producing a graft copolymer. Here, the amount of the unsaturated group-containing monomer used is not particularly limited, but is 0.01 to 40% by weight, especially 0.05 to 40% by weight based on the cyclic olefin copolymer.
It is preferably in the range of 20% by weight.

In order to carry out the graft copolymerization particularly efficiently, it is preferable to carry out the reaction in the presence of a radical generator. In this case, known radical generators such as organic peroxides and diazo compounds can be used. Specific examples include benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, and azobisisobutylnitrile. You can The amount of the radical generator used is 0.01% by weight or more based on the copolymer,
In particular, it is preferably 0.03 to 1% by weight.

As a method of graft copolymerization, specifically, a radical generator and an unsaturated group-containing monomer are added to a solution containing (a) a cyclic olefin-based copolymer, and the temperature is 40 to 40 ° C.
A method of stirring at 200 ° C. for several tens of minutes to several hours, (b) in a system substantially containing no solvent, at a temperature of 130 to 350 ° C. for 20 seconds to 30 minutes, preferably 40 seconds to 5 minutes The method of melt kneading can be suitably adopted.

The modified cyclic olefin copolymer of the present invention has a graft copolymerization monomer content of 0.01 to 30.
It is preferably in the range of wt%, particularly 0.05 to 15 wt%. If the graft amount is less than 0.01% by weight, the adhesive strength with other thermoplastic resins or metals or the compatibility with other resins may be insufficient, and if it exceeds 30% by weight, it is economically disadvantageous. In addition, the adhesiveness and compatibility with the polyolefin resin may decrease.

The modified cyclic olefin copolymer of the present invention has an intrinsic viscosity [η] of 0.02 to 20 dl / g, particularly 0.05 to 10 when measured in decalin at 135 ° C.
It is preferably dl / g. The intrinsic viscosity [η] is 0.
If it is less than 02 dl / g, the strength may remarkably decrease, and if it exceeds 20 dl / g, the moldability may remarkably deteriorate.

The modified cyclic olefin-based copolymer of the present invention is excellent in low-temperature characteristics, elastic recovery, compatibility with other resins, and adhesiveness, so that it is used as an industrial product, a member for automobiles, a member for home appliances, and a multilayer. Molding materials such as materials, or resin modifiers,
It can be used for various purposes such as a resin compatibilizer.

[0067]

EXAMPLES Next, the present invention will be specifically shown by Examples and Comparative Examples, but the present invention is not limited to the following Examples. First, prior to the production of the modified cycloolefin copolymer, the cycloolefin copolymer of the following reference example was produced.

Reference Example (Copolymerization of Ethylene with 2-Norbornene) Under a nitrogen atmosphere at room temperature, 15 liters of toluene, 23 mmols of triisobutylaluminum (TIBA), 38 micromoles of zirconium tetrachloride, and tetra ( Pentafluorophenyl)
Add 60 micromoles of anilinium borate in this order,
Subsequently, 2.4 liters of a toluene solution containing 70% by weight of 2-norbornene (16 mol of 2-norbornene) was added. After heating to 80 ° C, the ethylene partial pressure is 8
The reaction was carried out for 110 minutes while continuously introducing ethylene so as to obtain Kg / cm ² . After the reaction was completed, 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) was 2.93 Kg. The polymerization activity was 846 Kg / gZr.

The obtained cyclic olefin-based copolymer (a
The physical properties of 1) were as follows. 30 of ¹³ C-NMR
The sum of the peaks based on ethylene and the peaks based on methylene at the 5th and 6th positions of norbornene appearing around ppm and 3
The norbornene content calculated from the ratio with the peak based on the methylene group at the 7-position of norbornene appearing at around 2.5 ppm was 7.7 mol%. The intrinsic viscosity [η] measured in decalin at 135 ° C was 1.20 dl / g, and the crystallinity determined by the X-ray diffraction method was 1.0%. Vibron 11-EA manufactured by Toyo Boulding Co., Ltd. is used as a measuring device, and a measuring piece having a width of 4 mm, a length of 40 mm and a thickness of 0.1 mm is measured at a heating rate of 3 ° C./min and a frequency of 3.5 Hz. The glass transition temperature (Tg) was determined from the peak of the loss elastic modulus (E ″) of Tg was 0 ° C. ALC / GPC150C manufactured by Waters was used as a measuring device, and 1,2,4-trichlorobenzene solvent was used. , 135 ° C
Then, when the weight average molecular weight Mw, the number average molecular weight Mn, and the molecular weight distribution (Mw / Mn) were calculated in terms of polyethylene,
Mw is 58,100, Mn is 30,400, Mw / Mn
= 1.91. Perkin Elmer 7 series DSC at a temperature rising rate of 10 ° C./min.
The melting point (Tm) was measured in the range of 150 ° C.
Was 72 ° C. (broad peak) ° C.

Next, examples and comparative examples using the cyclic olefin copolymer a1 obtained in the above-mentioned reference example will be shown. Example 1 Under a nitrogen atmosphere, at 110 ° C., 50 g of the cyclic olefin copolymer (a1) obtained in the above Reference Example was dissolved in 500 ml of toluene in a 1 liter autoclave. Then, a toluene solution of maleic anhydride (5 g / 1
00 ml) and a toluene solution of dicumyl peroxide (0.5 g / 50 ml) were gradually added dropwise. After dropping over 2 hours, the reaction was continued for 3 hours. The reaction solution was poured into 1 liter of methanol to precipitate a polymer. This polymer was collected by filtration and dried to obtain 51.5 g of a modified cyclic olefin-based copolymer. The obtained modified cyclic olefin-based copolymer was heated at 190 ° C. and 100 kg / cm ² for 3 times.
It was hot pressed for a minute to obtain a film having a thickness of 100 μm. From this, a test piece with a length of 50 mm and a width of 15 mm was cut out and the physical properties were measured. The results are shown in Table 1.

Examples 2 to 4 Example 1 was repeated except that the kinds and amounts of the monomers were changed as shown in Table 1. The results are shown in Table 1.

Comparative Example 19 The cyclic olefin copolymer a1 was used without modification.
Heat-pressed at 0 ° C and 100 kg / cm ² for 3 minutes to obtain a thickness of 1
A film of 00 μm was obtained. From this, a test piece with a length of 50 mm and a width of 15 mm was cut out and the physical properties were measured. The results are shown in Table 1.

The measurement of each item was performed as follows. Intrinsic viscosity [η] Measured in decalin at 135 ° C. It was performed according to JIS-K7113 using a tensile modulus autograph. The tensile rupture strength autograph was performed according to JIS-K7113. Tensile elongation at break Autograph was performed according to JIS-K7113. Elastic recovery autograph, pulling speed 62mm / min, width 6m
m, 50 mm (L ₀ ) between clamps was stretched and stretched by 150%, held for 5 minutes, and then contracted suddenly without rebounding, and after 1 minute, the sheet length between clamps (L ₁ ) was measured and determined by the following formula. Elastic recovery rate (%) = [1-{(L ₁ −L ₀ ) / L ₀ }] ×
A PET film (having a thickness of 40 μm) of the same shape was superposed on a 100 peel strength test piece and pressure-bonded at 190 ° C. and 3.0 kg / cm ² for 10 seconds. The obtained laminated piece was subjected to a T-type peeling test at a pulling speed of 10 mm / min, and the peeling strength was defined as the load per 1 cm of the wearing width.

[0074]

[Table 1]

[0075]

As described above, the modified cycloolefin copolymer of the present invention is excellent in low-temperature properties, elastic recovery, compatibility with other resins, and adhesiveness with other materials.

Claims (3)

[Claims] 1. A cyclic olefin-based copolymer having a repeating unit derived from an α-olefin and a repeating unit derived from a cyclic olefin and having a glass transition temperature (Tg) of 30 ° C. or lower has at least an unsaturated group. A modified cyclic olefin-based copolymer, which is obtained by graft-copolymerizing one unsaturated group-containing monomer. 2. The modified cyclic olefin-based copolymer according to claim 1, wherein the cyclic olefin is a norbornene-based monomer. 3. The graft copolymerization monomer content is 0.0
The modified cyclic olefin-based copolymer according to claim 1 or 2, which has an intrinsic viscosity [η] of 1 to 30% by weight and measured in decalin at 135 ° C of 0.02 to 20 dl / g.