JP2001247629A - Olefinic copolymer bearing functional group, its production method and rubber composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an olefinic copolymer which gives an elastomer exhibiting high adhesion properties to and high compatibility with other materials as well as excellence in high coating properties and printing suitability, an elastomer having superior durability and further an elastomer free from or almost free from offensive odor, a method for producing the same and a rubber composition comprising the copolymer. SOLUTION: The copolymer comprises a constitutional unit (a) derived from ethylene, a constitutional unit (b) derived from a 3-12C α-olefin, a constitutional unit (c) derived from a cyclic olefin bearing a specific functional group and a constitutional unit (d) derived from an optionally employable unconjugated diene, and has an intrinsic viscosity [η], measured in decalin at 135 deg.C, of 0.1-10 dl/g.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an olefin copolymer having a functional group, a method for producing the same, and a rubber composition containing the olefin copolymer having a functional group. It has a functional group that is excellent in adhesiveness and compatibility with, has excellent paintability, printability and durability, and is suitable as a material for automobile parts, machine parts, electronic parts, civil engineering materials, etc. The present invention relates to an olefin copolymer, a method for producing the same, and a rubber composition containing the olefin copolymer having the functional group.

[0002]

2. Description of the Related Art Hitherto, olefin copolymer elastomers such as ethylene / α-olefin copolymer elastomer and ethylene / α-olefin / non-conjugated diene copolymer elastomer have been known as elastomer materials having excellent heat resistance and weather resistance. Therefore, it is widely used as a material for automobile parts, machine parts, civil engineering materials and the like. In addition, olefin copolymer elastomers are widely used as modifiers for resins such as polypropylene and polyethylene. However, such an olefin-based copolymer elastomer does not have a polar group or a functional group in the molecular structure, and therefore has low adhesion to metals, adhesion and compatibility to elastomers or resins other than polyolefins, There is a problem that the paintability and printability of the obtained molded article are low. For these reasons, an olefin copolymer having a functional group introduced by using a cyclic olefin having a functional group such as a carboxyl group or an amino group as a monomer component has been proposed (Japanese Patent Publication No. 43275/1979). Gazette, JP-A-1-2590
No. 12, JP-A-64-54009, Japanese Patent Application Laid-Open No.
-503963).

However, olefin copolymers having such functional groups introduced therein have the following problems. In other words, a structural unit derived from a cyclic olefin having a functional group has an active tertiary hydrogen atom (a hydrogen atom bonded to a tertiary carbon atom) generated by replacing a hydrogen atom with a functional group. In other words, a tertiary hydrogen atom is bonded to the carbon atom to which the functional group is bonded. When such a tertiary hydrogen atom is present in the copolymer, the tertiary hydrogen atom is separated from the carbon atom to easily generate a radical. Deterioration due to elimination of a substituent containing a functional group is likely to occur. Therefore, it is difficult to obtain an elastomer having excellent durability from the olefin copolymer into which the above functional group has been introduced. Further, for example, a cyclic olefin having a carboxyl group as a functional group has a strong odor, and when such a cyclic olefin is used as a monomer, the cyclic olefin is inevitably contained in the obtained copolymer. By surviving,
Since the copolymer also has a strong odor, there is an environmental or sanitary problem.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and a first object of the present invention is to provide high adhesiveness and compatibility with other materials, high paintability, An object of the present invention is to provide an olefin-based copolymer having a functional group capable of obtaining an elastomer having high printability, obtaining an elastomer having excellent durability, and obtaining an elastomer having no or little odor.
A second object of the present invention is to provide an elastomer having high adhesiveness and compatibility with other materials, high coatability and printability, and an elastomer having excellent durability and further having no odor or It is an object of the present invention to provide a method capable of reliably producing an olefin copolymer having a functional group from which a small amount of elastomer can be obtained. A third object of the present invention is to provide an elastomer having high adhesiveness and compatibility with other materials, high coatability and printability, and an elastomer having excellent durability, mechanical properties and abrasion resistance. It is an object of the present invention to provide a rubber composition which can be obtained and further obtains an elastomer having no or little odor.

[0005]

The olefin copolymer having a functional group of the present invention comprises a structural unit (a) derived from ethylene and a structural unit derived from an α-olefin having 3 to 12 carbon atoms (a). b) and a structural unit (c) represented by the following general formula (1), wherein the intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.1 to 10 dl / g. I do.

[0006]

Embedded image

[Wherein, X ¹ and X ² each independently represent a hydrogen atom, a hydrocarbon group or the following specific functional group, and at least one of X ¹ and X ² represents the following specific functional group It is. R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms;
Among R ¹ and R ² , those bonded to the carbon atoms to which the following specific functional groups are bonded are hydrocarbon groups having 1 to 10 carbon atoms. n shows the integer of 0-2. Specific functional groups:
A hydroxyl group or a hydrocarbon group having a hydroxyl group bonded thereto, a carboxyl group or a hydrocarbon group having a carboxyl group bonded thereto, a primary amino group, a secondary amino group or a hydrocarbon group having any of these amino groups bonded thereto; quaternary ammonium salts, tables bound active hydrogen to the nitrogen atom having at least one amide group or a hydrocarbon group which the amide group is bonded, as well as -CO-NH-CO-, which is composed of X ¹ and X ² A functional group selected from the group consisting of imide groups. ]

Further, the olefin copolymer having a functional group of the present invention comprises a structural unit (a) derived from ethylene,
A structural unit (b) derived from an α-olefin having 3 to 12 carbon atoms, and a structural unit (c) represented by the general formula (1).
And a structural unit (d) derived from a non-conjugated diene, wherein the intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.1 to 10 dl / g.

In the olefin copolymer having a functional group of the present invention, the structural unit (a) derived from ethylene is 5 to 90 mol%, and the α-olefin having 3 to 12 carbon atoms is used.
The structural unit (b) derived from an olefin is 5 to 60 mol%, and the structural unit (c) represented by the general formula (1) is 0.1 to 0.2 mol%.
It is preferable that the content of the structural unit (d) derived from the non-conjugated diene is 0 to 12 mol%, and the content of the non-conjugated diene is 0 to 12 mol%. In the olefin copolymer having a functional group according to the present invention, the structural unit (c) represented by the general formula (1) is used.
In the general formula (1), only ^one of X ¹ and X ² is a specific functional group, and R ¹ or R ² bonded to the carbon atom to which the specific functional group is bonded is a carbon number. Is 1
Or 2 hydrocarbon groups, especially X
Preferably, the other of ¹ and X ² is a hydrogen atom, and R ¹ or R ² bonded to the carbon atom to which the hydrogen atom is bonded is a hydrogen atom. Further, in the olefin copolymer having a functional group of the present invention, the glass transition temperature is preferably from -90 to 50 ° C, and furthermore,-
Preferably it is 70 to 10 ° C.

The process for producing an olefin-based copolymer having a functional group according to the present invention comprises a functional group-containing cyclic olefin represented by the following general formula (2): Reaction with an organometallic compound of a metal selected from the group consisting of: a reaction product obtained, ethylene, an α-olefin having 3 to 12 carbon atoms, and a non-conjugated diene used as necessary; A step of polymerizing in the presence of a catalyst comprising a metal compound and an organoaluminum compound.

[0011]

Embedded image

[In the formula, X ¹ and X ² each independently represent a hydrogen atom, a hydrocarbon group or the following specific functional group, and at least one of X ¹ and X ² represents the following specific functional group It is. R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms;
Among R ¹ and R ² , those bonded to the carbon atoms to which the following specific functional groups are bonded are hydrocarbon groups having 1 to 10 carbon atoms. n shows the integer of 0-2. Specific functional group: hydroxyl group or hydrocarbon group with hydroxyl group, carboxyl group or hydrocarbon group with carboxyl group, primary amino group, secondary amino group, or hydrocarbon with these amino groups bonded Or quaternary ammonium salts thereof, an amide group having at least one active hydrogen bonded to a nitrogen atom or a hydrocarbon group bonded to this amide group, and X ¹ and X
Functional groups selected from the group consisting of an imide group represented by -CO-NH-CO- constructed from ^2. ]

In the method for producing an olefin-based copolymer having a functional group according to the present invention, the organometallic compound of a metal selected from Group 2, 12 and 13 of the periodic table is an organoaluminum compound. Is preferred. Also,
The organometallic compound of a metal selected from Groups 2, 12, and 13 of the periodic table is added in an amount of 0.8 to 1 equivalent of the functional group in the functional group-containing cyclic olefin represented by the general formula (2). It is preferable to use the compound in a ratio of not less than the equivalent.

The rubber composition of the present invention is characterized by containing (A) the above-mentioned olefin copolymer having a functional group and (B) a vulcanizing agent and / or a crosslinking agent.

The rubber composition of the present invention may contain (C) an olefin copolymer having no functional group. In such a rubber composition, the olefin copolymer having no functional group (C) is a copolymer comprising a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 to 12 carbon atoms. A polymer, and / or
Α- having a structural unit derived from ethylene and a carbon number of 3 to 12
It is preferable that the copolymer is a copolymer comprising a structural unit derived from an olefin and a structural unit derived from a non-conjugated diene.
Further, the weight ratio of (A) the olefin-based copolymer having a functional group to (C) the olefin-based copolymer having no functional group may be 1:99 to 99: 1 by weight. preferable.

[0016]

Embodiments of the present invention will be described below in detail. The olefin copolymer having a functional group of the present invention (hereinafter, also referred to as “functional group-containing olefin copolymer”) is a structural unit (a) derived from ethylene (hereinafter simply referred to as “structural unit (a)”). Also called.)
And a structural unit (b) derived from an α-olefin having 3 to 12 carbon atoms (hereinafter also referred to as “specific α-olefin”) (hereinafter, also simply referred to as “structural unit (b)”).
And a structural unit (c) represented by the general formula (1) (hereinafter, also simply referred to as “structural unit (c)”),
If necessary, a structural unit (d) derived from a non-conjugated diene
(Hereinafter, also simply referred to as “structural unit (d)”).

In the functional group-containing olefin copolymer of the present invention, the structural unit (a) is preferably contained in the range of 5 to 90 mol% of all the structural units, more preferably 10 to 85 mol%. %, Particularly preferably 15 to 80 mol%. When the content ratio of the structural unit (a) is 5 mol% or more, it becomes easy to copolymerize a functional group-containing cyclic olefin represented by the following general formula (2), and excellent durability is obtained. Having an elastomer easily obtained. On the other hand, when the proportion of the structural unit (a) is 90 mol% or less, a copolymer exhibiting behavior as an elastomer is easily obtained.

The specific α for forming the structural unit (b)
-Olefin is an α-olefin having 3 to 12 carbon atoms, and specific examples thereof include propylene, 1-butene, 1-pentene, 4-methyl-pentene-1, 1-hexene, 1-heptene, 1-octene, 1-decene, 1
-Dodecene, styrene, p-methylstyrene and the like. These compounds can be used alone or in combination of two or more. Α having 12 or less carbon atoms
By using an olefin, the copolymerizability of the α-olefin with another monomer is likely to be good.

The structural unit (b) is 5% of all structural units.
It is preferably contained in the range of ~ 60 mol%,
More preferably 10 to 55 mol%, particularly preferably 15 mol%.
~ 50 mol%. When the content ratio of the structural unit (b) is 5 mol% or more, an elastomer having sufficient elasticity is easily obtained. On the other hand, when the proportion of the structural unit (b) is 60 mol% or less, the obtained elastomer tends to have good durability.

The structural unit (c) is a structural unit represented by the above general formula (1) and includes a functional group-containing cyclic olefin represented by the above general formula (2) (hereinafter referred to as a “specific functional group-containing cyclic olefin”). Cyclic olefin "). In the general formulas (1) and (2),
The groups X ¹ and X ² are each independently a hydrogen atom, a hydrocarbon group or a specific functional group, and at least one of X ¹ and X ² is a specific functional group. Here, the specific functional group is a hydroxyl group, a hydrocarbon group bonded with a hydroxyl group, a carboxyl group, a hydrocarbon group bonded with a carboxyl group, a primary amino group, a secondary amino group,
A hydrocarbon group having a primary amino group or a secondary amino group bonded thereto, a quaternary ammonium salt of these amino groups or a hydrocarbon group having the amino group bonded thereto, having at least one active hydrogen bonded to a nitrogen atom A functional group selected from the group consisting of an amide group, a hydrocarbon group to which the amide group is bonded, and an imide group represented by —CO—NH—CO— composed of X ¹ and X ² ; The hydrocarbon group having a group bonded thereto, the hydrocarbon group having a carboxyl group bonded thereto, the hydrocarbon group having an amino group bonded thereto or a quaternary ammonium salt thereof are preferably those having 1 to 5 carbon atoms excluding the substituent. The groups R ¹ and R ² are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and are bonded to a carbon atom to which a specific functional group is bonded among the groups R ¹ and R ^2. This is a hydrocarbon group having 1 to 10 carbon atoms. The value of the number of repetitions n is an integer of 0 to 2.

As the structural unit (c), in the general formula (1), only ^one of the groups X ¹ and X ² is a specific functional group, and is bonded to a carbon atom to which the specific functional group is bonded. The group R ¹ or the group R ² is preferably a hydrocarbon group having 1 or 2 carbon atoms, in that the decomposition of the polymer hardly occurs and an elastomer having excellent durability is obtained, and in particular, And the other of the groups X ¹ and X ² is a hydrogen atom, and the group R ¹ or the group R ² bonded to the carbon atom to which the hydrogen atom is bonded is preferably a hydrogen atom. Further, the specific functional group, -COOH (carboxyl group), - NH ₂ (amino group), - NHCH
₃ (aminomethyl ^{_{group), - CONH 2, -CONR 3}} H
(Provided that R ³ represents an alkyl group) and the like,
Among these, -COOH (carboxyl group), -C
ONH ₂ and —CONR ³ H are more preferred. Also,
In the general formula (2), when the value of the number of repetitions n is 3 or more, it becomes difficult to copolymerize the functional group-containing cyclic olefin with another monomer.

Specific agents for forming the structural unit (c)
Functional group-containing cyclic olefins are functionalized with cyclopentadiene.
Group-containing olefin by Diels-Alder reaction
And, if necessary, a hydrolysis reaction.
Manufactured. Such specific functional group-containing cyclic olefins
Specific examples of quinine include 5,6-dimethyl-5,6-di
Hydroxy-bicyclo [2.2.1] -2-heptene,
5,6-dimethyl-5,6-dicarboxy-bicyclo
[2.2.1] -2-heptene, 5,6-diethyl-
5,6-dicarboxy-bicyclo [2.2.1] -2-
Heptene, 5,6-dimethyl-5,6-bis (carboxy
Cimethyl) -bicyclo [2.2.1] -2-heptene,
5,6-diethyl-5,6-bis (carboxymethyl)
-Bicyclo [2.2.1] -2-heptene, 5,6-di
Methyl-5,6-bis (hydroxymethyl) -bicyclo
[2.2.1] -2-heptene, 5,6-diethyl-
5,6-bis (hydroxymethyl) -bicyclo [2.
2.1] -2-Heptene, 5,6-dimethyl-5,6-
Bis (aminomethyl) -bicyclo [2.2.1] -2-
Heptene, 5,6-diethyl-5,6-bis (amino
Tyl) -bicyclo [2.2.1] -2-heptene, 5,
6-dimethyl-5,6-bis (aminopropyl) -bis
Black [2.2.1] -2-heptene, 5,6-dimethyl
-5,6-bis (aminocarbonyl) -bicyclo [2.
2.1] -2-Heptene, 5,6-dimethyl-5,6-
Bis (N-methyl-aminocarbonyl) -bicyclo
[2.2.1] -2-Heptene, 5,6-dimethyl-
5,6-bis (N-propyl-aminocarbonyl) -bi
Cyclo [2.2.1] -2-heptene, 5,6-diethyl
Ru-5,6-bis (aminocarbonyl) -bicyclo
[2.2.1] -2-heptene, 5,6-diethyl-
5,6-bis (N-ethyl-aminocarbonyl) -bis
Black [2.2.1] -2-heptene, 5,6-dimethyl
-Bicyclo [2.2.1] -2-heptene-5,6-di
Carboximide, 5-methyl-5-hydroxy-bicyclo
Black [2.2.1] -2-heptene, 5-methyl-5-
Carboxy-bicyclo [2.2.1] -2-heptene,
5-ethyl-5-carboxy-bicyclo [2.2.1]
-2-heptene, 5-methyl-5-hydroxymethyl-
Bicyclo [2.2.1] -2-heptene, 5-ethyl-
5-hydroxymethyl-bicyclo [2.2.1] -2-
Heptene, 5-methyl-5-carboxymethyl-bisic
B [2.2.1] -2-heptene, 5-ethyl-5-ca
Ruboxymethyl-bicyclo [2.2.1] -2-hepte
5-methyl-5-aminomethyl-bicyclo [2.
2.1] -2-Heptene, 5-ethyl-5-aminomethyl
Rubicyclo [2.2.1] -2-heptene, 5-methyl
Ru-5-aminopropyl-bicyclo [2.2.1] -2
-Heptene, 5-methyl-5-aminocarbonyl-bis
Black [2.2.1] -2-heptene, 5-methyl-5-
N-methyl-aminocarbonyl-bicyclo [2.2.
1] -2-heptene, 5-methyl-5-N-propyl-
Aminocarbonyl-bicyclo [2.2.1] -2-hep
Ten, 5-ethyl-5-aminocarbonyl-bicyclo
[2.2.1] -2-heptene, 5-ethyl-5-N-
Ethyl-aminocarbonyl-bicyclo [2.2.1]-
2-heptene, 8,9-dimethyl-8,9-dicarboxy
C-tetracyclo [4.4.0.1^{2, Five}. 1^7,10] -3
-Dodecene, 8,9-diethyl-8,9-dicarboxy
-Tetracyclo [4.4.0.1^{2, Five}. 1^7,10] -3-
Dodecene, 8,9-dimethyl-8,9-bis (hydroxy
Cimethyl) -tetracyclo [4.4.0.1^2,5. 1
^7,10] -3-dodecene, 8,9-diethyl-8,9-bi
(Hydroxymethyl) -tetracyclo [4.4.0.
1^2,5. 1^7,10] -3-dodecene, 8,9-dimethyl-
8,9-bis (aminomethyl) -tetracyclo [4.
4.0.1.^2,5. 1^7,10] -3-dodecene, 8,9-di
Ethyl-8,9-bis (aminomethyl) -tetracyclo
[4.4.0.1^2,5. 1^7,10-3-dodecene, 8,
9-dimethyl-8,9-bis (aminocarbonyl) -te
Toracyclo [4.4.0.1^2,5. 1^7,10] -3-Dode
Sen, 8,9-dimethyl-8,9-bis (N-methyl-
Aminocarbonyl) -tetracyclo [4.4.0.1
^2,5. 1^7,10] -3-dodecene, 8,9-diethyl-
8,9-bis (aminocarbonyl) -tetracyclo
[4.4.0.1^2,5. 1^7,10-3-dodecene, 8,
9-diethyl-8,9-bis (N-ethyl-aminocar
Bonyl) -tetracyclo [4.4.0.1^2,5.
1^7,10] -3-dodecene, 8-methyl-8-carboxy
-Tetracyclo [4.4.0.1^2,5. 1^7,10] -3-
Dodecene, 8-ethyl-8-carboxy-tetracyclo
[4.4.0.1^2,5. 1^7,10] -3-dodecene, 8-
Methyl-8-hydroxymethyl-tetracyclo [4.
4.0.1.^2,5. 1 ^7,10] -3-dodecene, 8-ethyl
-8-hydroxymethyl-tetracyclo [4.4.0.
1^2,5. 1 ^7,10] -3-dodecene, 8-methyl-8-a
Minomethyl-tetracyclo [4.4.0.1^2,5. 1
^7,10] -3-dodecene, 8-ethyl-8-aminomethyl
-Tetracyclo [4.4.0.1^2,5. 1^7,10] -3-
Dodecene, 8-methyl-8-aminocarbonyl-tetra
Cyclo [4.4.0.1^2,5. 1 ^7,10] -3-Dodece
8-methyl-8-N-methyl-aminocarbonyl-
Tetracyclo [4.4.0.1^2,5. 1^7,10] -3-do
Decene, 8-ethyl-8-aminocarbonyl-tetracy
Black [4.4.0.1^2,5. 1 ^7,10-3-dodecene,
8-ethyl-8-N-ethyl-aminocarbonyl-tetra
Lacyclo [4.4.0.1^2,5. 1^7,10] -3-Dodece
And the like.

The structural unit (c) is 0.01 in all structural units.
Preferably, it is contained in the range of ~ 30 mol%,
More preferably, it is 0.05 to 10 mol%, particularly preferably 0.1 to 5 mol%. When the content of the structural unit (c) is at least 0.01 mol%, the resulting elastomer tends to have good adhesion, compatibility, and coating properties to metals, elastomers other than polyolefins, and resins. . On the other hand, when the ratio of the structural unit (c) is 3
When the content is 0 mol% or less, the copolymerization of the specific functional group-containing cyclic olefin with another monomer becomes good, and the obtained copolymer easily obtains rubber elasticity as an elastomer. As a result, a high molecular weight copolymer is easily obtained.

The structural unit (d) is a structural unit derived from a non-conjugated diene, and is contained in the copolymer as required. Specific examples of the non-conjugated diene for forming the structural unit (d) include 1,4-hexadiene,
Linear non-cyclic dienes such as 1,6-octadiene and 1,5-hexadiene, 5-methyl-1,4-hexadiene,
3,7-dimethyl-1,6-octadiene, 5,7-dimethyl-1,6-octadiene, 3,7-dimethyl-
Branched non-cyclic dienes such as 1,7-octadiene, 7-methyl-1,6-octadiene and dihydromyrcene;
Tetrahydroindene, methyltetrahydroindene,
Dicyclopentadiene, bicyclo- (2,2,1) -hepta-2,5-diene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene Alicyclic dienes such as -2-norbornene, 5-cyclohexylidene-2-norbornene, and 5-vinyl-2-norbornene; These compounds can be used alone or in combination of two or more. Preferred among the non-conjugated dienes are
Examples thereof include 1,4-hexadiene, 5-methylene-2-norbornene, and 5-ethylidene-2-norbornene.

The structural unit (d) is 0 to 12 in all the structural units.
It is preferably contained in such a ratio as to be mol%, more preferably 0 to 8 mol%, and particularly preferably 0 to 5 mol%. When the content of the structural unit (d) is 12 mol% or less, the resulting elastomer tends to have good durability.

The functional group-containing olefin copolymer of the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C.
Is in the range of 0.1 to 10 dl / g, preferably 0.1 to 7 dl / g, particularly preferably 0.1 to 5 dl / g.
dl / g. This intrinsic viscosity [η] is 0.1 dl / g
As described above, an elastomer having rubber elasticity is easily obtained by being vulcanized or crosslinked. On the other hand, when the intrinsic viscosity [η] is 10 dl / g or less, the copolymer tends to have good moldability. Further, the functional group-containing olefin-based copolymer of the present invention was obtained at 135 ° C. by gel permeation chromatography.
Has a weight average molecular weight Mw of 1,000 to 3,000 in terms of polystyrene measured using an o-dichlorobenzene solvent.
000, more preferably 3,
000 to 1,000,000, particularly preferably 5,000
It is preferably from 0 to 700,000, and the number average molecular weight Mn in terms of polystyrene is preferably from 500 to 1,000,000, more preferably from 1,000 to 500,000,
Particularly preferably, it is 2,000 to 300,000.

The glass transition temperature of the functional group-containing olefin copolymer of the present invention is -90 to 50 ° C., especially -7.
The temperature is preferably from 0 to 10 ° C., whereby an elastomer having sufficient elasticity is obtained. Here, the glass transition temperature of the functional group-containing olefin-based copolymer can be measured by a scanning differential thermal analyzer (DSC).

According to the functional group-containing olefin copolymer of the present invention, since the structural unit (c) has a specific functional group (X ¹ and / or X ² ), it has high adhesiveness to metal. In addition, an elastomer having high adhesiveness and compatibility with polymers other than olefin-based elastomers and resins, and further having excellent coatability and printability can be obtained. In the structural unit (c), a hydrogen atom is not bonded to a carbon atom to which a specific functional group (X ¹ and / or X ² ) is bonded. Therefore, a radical is released from the bonded carbon atom to form a radical. Since there is no tertiary hydrogen atom that is likely to be generated, cutting of the molecular chain due to generation of radicals, oxidation and elimination of substituents including functional groups are suppressed, and as a result, excellent durability with or without deterioration Property is obtained. Further, in the structural unit (c), since the aliphatic hydrocarbon group is bonded to the carbon atom to which the specific functional group (X ¹ and / or X ² ) is bonded, the specific functional group is, for example, a carboxyl group. In some cases, the specific functional group-containing cyclic olefin used as the monomer has no or little odor, so that a copolymer having no or little odor is obtained.

According to the functional group-containing olefin copolymer of the present invention, since it has the above properties, it is possible to obtain an elastomer suitable for materials such as automobile parts, machine parts, and building materials. Further, since the functional group-containing olefin copolymer of the present invention has high compatibility with other polymers, other elastomer materials such as nitrile rubber, chloroprene rubber, chlorinated polyethylene rubber, halogenated butyl rubber, acrylic rubber, When cross-linking is performed by mixing with an ethylene / acryl copolymer rubber, hydrogenated nitrile rubber, or the like, an elastomer having good co-crosslinking properties can be obtained. The functional group-containing olefin copolymer of the present invention includes polypropylene, polyethylene, hydrogenated styrene / butadiene random copolymer, hydrogenated styrene / butadiene block copolymer, hydrogenated styrene / isoprene block copolymer, and the like. It can be used as a modifier, and such a material is suitable as an exterior or interior material for automobiles such as various films, bumpers, instrument panels, and door trims.

Further, according to the functional group-containing olefin copolymer of the present invention, by utilizing the functional group in the structural unit (c) as a starting point, a polyester such as polybutylene terephthalate and polyethylene terephthalate can be obtained.
A graft copolymer with polyamide and polyurethane can be obtained, whereby a resin having improved impact resistance, a thermoplastic elastomer having high heat resistance, and the like can be obtained.

The functional group-containing olefin polymer as described above can be produced as follows. First,
By reacting an organometallic compound (hereinafter, referred to as a “specific organometallic compound”) with a metal selected from Groups 2, 12, and 13 of the periodic table and a specific functional group-containing cyclic olefin. The masking treatment is performed on the functional group (group X ¹ and / or group X ² ) of the specific functional group-containing cyclic olefin.

Specific examples of the specific organometallic compound used for the masking treatment include diethyl zinc, dibutyl magnesium, ethyl magnesium chloride, butyl magnesium chloride, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, diisobutyl hydride. Aluminum, diethylaluminum hydride, ethylaluminum dihydride, diethylaluminum ethoxide, ethylaluminum diethoxide, dibutylaluminum ethoxide, dibutylaluminum butoxide, diisobutylaluminum dibutoxide, diisobutylaluminum isopropoxide, diisobutylaluminum 2-ethylhexide, Isobutyl aluminum butoxide, isobutyl aluminum 2-ethylhexide, diethylaluminum chloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquichloride, methylalumoxane, ethylalumoxane, butylalumoxane obtained by reaction of water or copper sulfate hydrate with trialkylaluminum And the like. Of these, organoaluminum compounds are preferred, and particularly preferred organoaluminum compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, diisobutylaluminum hydride, diethylaluminum chloride, ethylaluminum sesquichloride and the like.

The masking treatment, that is, the reaction between the specific functional group-containing cyclic olefin and the specific organometallic compound is carried out in the presence of an inert solvent or a diluent and under an inert gas such as nitrogen gas, argon gas, helium gas or the like. It is preferably performed in an atmosphere. Here, as the inert solvent or diluent, aliphatic hydrocarbons such as butane, pentane, hexane, heptane and octane, cyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane, benzene, toluene, xylene , Chlorobenzene,
Aromatic compounds such as dichloroethane and dichloromethane, and halogenated hydrocarbon compounds can be used.

The specific organometallic compound is used in an amount of 0.8 equivalent or more, preferably 0.9 to 1.5 equivalent, per equivalent of the functional group in the specific functional group-containing cyclic olefin. preferable. If this ratio is too low, a large amount of functional groups that are not masked remain, so that the catalyst activity may decrease in the polymerization treatment described below and the polymerization reaction may not proceed sufficiently. The reaction conditions of the specific functional group-containing cyclic olefin and the specific organometallic compound vary depending on the type of the specific organometallic compound and the specific functional group-containing cyclic olefin used, but the reaction time is usually 2 minutes to 10 minutes. Time, preferably 10 minutes ~
The reaction time is usually -10 to 60C, preferably 10 to 40C.

The specific functional group-containing cyclic olefin masked in this manner is preferably stored at a temperature of 30 ° C. or lower until subjected to the polymerization treatment, whereby the occurrence of side reactions during the storage is caused. Can be prevented. Also, unreacted metal in the masked compound
When a carbon bond is present, isopropanol having a branched structure, sec-butanol, tert-butanol,
Alcohols such as -ethylhexanol, 2,6-di-tert-butylcresol, 2,6-di-tert
-Butylphenol, 2,6-dimethylcresol,
Phenols such as 2,6-dimethylphenol can also be added.

In the production method of the present invention, a specific functional group-containing cyclic olefin masked, ethylene, a specific α-olefin, and a non-conjugated diene used as required are polymerized. . In the polymerization of the monomer, a catalyst comprising a transition metal compound, preferably a compound of a metal selected from Groups 4 and 5 of the periodic table, and an organoaluminum compound is used. As the catalyst, it is preferable to use a catalyst capable of obtaining a copolymer in which structural units are relatively randomly arranged in a copolymerization reaction of ethylene, α-olefin and non-conjugated diene. Specific catalyst systems include the following.

(1) A catalyst system comprising a vanadium compound soluble in a hydrocarbon compound and an organoaluminum compound, wherein at least one of the vanadium compound and the organoaluminum compound contains at least one chlorine atom. Here, as the vanadium compound, a compound represented by the following general formula (3), VCl ₄ , VO (aca
c) ₂ , V (acac) ₃ (where “acac” represents an acetylacetonate group), a compound represented by the following general formula (4), or the like can be used.

[0038]

Embedded image Formula _{(3): O = VCl k} (OR 4) 3-k

(In the formula, R ⁴ represents a hydrocarbon group such as an ethyl group, a propyl group, a butyl group and a hexyl group.
Indicates an integer of 3. )

[0040]

Embedded image General formula (4): VCl ₃ · mZ

(Where Z is tetrahydrofuran, 2-
This shows a Lewis base that forms a complex that is soluble in hydrocarbon compounds such as methyl-tetrahydrofuran, 2-methoxymethyl-tetrahydrofuran, and dimethylpyridine. m is 2-3
Is an integer. )

Examples of the organoaluminum compound include a trialkylaluminum compound represented by the following general formula (5), an alkylaluminum hydride represented by the following general formula (6) or the following general formula (7), 8), chlorinated alkyl aluminum represented by the following general formula (9) or (10), alkoxy- or phenoxy-substituted organoaluminum represented by the following general formula (11) or (12), and water Methylalumoxane (MAO), ethylalumoxane, butylalumoxane, etc. obtained by the reaction with the above trialkylaluminum compound can be used.

[0043]

Embedded image

In this catalyst system, the vanadium compound and the organoaluminum compound are further added with an ester of an organic or inorganic acid, an ether, an amine,
An oxygen-containing or nitrogen-containing electron donor such as a ketone and an alkoxysilane can be added.

(2) A catalyst system comprising a titanium or zirconium halide supported on silica or magnesium chloride and an organic aluminum. Here, as titanium halide or zirconium halide, titanium tetrachloride, titanium tetrabromide, zirconium tetrachloride, or the like can be used. As the organic aluminum compound, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum,
Methylalumoxane or the like can be used. Also,
In this catalyst system, dioctyl phthalate, tetraalkoxysilane, diphenyldimethoxysilane, and the like can be further added to the above compounds.

(3) The ligand is selected from titanium, zirconium and halfnium having one or two cyclopentadienyl or indenyl groups having a substituent selected from hydrogen, an alkyl group and an allyl group. A catalyst system comprising a transition metal compound of a selected metal and an organoaluminum compound containing at least 50 mol% of methylalumoxane.

Specific examples of the above transition metal compound include bis (cyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) diethyl zirconium, bis (cyclopentadienyl) methyl zirconium monochloride, and ethylenebis (cyclopentane). Dienyl) diuconium dichloride, ethylene bis (cyclopentadienyl) methyl zirconium monochloride, methylene bis (cyclopentadienyl) zirconium dichloride, ethylene bis (indenyl) zirconium dichloride, ethylene bis (indenyl) dimethyl zirconium, ethylene bis ( Indenyl) diphenylzirconium, ethylenebis (4,5,6,7-tetrahydro-1
-Indenyl) dimethyl zirconium, ethylenebis (4-methyl-1-indenyl) zirconium dichloride, ethylenebis (2,3-dimethyl-1-indenyl) zirconium dichloride, dimethylsilylbis (cyclopentadienyl) zirconium dichloride,
Dimethylsilylbis (indenyl) zirconium dichloride, dimethylsilylbis (dimethylcyclopentadienyl) zirconium dichloride, dimethylmethyl (fluorenyl) (cyclopentadienyl) zirconium dichloride, diphenylmethyl (fluorenyl)
(Cyclopentadienyl) zirconium dichloride,
Diphenylsilylbis (indenyl) zirconium dichloride, dimethylsilylbis (2-methyl-4-phenyl-indenyl) zirconium dichloride, bis (cyclopentadienyl) dimethyltitanium, bis (cyclopentadienyl) methyltitanium monochloride, ethylenebis (Indenyl) titanium dichloride, ethylenebis (4,5,6,7-tetrahydro-
1-indenyl) titanium dichloride, methylenebis (cyclopentadienyl) titanium dichloride,
η ¹ : η ⁵ -{[(tert-butyl-amido) dimethylsilyl] (2,3,4,5-tetramethyl-1-cyclopentadienyl)} titanium dichloride, bis (1,1,1-tri Fluoro-3-phenyl-2,4-
(Butadionato) titanium dichloride and the like.

(4) A metallocene catalyst system comprising bisalkyl-substituted or N-alkyl-substituted salicylaldimine, titanium, zirconium or halfnium dichloride, and methylalumoxane (MAO).

The polymerization of the monomer is preferably carried out in the presence of an appropriate solvent or diluent. Such solvents or diluents include, for example, aliphatic hydrocarbons,
Alicyclic hydrocarbons, aromatic hydrocarbons and their halides can be used. Specifically, butane, pentane, hexane, heptane, 2-butene, 2-
Methyl-2-butene, cyclopentane, methylcyclopentane, cyclohexane, isooctane, benzene, toluene, xylene, chlorobenzene, dichloromethane,
Dichloroethane and the like. These solvents or diluents have a water concentration of 2 by distillation or adsorption.
It is preferable to use in a state where the concentration is 0 ppm or less.

The polymerization reaction is carried out at 0 to 150 ° C., especially at 10 to 1
It is preferably carried out at a temperature of 00 ° C. In the polymerization reaction, a molecular weight regulator can be used as necessary, and specific examples thereof include hydrogen, diethyl zinc, and diisobutylaluminum hydride. Further, the reactor for performing the polymerization reaction may be any of a batch type and a continuous type. As the continuous reactor, a tube reactor, a tower reactor, a tank reactor, or the like can be used.

In the present invention, after subjecting the monomer to the polymerization treatment as described above, the resulting copolymer is subjected to a demasking treatment, whereby the desired functional group-containing olefin copolymer is obtained. can get. When a specific functional group-containing cyclic olefin in which the specific functional group (group X ¹ and / or group X ² ) is a hydroxyl group or a carboxyl group is used, the demasking treatment is performed as follows.
Formic acid, oxalic acid, fumaric acid, lactic acid, dioctyl monophosphate, trifluoroacetic acid, dodecylbenzenesulfonic acid,
The reaction is performed using an acid having a relatively high acidity such as a monophosphate of nonylphenoxypolyethylene glycol, a diphosphate of nonylphenoxypolyethylene glycol, a monophosphate of lauroxypolyethylene glycol, and a diphosphate of lauroxypolyethylene glycol. On the other hand, when a specific functional group (group X ¹ and / or group X ² ) whose specific functional group (group X ¹ and / or group X ² ) is an amino group or an amide group is used as the specific functional group-containing cyclic olefin, the demasking treatment is performed using t-butanol. Alcoholates with lithium, sodium or potassium, alcoholates with amyl alcohol, lithium, sodium or potassium, lithium salts of octanoic acid, sodium or potassium salts, lithium or potassium salts of nonylphenol, etc. ,
The reaction is performed using an alkali metal salt of phenol or an organic carboxylic acid.

In the production method of the present invention, the polymer solution containing the functional group-containing olefin copolymer thus obtained is passed through an adsorption column filled with silica, alumina, diatomaceous earth and the like. It is preferable to remove the remaining demasking agent, polymerization catalyst, etc. by washing the polymer solution by adding a large amount of water, alcohol, or the like to the polymer solution. For the purpose of improving the stability of the functional group-containing olefin-based copolymer, a known phenol-based, phosphorus-based, sulfur-based, or other antioxidant can be added to the polymer solution. After removing the solvent by blowing steam into the polymer solution, solids are separated from the obtained slurry, and further dewatered and dried using a screw-type squeezing machine, an extruder, a heating roll, and the like. By doing so, a solid functional group-containing olefin-based copolymer is obtained. Alternatively, the polymer solution is concentrated by heating, and then dried using a vented extruder to obtain a solid functional group-containing olefin copolymer.

According to the above method, the functional group in the specific functional group-containing cyclic olefin is masked with the specific organometallic compound, so that the functional group is reliably masked. Does not decrease and the polymerization reaction is not hindered. As a result, the desired functional group-containing olefin copolymer can be reliably produced.

The rubber composition of the present invention contains the component (A) composed of the above-mentioned functional group-containing olefin copolymer and the component (B) composed of a vulcanizing agent and / or a crosslinking agent. Accordingly, the composition further comprises a component (C) comprising an olefin copolymer having no functional groups.

The vulcanizing agent as the component (B) used in the rubber composition of the present invention is not particularly limited. Specific examples thereof include powdered sulfur, precipitated sulfur, colloidal sulfur, and insoluble sulfur. Sulfur; inorganic vulcanizing agents such as sulfur chloride, selenium, tellurium; morpholine disulfide, alkylphenol disulfides, thiuram disulfides,
Examples thereof include sulfur-containing organic compounds such as dithiocarbamates. These vulcanizing agents can be used alone or in combination of two or more. The use ratio of the vulcanizing agent is usually 0.1 to 100 parts by weight of the component (A).
It is 1 to 10 parts by weight, preferably 0.5 to 5 parts by weight.

In the rubber composition of the present invention, a vulcanization accelerator can be used together with the vulcanizing agent. Specific examples of such a vulcanization accelerator include aldehyde ammonias such as hexamethylenetetramine; guanidines such as diphenylguanidine, di (o-tolyl) guanidine and o-tolylpiguanide; thiocarbanilide and di (o-tolyl) thiourea. Thioureas such as N, N'-diethylthiourea, tetramethylthiourea, trimethylthiourea and dilaurylthiourea; mercaptobenzothiazole, dibenzothiazole disulfide, 2- (4-
Morpholinothio) benzothiazole, 2- (2,4-
Dinitrophenyl) -mercaptobenzothiazole,
Thiazoles such as (N, N'-diethylthiocarbamoylthio) benzothiazole; Nt-butyl-2-benzothiazylsulfenamide, N, N'-dicyclohexyl-2-benzothiazylsulfenamide, N , N '
Sulfenamides such as diisopropyl-2-benzothiazylsulfenamide, N-cyclohexyl-2-benzothiazylsulfenamide; tetramethylthiuram disulfide, tetraethylthiuram disulfide,
Thiurams such as tetra-n-butylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylenethiuram tetrasulfide; zinc dimethylthiocarbamate, zinc diethylthiocarbamate, di-n-
Carbamates such as zinc butylthiocarbamate, zinc ethylphenyldithiocarbamate, sodium dimethyldithiocarbamate, copper dimethyldithiocarbamate, tellurium dimethylthiocarbamate and iron dimethylthiocarbamate; xanthates such as zinc butylthioxanthate; Can be mentioned. These vulcanization accelerators can be used alone or in combination of two or more. The use ratio of the vulcanization accelerator is usually 0.1 to 20 parts by weight, based on 100 parts by weight of the component (A).
Preferably it is 0.2 to 10 parts by weight.

Further, in addition to the vulcanizing agent and the vulcanization accelerator, a vulcanization acceleration aid can be added to the rubber composition of the present invention, if necessary. Specific examples of such vulcanization accelerators include magnesium oxide, zinc white, litharge,
Metal oxides such as red lead and white lead; organic acids or organic acid salts such as stearic acid, oleic acid and zinc stearate; and among them, zinc white and stearic acid are particularly preferable. These vulcanization accelerators can be used alone or in combination of two or more. The use ratio of the vulcanization accelerator is usually 0.5 to 20 parts by weight based on 100 parts by weight of the component (A).

The crosslinking agent as the component (B) used in the rubber composition of the present invention is not particularly limited.
Specific examples thereof include 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, and 2,5-dimethyl-2-. 5-di (t
Organic peroxides such as -butylperoxy) hexane and 1,3-bis (t-butylperoxyisopropyl) benzene. These crosslinkers are 1
Species can be used alone or in combination of two or more. The proportion of the crosslinking agent to be used is generally 0.1 to 15 parts by weight, preferably 0.5 to 15 parts by weight, per 100 parts by weight of the component (A).
10 parts by weight.

In the rubber composition of the present invention, a crosslinking aid can be used together with the crosslinking agent. Specific examples of such a crosslinking aid include sulfur, sulfur or a sulfur compound such as dipentamethylenethiuram tetrasulfide; ethylene diacrylate, ethylene dimethacrylate, polyethylene diacrylate, polyethylene dimethacrylate, divinylbenzene, diallyl phthalate,
Examples thereof include polyfunctional monomers such as triallyl cyanurate, metaphenylene bismaleimide, and toluylene bismaleimide; and oxime compounds such as p-quinone oxime and p, p'-dibenzoylquinone oxime. These crosslinking aids can be used alone or in combination of two or more. The use ratio of the crosslinking assistant is usually 0.5 to 100 parts by weight of the component (A).
20 parts by weight.

In the rubber composition of the present invention, the component (C) is an olefin copolymer having no functional groups, and is contained as necessary. The olefin copolymer having no functional group is not particularly limited as long as it is generally used for a rubber composition, but the structural unit derived from ethylene and the carbon number of 3 to 12 are used.
A copolymer comprising a structural unit derived from an α-olefin or a structural unit derived from ethylene;
It is preferable to use a copolymer consisting of structural units derived from α-olefins of Nos. 1 to 12 and structural units derived from non-conjugated dienes. Here, as a specific example of the α-olefin having 3 to 12 carbon atoms, a specific α-olefin for forming the structural unit (b) in the functional group-containing olefin copolymer as the component (A) is Examples illustrated are given. Specific examples of the non-conjugated diene include those exemplified as the non-conjugated diene for forming the structural unit (d) in the functional group-containing olefin copolymer as the component (A).

The olefin copolymer having no functional group as the component (C) has a weight average molecular weight Mw in terms of polystyrene measured by gel permeation chromatography at 135 ° C. using an o-dichlorobenzene solvent. It is preferably from 1,000 to 3,000,000, more preferably from 3,000 to 2,500,000,
Particularly preferably, it is 5,000 to 2,000,000, and the number average molecular weight Mn in terms of polystyrene is 500 to 1,
00000, more preferably 1,500 to 800,000, particularly preferably 2,500.
0 to 600,000.

When the component (C) is contained in the rubber composition of the present invention, the ratio of the component (A) to the component (C) is preferably from 1:99 to 99: 1 by weight. , More preferably 1:99 to 50:50, and still more preferably 3:97 to 30:70.

Further, the rubber composition of the present invention may contain a filler or a softener. Specific examples of the filler include SRF (Semi-Reinforc).
ingFurnace), FEF (Fast Extr)
usion Furnace), HAF (High A)
brain Furnace), ISAF (Int
ermediate super abrasion
Furnace), SAF (Super Abrasi)
on Furnace), FT (Fine Therm)
al), carbon black such as MT (Medium Thermal), inorganic fillers such as fine particles of magnesium silicate, calcium carbonate, magnesium carbonate, clay and talc.
These fillers can be used alone or in combination of two or more. The proportion of filler used is (A)
It is usually 10 to 200 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the component.

Specific examples of the softener include process oils such as aromatic oils, naphthenic oils and paraffin oils, vegetable oils such as palm oil, and synthetic oils such as alkylbenzene oil, which are usually used as rubber compounding agents. Among them, process oils are preferable, and paraffin oil is particularly preferable. These softeners can be used alone or in combination of two or more. The use ratio of the softening agent is usually 10 to 130 parts by weight, preferably 20 to 100 parts by weight based on 100 parts by weight of the component (A).

According to the rubber composition of the present invention, since the functional group-containing olefin copolymer is contained as the component (A), the rubber composition has high adhesiveness and compatibility with other materials,
High paintability and printability, and excellent durability,
An elastomer having mechanical properties and abrasion resistance and having little or no odor is obtained.

[0066]

EXAMPLES The present invention will now be described by way of specific examples, which should not be construed as limiting the invention thereto.

<Example 1> A 2-L separable flask purged with nitrogen was charged with 960 mL of hexane and 5-methyl-5-
5 mL of a 0.5 mol / L hexane solution of carboxy-bicyclo [2.2.1] -2-heptene (5-methyl-5
-Carboxy-bicyclo [2.2.1] -2-heptene 2.5 mmol). Then, while stirring this mixture, 2.5 mmol of Al ₂ (C ₂ H ₅ ) ₃ Cl ₃ was added.
By adding and reacting, a masking treatment of a carboxyl group in 5-methyl-5-carboxy-bicyclo [2.2.1] -2-heptene was performed. afterwards,
Ethylene (feed rate: 5 L / min) /
While continuously supplying a mixed gas of propylene (supply ratio: 5 L / min) / hydrogen (supply ratio: 0.5 L / min), the concentration of Al ₂ (C ₂ H ₅ ) ₃ Cl ₃ as a polymerization catalyst was reduced to 0. 1.85 mL of a 0.81 mol / L hexane solution
(Al ₂ (C ₂ H ₅ ) ₃ Cl ₃ 1.5 mmol) was added, and then 1.5 mL of a hexane solution having a VCl ₄ concentration of 0.10 mol / L (VCl ₄ 0.15 mmol) was added. A copolymerization reaction of ethylene, propylene and 5-methyl-5-carboxy-bicyclo [2.2.1] -2-heptene was performed at 20 ° C. for 20 minutes.

A demasking treatment was performed by adding a methanol solution containing 40 mmol of oxalic acid to the obtained polymer solution and stirring for 10 minutes. Next, after adding 1 L of water to the polymer solution and stirring for 10 minutes, only the polymer solution (organic layer) is recovered, and the polymer solution is washed three times with 1 L of water to remove residual oxalic acid. And the like. Then, the solvent was removed by blowing steam into the polymer solution. Thereafter, a solid content was separated from the obtained slurry, and the solid content was dried by a heating roll to obtain 16.5 g of a solid functional group-containing olefin-based copolymer. No odor was recognized in the functional group-containing olefin copolymer obtained above.

When the functional group-containing olefin copolymer was analyzed, the content of the structural unit derived from ethylene was 56.1 mol%, and the content of the structural unit derived from propylene was 43.7 mol%. The content ratio of the structural unit derived from -methyl-5-carboxy-bicyclo [2.2.1] -2-heptene was 0.2 mol%. The intrinsic viscosity [η] measured in decalin at 135 ° C. was 1.7 dl / g, and the weight average molecular weight Mw in terms of polystyrene measured by gel permeation chromatography was 1 dl / g.
The polymer had a number average molecular weight Mn of 9.6 × 10 ⁴ and a polystyrene equivalent of 7.0 × 10 ⁴ . The glass transition temperature measured by a scanning differential thermal analyzer (DSC) was -57.
5 ° C.

The obtained functional group-containing olefin copolymer was pressed with an electric heating machine at 160 ° C. for 10 minutes, and the functional group-containing olefin copolymer was analyzed. The content ratio of structural units derived from -5-carboxy-bicyclo [2.2.1] -2-heptene is 0.2 mol%, which is equivalent to the value before the press treatment, and has excellent durability. Was confirmed. Further, the obtained functional group-containing olefin copolymer was subjected to a 90 ° peel test on a polyester film according to the peel test method of JIS Z 0237, and the peel strength (Newton / 2.5
cm) was 0.8.

Example 2 5-Methyl-5-carboxy
Masking of bicyclo [2.2.1] -2-heptene
In processing, Al_Two(C_TwoH_Five)_ThreeCl_ThreeInstead of
Al (i-C_FourH ₉)_ThreeExample 1 except that
In the same manner as described above, the functional group-containing olefin copolymer 15.0
g was obtained. To the obtained functional group-containing olefin copolymer
Analysis of the structural units derived from ethylene
Content is 70.0 mol%, structure derived from propylene
The content of the unit is 29.7 mol%, and 5-methyl-5-ca
Derived from ruboxy-bicyclo [2.2.1] -2-heptene
The resulting structural unit content was 0.3 mol%. Ma
The intrinsic viscosity [η] measured in decalin at 135 ° C. is
1.9 dl / g by gel permeation chromatography
Weight average molecular weight Mw of 17
000, polystyrene reduced number average molecular weight Mn is 7
It was 5,000. In addition, a scanning differential thermal analyzer (DS)
The glass transition temperature measured by C) is -52.0 ° C.
there were.

The obtained functional group-containing olefin copolymer was subjected to press treatment at 160 ° C. for 10 minutes using an electric heating press, and the functional group-containing olefin copolymer was analyzed. The content ratio of the structural unit derived from -5-carboxy-bicyclo [2.2.1] -2-heptene is 0.3 mol%, which is equivalent to the value before the press treatment, and has excellent durability. Was confirmed. Further, the obtained functional group-containing olefin copolymer was subjected to a 90 ° peel test on a polyester film according to the peel test method of JIS Z 0237, and the peel strength (Newton / 2.5
cm) was 1.0.

<Embodiment 3> In the masking process, 5
-Methyl-5-carboxy-bicyclo [2.2.1]-
The amount of 2-heptene used was changed from 2.5 mmol to 10.0 m.
mol and Al ₂ (C ₂ H ₅ ) ₃ Cl ₃
Was changed from 2.5 mmol to 10.0 mmol, and a functional group-containing olefin copolymer was used in the same manner as in Example 1 except that VOCl ₃ was used instead of VCl ₄ as a polymerization catalyst. 7 g were obtained. When the obtained functional group-containing olefin copolymer was analyzed, the content of structural units derived from ethylene was 56.8 mol%, and the content of structural units derived from propylene was 42.
The content of structural units derived from 4 mol% and 5-methyl-5-carboxy-bicyclo [2.2.1] -2-heptene was 0.8 mol%. The intrinsic viscosity [η] measured in decalin at 135 ° C. was 1.2 dl / g, the weight average molecular weight Mw in terms of polystyrene measured by gel permeation chromatography was 250,000, and the number average molecular weight Mn in terms of polystyrene was 100, 000. The glass transition temperature measured by a scanning differential thermal analyzer (DSC) was -53.3 ° C.

The obtained functional group-containing olefin copolymer was subjected to press treatment at 160 ° C. for 10 minutes using an electric heating press, and the functional group-containing olefin copolymer was analyzed. The content ratio of structural units derived from -5-carboxy-bicyclo [2.2.1] -2-heptene is 0.8 mol%, which is equivalent to the value before the press treatment, and has excellent durability. Was confirmed. Further, the obtained functional group-containing olefin copolymer was subjected to a 90 ° peel test on a polyester film according to the peel test method of JIS Z 0237, and the peel strength (Newton / 2.5
cm) was 0.8.

Comparative Example 1 Instead of 5-methyl-5-carboxy-bicyclo [2.2.1] -2-heptene, 5
16.5 g of a functional group-containing olefin copolymer was obtained in the same manner as in Example 1, except that -carboxy-bicyclo [2.2.1] -2-heptene was used. In the above, a strong odor was recognized in the obtained functional group-containing olefin copolymer. When the obtained functional group-containing olefin copolymer was analyzed, the content of structural units derived from ethylene was 56.8 mol%, the content of structural units derived from propylene was 43.0 mol%, and 5- The content ratio of the structural unit derived from carboxy-bicyclo [2.2.1] -2-heptene was 0.2 mol%. The intrinsic viscosity [η] measured in decalin at 135 ° C. is 1.8 dl / g, and the weight average molecular weight Mw in terms of polystyrene measured by gel permeation chromatography is 2 dl / g.
The polystyrene equivalent number average molecular weight Mn was 0.1 × 10 ⁴ , and 7.2 × 10 ⁴ . The glass transition temperature measured by a scanning differential thermal analyzer (DSC) was -57.
It was 0 ° C.

The obtained functional group-containing olefin copolymer was subjected to a press treatment at 160 ° C. for 10 minutes using an electric heating press, and the functional group-containing olefin copolymer was analyzed. The content of structural units derived from -bicyclo [2.2.1] -2-heptene is 0.1 mol%, which is extremely lower than the value before the press treatment and has low durability. Was confirmed.

<Comparative Example 2> Instead of 5-methyl-5-carboxy-bicyclo [2.2.1] -2-heptene, 5
Functional group-containing olefin-based copolymer in the same manner as in Example 1 except that the masking treatment and the demasking treatment were not performed using methyl carboxy-bicyclo [2.2.1] -2-heptene. As a result, the yield was 2.0 g, and it was confirmed that the polymerization reaction did not sufficiently proceed.

<Comparative Example 3> Instead of 5-methyl-5-carboxy-bicyclo [2.2.1] -2-heptene, 5
-Carboxy-bicyclo [2.2.1] -2-heptene tert-butyl ester was used, except that the masking treatment and the demasking treatment were not carried out in the same manner as in Example 1. Production was attempted, but no olefin copolymer was obtained, and it was confirmed that the polymerization reaction did not proceed.

<Comparative Example 4> An olefin compound was prepared in the same manner as in Example 1 except that neither 5-methyl-5-carboxy-bicyclo [2.2.1] -2-heptene nor a masking agent was used. A copolymer was produced. When the obtained olefin-based copolymer was analyzed, the content of structural units derived from ethylene was 56.8 mol%, and the content of structural units derived from propylene was 43.2 mol%.
Met. The intrinsic viscosity [η] measured in decalin at 135 ° C. was 1.75 dl / g. Further, the glass transition temperature measured by a scanning differential thermal analyzer (DSC) was -58.9 ° C. The obtained olefin copolymer was subjected to a 90 ° peel test on a polyester film in accordance with the peel test method of JIS Z 0237. The peel strength (Newton / 2.5 cm) was 0.1. Adhesion was extremely low as compared with the olefin copolymers according to Nos. 1 to 3.

Example 4 2000 mL of hexane and 5-methyl-5 were placed in a 3 L separable flask purged with nitrogen.
70 mL of a 0.5 mol / L hexane solution of -carboxy-bicyclo [2.2.1] -2-heptene (35 mmol of 5-methyl-5-carboxy-bicyclo [2.2.1] -2-heptene) was added. . Then, 42 mmol of Al (iso-C ₄ H ₉ ) ₃ was added while stirring this mixture.
By adding and reacting, a masking treatment of a carboxyl group in 5-methyl-5-carboxy-bicyclo [2.2.1] -2-heptene was performed. afterwards,
The obtained solution was added with 5-ethylidene-2-norbornene 2m.
1 and then ethylene (feed rate: 5 L / mi)
n) / propylene (supply amount: 5 L / min) / hydrogen (supply amount: 0.5 L / min) While continuously supplying a mixed gas, Al ₂ (C ₂ H ₅ ) ₃ Cl ₃ was used as a polymerization catalyst. 104 mL of 0.81 mol / L hexane solution (Al
₂ (C ₂ H ₅ ) ₃ Cl ₃ 84 mmol) and then add 24 ml of a 0.10 mol / L hexane solution of VCl ₄
L (2.4 mmol of VCl ₄ ) was added at 25 ° C.
Minute, ethylene, propylene, 5-methyl-5
A copolymerization reaction of -carboxy-bicyclo [2.2.1] -2-heptene and 5-ethylidene-2-norbornene was performed.

630 mmol was added to the obtained copolymer solution.
Was removed by adding a butanol solution containing lactic acid and stirring for 10 minutes. Next, after adding 1 L of water to the copolymer solution and stirring for 10 minutes, only the copolymer solution (organic layer) is recovered, and the copolymer solution is washed three times with 1 L of water to obtain a residual solution. Lactic acid and the like were removed. Then, the solvent was removed by blowing steam into the copolymer solution. Then, the solid content is separated from the obtained slurry,
This was dried by a heating roll to obtain 30 g of a solid functional group-containing olefin copolymer.
This functional group-containing olefin copolymer is referred to as a “copolymer (A
1) ". No odor was observed in the copolymer (A1).

When the copolymer (A1) was analyzed, the content of the structural unit derived from ethylene was 64.7.
Mol%, the content of structural units derived from propylene is 3
3 mol%, the content of structural units derived from 5-methyl-5-carboxy-bicyclo [2.2.1] -2-heptene is 1.0 mol%, and the structure derived from 5-ethylidene-2-norbornene The content ratio of the unit was 1.3 mol%. The intrinsic viscosity [η] of the copolymer (A1) measured in decalin at 135 ° C. was 1.77 dl / g,
The polystyrene equivalent weight average molecular weight Mw measured by gel permeation chromatography was 18.7 × 10 ⁴ , and the polystyrene equivalent number average molecular weight Mn was 8.2 × 10 ⁴ . Further, the glass transition temperature measured by a scanning differential thermal analyzer (DSC) was -47.4 ° C.

100 weight of the copolymer (A1) and carbon black (trade name: Sheets S manufactured by Tokai Carbon Co., Ltd.)
O) 50 parts by weight, stearic acid 1 part by weight, and process oil (trade name: Fukkol 205, manufactured by Fujikosan Co., Ltd.)
0N) and 10 parts by weight were kneaded for 180 seconds under the conditions of a rotation speed of 60 rpm and a temperature of 50 ° C. by a Labo Plastomill having a content of 250 mL. 5 parts by weight of zinc oxide, 1 part by weight of tetramethylthiuram disulfide as a vulcanization accelerator, 5 parts by weight of mercaptobenzothiazole, and 0.5 part by weight of sulfur are added to the obtained kneaded product, and the mixture is maintained at 50 ° C. The rubber composition was obtained by kneading for 5 minutes using a 10-inch roll machine.

<Examples 5 to 7> 5-Methyl-5-carboxy-bicyclo [2.2.1] -2-heptene and 5
-Functional group content in which each structural unit was contained in the proportions shown in Table 1 below in the same manner as in Example 4 except that the amount of ethylidene-2-norbornene was changed and the supply amounts of ethylene and propylene were changed. An olefin copolymer was produced. The resulting functional group-containing olefin copolymer,
"Copolymer (A2)" and "Copolymer (A3)" respectively
And "Copolymer (A4)". Intrinsic viscosity [η] of the obtained copolymers (A2) to (A4) measured in decalin at 135 ° C., weight average molecular weight Mw in terms of polystyrene measured by gel permeation chromatography, number average in terms of polystyrene Table 1 shows the molecular weight Mn and the glass transition temperature measured by a scanning differential thermal analyzer (DSC). Instead of copolymer (A1), copolymer (A2), copolymer (A3) and copolymer (A4)
A rubber composition was obtained in the same manner as in Example 4, except for using.

Example 8 The amount of 5-methyl-5-carboxy-bicyclo [2.2.1] -2-heptene was changed without using 5-ethylidene-2-norbornene, and ethylene and propylene were used. A functional group-containing olefin copolymer containing structural units in the proportions shown in Table 1 below was produced in the same manner as in Example 4 except that the supply amount was changed. This functional group-containing olefin copolymer is referred to as “copolymer (A5)”. Intrinsic viscosity [η] of the obtained copolymer (A5) measured in decalin at 135 ° C., weight average molecular weight Mw in terms of polystyrene measured by gel permeation chromatography, number average molecular weight Mn in terms of polystyrene, scanning differential heat Table 1 shows the glass transition temperature measured by an analyzer (DSC). Copolymer (A1)
Instead of 100 parts by weight, 10 parts by weight of the copolymer (A5) and 90 parts by weight of an ethylene / propylene / 5-ethylidene-2-norbornene copolymer (hereinafter, referred to as “copolymer (C1)”) are used. A rubber composition was obtained in the same manner as in Example 4 except for the fact that the rubber composition was used.

In the above, the copolymer (C1) has a structural unit derived from ethylene of 65.3 mol%, a structural unit derived from propylene of 33.6 mol%, and a structural unit derived from 5-ethylidene-2-norbornene. 1.1 mol% of structural units
The intrinsic viscosity [η] measured in decalin at 135 ° C. is 1.75 dl / g, and the weight average molecular weight Mw in terms of polystyrene measured by gel permeation chromatography is 1
7.3 × 10 ⁴ and polystyrene reduced number average molecular weight Mn of 7.5 × 10 ⁴ . Further, the copolymer (A5)
10 parts by weight and 90 parts by weight of the copolymer (C1) were kneaded to prepare a copolymer mixture, and the intrinsic viscosity [η] of the copolymer mixture in decalin at 135 ° C. was measured. It was 58 dl / g. The proportion of each structural unit in the copolymer mixture was 64.9 mol% for the structural unit derived from ethylene, 34 mol% for the structural unit derived from propylene, and 5-methyl-5-carboxy-bicyclo [2 2.2.1] -2-heptene-derived structural unit is 0.1 mol%, and 5-ethylidene-2-norbornene-derived structural unit is 1.0 mol%.

<Comparative Examples 5 to 7> Without using 5-methyl-5-carboxy-bicyclo [2.2.1] -2-heptene, the amount of 5-ethylidene-2-norbornene was changed, and ethylene and Except that the supply amount of propylene was changed, an olefin copolymer having no functional group was produced in the same manner as in Example 4 in which each structural unit was contained at the ratio shown in Table 1 below. The obtained olefin-based copolymer was referred to as “copolymer (X1)” and “copolymer (X
2) "and" Copolymer (X3) ". Intrinsic viscosity [η] of the obtained copolymers (X1) to (X3) measured in decalin at 135 ° C., weight average molecular weight Mw in terms of polystyrene measured by gel permeation chromatography, number average in terms of polystyrene Molecular weight Mn,
Table 1 shows the glass transition temperature measured by a scanning differential thermal analyzer (DSC). Instead of the copolymer (A1),
A rubber composition was obtained in the same manner as in Example 4, except that the copolymer (X1), the copolymer (X2) and the copolymer (X3) were used.

[0088]

[Table 1]

[Evaluation of Rubber Composition] For each of the rubber compositions obtained in Examples 4 to 8 and Comparative Examples 5 to 7, a roll winding test, an adhesion test and a tensile test were carried out as follows. , Hardness test and DIN abrasion test. For the tensile test, the hardness test and the DIN abrasion test, each of the rubber compositions was pressed at 150 kgf / cm ² with a hot press machine heated to 160 ° C.
By heating for 0 minutes to produce a vulcanized rubber sheet,
A test piece was prepared from the vulcanized rubber sheet.

(1) Roll winding test: Examples 4 to 8
And about each of the rubber compositions obtained in Comparative Examples 5 to 7, the roll interval was masticated by a roll machine set to 1 mm, 2 mm and 3 mm, and the wrapping property of the rubber composition on the rolls was as follows. The evaluation was performed according to the five-point standard. 5. The rubber band is completely adhered to the surface of one roll, and the bank rotates smoothly. 4. From the bank to the top of one roll, the rubber band occasionally separates from the surface of one roll. 3. Between the bank and the top of one roll, the rubber band frequently separates from the surface of one roll. 2. The rubber band hangs down without sufficiently adhering to the surface of one of the rolls, and mastication cannot be performed unless a hand is attached to the rubber band. 1. The rubber band hangs down without adhering to the surface of one of the rolls, and mastication cannot be performed unless a hand is attached to the rubber band.

(2) Adhesion: Each of the rubber compositions obtained in Examples 4 to 8 and Comparative Examples 5 to 7 was subjected to JIS.
An adhesion test was performed on a metal plate in accordance with K6256 to examine the state of peeling or destruction. However, as a metal plate (cast iron), a primer (manufactured by Toyo Chemical Laboratory)
After coating the product name: Metaloc P) and drying it for 30 minutes or more, further apply an adhesive (manufactured by Toyo Chemical Laboratory) to its surface
(Product name: Metaloc FC) was used and dried for 30 minutes or more.

(3) Tensile test: Tensile strength T _B (MPa) and elongation at break E in accordance with JIS K6301
_B (%) was measured. (4) Hardness test: Durometer hardness was measured according to JIS K6253. (5) DIN abrasion test: A wear resistance index was measured in accordance with JIS K6264. The results are shown in Table 2 above.

[0093]

[Table 2]

As is evident from Table 2, the rubber compositions according to Examples 4 to 8 are excellent in workability such as roll wrapping property, and have good adhesion to metal, mechanical strength and abrasion resistance. An excellent elastomer is obtained. On the other hand, the elastomers obtained from the rubber compositions according to Comparative Examples 5 to 7 had low processability and low metal adhesion.

[0095]

As described above, according to the olefin copolymer having a functional group of the present invention, the adhesiveness and compatibility with other materials are high, the coating property and the printability are high, and excellent. An elastomer having high durability and no or little odor is obtained. Further, according to the production method of the present invention, an elastomer having high adhesiveness and compatibility with other materials, high coatability and printability, and also having excellent durability and further having no or little odor can be obtained. An olefin-based copolymer having a functional group can be reliably produced. In addition, according to the rubber composition of the present invention, the adhesiveness and compatibility with other materials are high, the coatability and printability are high, and further, it has excellent durability, mechanical properties and abrasion resistance, Furthermore, an elastomer having no or little odor can be obtained, and a rubber molded article can be produced at low cost. The elastomer obtained by the present invention is suitable as a material for automobile parts such as weather strips and sponges, mechanical parts, electronic parts, civil engineering materials and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) C08F 232: 00) C08F 232: 00) (72) Inventor Katsutoshi Sawada 2-11-24 Tsukiji 2-chome, Chuo-ku, Tokyo No. within JSR Co., Ltd. (72) Inventor Akira Tsuji F-term in JSR Co., Ltd. 2--11-24 Tsukiji, Chuo-ku, Tokyo (reference) 4J002 BB02W BB02X BB15W BB15X DA046 DD006 EK066 EV076 EV136 EV166 EV346 FD146 FD150 GM00 GN00 GQ00 4J028 AA01A AB00A AB01A AC04A AC24A AC27A AC28A AC32A BA00A BA01B BB00A BB01B BC09B BC15B BC16B BC17B BC19B BC24B BC27B CA02C CA16A CA28A CB27C CB42C CB53C CB62C CB92C EB02 EB03 EB04 EB05 EB07 EB08 EB09 EB10 EB15 EB16 EB17 EB18 EC04 EC06 FA09 4J100 AA02P AA03Q AA04Q AA07Q AA15Q AA16Q AA17Q AA19Q AA21Q AB02Q AB03Q AR09R AR11R AR22S AR36R AS11S AS15S AU 21S BA03R BA16R BA20R BA29R BA30R BA35R BC04S CA04 CA05 DA09 DA25 FA10 JA28 JA43 JA67

Claims (13)

[Claims] 1. A structural unit (a) derived from ethylene, a structural unit (b) derived from an α-olefin having 3 to 12 carbon atoms, and a structural unit (c) represented by the following general formula (1) ), Wherein the intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.
An olefin copolymer having a functional group, which is 1 to 10 dl / g. Embedded image [In the formula, X ¹ and X ² each independently represent a hydrogen atom, a hydrocarbon group or the following specific functional group, and X ¹
And at least one of X ² is the following specific functional group. R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ¹ and R ² are bonded to a carbon atom to which the following specific functional group is bonded. Is a hydrocarbon group having 1 to 10 carbon atoms. n shows the integer of 0-2. Specific functional group: a hydroxyl group or a hydrocarbon group having a hydroxyl group bonded thereto,
A carboxyl group or a hydrocarbon group having a carboxyl group bonded thereto, a primary amino group, a secondary amino group or a hydrocarbon group having these amino groups bonded thereto, or a quaternary ammonium salt thereof, or an active hydrogen bonded to a nitrogen atom An amide group having at least one or a hydrocarbon group having the amide group bonded thereto, and -C composed of X ¹ and X ^2.
A functional group selected from the group consisting of imide groups represented by O-NH-CO-. ] 2. A structural unit (a) derived from ethylene, a structural unit (b) derived from an α-olefin having 3 to 12 carbon atoms, and represented by the general formula (1) according to claim 1. And a structural unit (d) derived from a non-conjugated diene, and have an intrinsic viscosity [η] of 0. 13 measured in decalin at 135 ° C.
An olefin copolymer having a functional group, which is 1 to 10 dl / g. 3. The structural unit (a) derived from ethylene is 5
To 90 mol%, the structural unit (b) derived from an α-olefin having 3 to 12 carbon atoms is 5 to 60 mol%, and the general formula (1)
0.01 to 30 mol% of the structural unit (c) represented by the formula, and 0 to 12 mol% of the structural unit (d) derived from the non-conjugated diene
The olefin-based copolymer having a functional group according to claim 1 or 2, wherein 4. The structural unit (c) is a compound represented by the general formula (1) wherein only ^one of X ¹ and X ² is a specific functional group, and is bonded to a carbon atom to which the specific functional group is bonded. 4. The olefin copolymer having a functional group according to claim 1, wherein R ¹ or R ² is a hydrocarbon group having 1 or 2 carbon atoms. 5. The structural unit (c) is a compound represented by the general formula (1) wherein only ^one of X ¹ and X ² is a specific functional group, and is bonded to a carbon atom to which the specific functional group is bonded. R ¹ or R ² is a hydrocarbon group having 1 or 2 carbon atoms, and the other of X ¹ and X ² is a hydrogen atom, and is bonded to a carbon atom to which the hydrogen atom is bonded R
^The olefin copolymer having a functional group according to any one of claims 1 to 3, wherein ¹ or R ² is a hydrogen atom. 6. The olefin copolymer having a functional group according to claim 1, wherein the glass transition temperature is -90 to 50 ° C. 7. A functional group-containing cyclic olefin represented by the following general formula (2), and a cyclic group 2 or 12 or a periodic table 1
Reacting an organometallic compound with a metal selected from Group 3; the resulting reaction product; ethylene;
An olefin copolymer having a functional group, characterized by comprising a step of polymerizing an α-olefin of the formula (I) and a non-conjugated diene used as necessary in the presence of a catalyst comprising a transition metal compound and an organoaluminum compound. Manufacturing method of coalescence. Embedded image [In the formula, X ¹ and X ² each independently represent a hydrogen atom, a hydrocarbon group or the following specific functional group, and X ¹
And at least one of X ² is the following specific functional group. R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ¹ and R ² are bonded to a carbon atom to which the following specific functional group is bonded. Is a hydrocarbon group having 1 to 10 carbon atoms. n shows the integer of 0-2. Specific functional group: hydroxyl group or hydrocarbon group with hydroxyl group, carboxyl group or hydrocarbon group with carboxyl group, primary amino group, secondary amino group, or hydrocarbon with these amino groups bonded Or quaternary ammonium salts thereof, an amide group having at least one active hydrogen bonded to a nitrogen atom or a hydrocarbon group bonded to this amide group, and X ¹ and X
Functional groups selected from the group consisting of an imide group represented by -CO-NH-CO- constructed from ^2. ] 8. The olefin group having a functional group according to claim 7, wherein the organometallic compound of a metal selected from Groups 2, 12, and 13 of the periodic table is an organoaluminum compound. A method for producing a copolymer. 9. An organometallic compound based on a metal selected from Group 2 of the Periodic Table, Group 12 and Group 13 of the periodic table, wherein 1 equivalent of a specific functional group in the functional group-containing cyclic olefin represented by the general formula (2) is used. 9. The method for producing an olefin-based copolymer having a functional group according to claim 7, wherein the olefin-based copolymer is used in a ratio of 0.8 equivalent or more with respect to. 10. A composition comprising (A) the olefin copolymer having a functional group according to any one of claims 1 to 6, and (B) a vulcanizing agent and / or a crosslinking agent. A rubber composition comprising: 11. The method according to claim 10, wherein (C) an olefin copolymer having no functional group is contained.
3. The rubber composition according to item 1. 12. The olefin copolymer having no functional group (C) has a structural unit derived from ethylene and a carbon number of 3 to 3.
A copolymer comprising a structural unit derived from an α-olefin of 12 and / or a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 to 12 carbon atoms and a non-conjugated diene. The rubber composition according to claim 11, which is a copolymer comprising a structural unit. 13. (A) the olefin copolymer having a functional group according to any one of claims 1 to 4,
The rubber composition according to claim 11 or 12, wherein the weight ratio of the (C) functional group-free olefin copolymer is 1:99 to 99: 1.