JPH1180269A - Unsaturated copolymer, preparation thereof and composition containing said copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an α-olefin/conjugate diene copolymer having an excellent cold resistance, an excellent crosslinking efficiency and an excellent modifying efficiency. SOLUTION: A copolymer comprises a 2-12C α-olefin and a conjugate diene monomer of the formula (wherein R<2> stands for a hydrogen atom, a 1-8C alkyl or aryl group), in which copolymer (a) a 1, 2 adduct (including a 3, 4 adduct) derived from the conjugate diene monomer forms a double bond in a side chain of the copolymer, a 1, 4 adduct forms a double bond in a principal chain and the ratio of the double bonds in side chains derived from 1, 2 adducts to the double bonds in principal chains derived from 1, 4 adducts is 10/90-99/1, (b) the principal chains of the copolymer contain five-member rings, and (c) the ratio of double bonds of all adducts to the five-member rings (the total of double bonds of all adducts/five-member rings) is 20/80-90/10.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an unsaturated copolymer, a method for producing the same, and a composition containing the copolymer. More specifically, the present invention relates to weather resistance, heat resistance, cold resistance, crosslinking efficiency, and oil resistance. The present invention relates to an unsaturated copolymer excellent in such properties, a method for producing the same, and a composition containing the copolymer.

[0002]

BACKGROUND OF THE INVENTION Conventionally, butadiene rubber (B
R), isoprene rubber (IR), styrene / butadiene rubber (SBR), and other soft resins are used for molded articles such as tires. Such soft resins are used for weather resistance and heat resistance. When used for various molded products such as automobile parts that require cold resistance, etc., the resin is oxidized and deteriorated, and the physical properties tend to decrease, and the weather resistance, heat resistance,
Further improvement in cold resistance is required.

[0003] When a soft resin molded article is used under severe conditions as described above, the deterioration of physical properties is caused by the fact that 2
This is because the heavy bond portion is oxidized and deteriorated.
It is preferable to reduce the number of heavy bonds as much as possible.

When a soft resin such as SBR, EPR, ethylene / propylene / non-conjugated diene copolymer (EPT) is used as a rubber molded product, peroxide crosslinking, radical modification and the like are carried out. In addition, an inexpensive elastomer having a high reaction efficiency, a small decrease in physical properties after the reaction, and the like is required.

[0005] Particularly, in peroxide crosslinking, if the crosslinking efficiency is low, a large amount of peroxide is required, so that the main chain of the soft resin may cause a decomposition reaction. In addition, when a large amount of peroxide is used, a problem may occur in that a peroxide or the like remains in the obtained crosslinked product.

[0006] In the conventional EPT and the like, the crosslinking efficiency and the like are not yet sufficient, and particularly when peroxide crosslinking is performed, the physical properties after crosslinking may not be sufficient, and the compression set and the like are further improved. Is required.

The inventors of the present invention have conducted intensive studies to solve such problems, and as a result, they have found that an α-olefin, a specific conjugated diene monomer and, if necessary, an aromatic vinyl compound are copolymerized. A random copolymer obtained by the above method, which has a large content of a diene-derived 1,2 adduct (in this specification, sometimes referred to as a 1,2 adduct including a 3,4 adduct). Double bonds are present in the main chain and side chains in the polymer at a specific ratio, and the copolymer has a 5-membered ring structure, and the double bond and the 5-membered ring structure are specified. The unsaturated copolymer present in a quantitative ratio is compatible, weather-resistant, heat-resistant,
The inventors have found that the present invention has excellent cold resistance, low glass transition temperature, excellent cold resistance, excellent cross-linking efficiency and modification efficiency, can be industrially produced efficiently, and the like, and have completed the present invention.

The following literatures are known for ethylene / 1,3-butadiene copolymer. `` Journal of Polymer Science: Part B: Polymer Phy
Sics, Vol. 26, 2113-2126 (1988) ", describes an ethylene / 1,3-butadiene copolymer produced using a supported Ziegler catalyst. According to this document, the copolymer has a phthalocyanine-phthalocyanine bond and is block copolymerizable. The activity of the catalyst is as low as 10 kg / gTi or less. The butadiene unit is mainly a trans 1,4 adduct, and methyl methacrylate (MMA) or maleic anhydride is grafted to a double bond site in the adduct to produce a graft such as MMA. ing.

[0009] Makromol.Chem. 179, 2173-2185 (197
8) "describes an ethylene / 1,3-butadiene copolymer produced using a vanadium catalyst. According to this document, the 1,2-butadiene 1,2 adduct is hardly contained, and the trans 1,4 adduct is mainly used, and the catalyst has low activity.

[0010] Polymer Bulletin 31, 271-278 (199
3) "describes an ethylene / propylene / 1.3-butadiene copolymer produced using a Ziegler catalyst. According to this document, it was confirmed that 1,3-butadiene 1,2 adduct, 1,4 adduct and propylene unit were present in the copolymer, but the activity of the catalyst used was Low activity of 10 kg / gTi or less.

The catalysts described in (1) to (4) have low activity, and the obtained copolymer does not have a 5-membered ring structure and a 3-membered ring structure. In addition, the copolymer described in the above literature does not have a 1,2 adduct of butadiene.

[0012] "Makromol. Chem. 192, 2591-2601 (199
1) "describes an ethylene / 1.3-butadiene copolymer and an ethylene / propylene / 1.3-butadiene copolymer produced using a biscyclopentadienyl-type metallocene catalyst. According to this document, the copolymer is:
Although it has a 1,4-adduct and a 5-membered ring structure,
It does not have a 1,2 adduct or a three-membered ring structure. Also, the catalytic activity is as low as 5 kg / mMZr.

International Patent Application Publication: WO 88/046
72 (filed 1986; corresponding US Pat.
2, filed March 2, 1993, corresponding European patent EP0
275676B1, filed Sep. 7, 1994) describes an ethylene / 1.3-butadiene copolymer produced using a biscyclopentadienyl-type metallocene catalyst. According to this publication, the copolymer comprises 1,2
Although the adducts, 1,4-adducts, and those having a 5-membered ring structure have no description of their quantitative ratios, the amount of particularly useful 1,2-adduct is very small in the Examples, and the 3-membered No mention is made of the ring structure. The activity of the catalyst is 1 kg / mMZrh
Very low activity with:

[0014]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art as described above, and is excellent in compatibility with other polar group-containing resins, weather resistance, heat resistance and cold resistance. It is an object of the present invention to provide an unsaturated copolymer having excellent low temperature, low glass transition temperature, excellent cold resistance, excellent crosslinking efficiency and modification efficiency, and excellent economic efficiency.

Another object of the present invention is to provide a method by which an unsaturated copolymer having the above-mentioned excellent properties can be efficiently and industrially produced. Another object of the present invention is to provide a modified product of the above unsaturated copolymer.

[0016]

SUMMARY OF THE INVENTION The first unsaturated copolymer according to the present invention (also referred to simply as "copolymer") has 2 to 12 carbon atoms.
(A) and a conjugated diene monomer represented by the following formula (I-a), wherein (a) the conjugated diene monomer (I- The 1,2 adduct (including the 3,4 adduct) derived from a) forms a double bond in the side chain in the copolymer, and the 1,4 adduct is Has a double bond in the main chain thereof, and the ratio of the double bond of the side chain derived from the 1,2 adduct to the double bond of the main chain derived from the 1,4 adduct (1,2 (The side chain double bond derived from the adduct / 1, the main chain double bond derived from the 1,4 adduct) is 10/90 to 99/1, and (b) the 5-membered ring in the main chain of the copolymer. (C) the ratio of the double bond to the 5-membered ring of the all adducts (total double bond of all adducts / 5-membered ring)
Is 20/80 to 90/10.

[0017]

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[In the formula (Ia), R ² is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group. ].
In the first unsaturated copolymer, the conjugated diene monomer is desirably 1,3-butadiene.

In a preferred embodiment of the present invention, the first unsaturated copolymer contains the above-mentioned α-olefin,
Ethylene alone or ethylene and carbon number 3 ~
In this case, ethylene / α-olefin having 3 to 12 carbon atoms (molar ratio) is desirably 99/1 to 40/60.

In a preferred embodiment of the present invention, the copolymer preferably further has a cyclopropane ring in the main chain. In a preferred embodiment of the present invention, the copolymer preferably contains a total of 0.01 to 30% by mole of structural units derived from a conjugated diene monomer.

In a preferred embodiment of the present invention, the copolymer has an iodine value of 1 to 50 g / 100 g,
The intrinsic viscosity [η] measured in decalin at 5 ° C. is 0.0
It is preferably in the range of 1 to 10 dl / g, and the glass transition temperature Tg is preferably 25 ° C. or less.

In the first modified unsaturated copolymer according to the present invention, the above-mentioned copolymer is selected from the group consisting of (i) an unsaturated carboxylic acid or a derivative thereof, and (ii) an aromatic vinyl compound. It is graft-modified with at least one compound, and the amount of grafting of these unsaturated carboxylic acids or derivatives thereof is in the range of 0.01 to 30% by weight.

The first unsaturated copolymer-based elastomer composition according to the present invention is characterized by containing (a) the copolymer described above and (b) a crosslinking agent and / or a filler. I have.

In the present invention, the above unsaturated copolymer is obtained by combining an α-olefin having 2 to 12 carbon atoms with at least one conjugated diene monomer represented by the above formula (Ia). When the catalyst is produced by copolymerization with a catalyst in the presence of a catalyst, the above-mentioned catalyst is used as the above component (a) and one or more components selected from the following components (b), (c) and (d). And at least one catalyst system comprising a compound. (A): transition metal complex represented by the following formula (II) or formula (III)

[0025]

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[In the formulas (II) and (III), M is Ti, Z
r, Hf, Nd, Sm or Ru, wherein Cp1 and Cp2 are a cyclopentadienyl group which is π-bonded to M,
X ¹ and X ² are an anionic ligand or a neutral Lewis base ligand, and Y is a nitrogen atom, an oxygen atom, a phosphorus atom, or a sulfur atom. And Z is a C, O, B, S, Ge, Si or Sn atom or a group containing these atoms. (B): a compound that reacts with the transition metal M in the component (a) to form an ionic complex (c): an organoaluminum compound (d): alumoxane.

The second unsaturated copolymer according to the present invention comprises:
An α-olefin having 2 to 12 carbon atoms and the following formula (I-b)
And a conjugated diene monomer represented by the formula:

[0028]

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[In the formula (Ib), R ¹ has 1 to 8 carbon atoms.
Is an alkyl group or an aryl group. In a preferred embodiment of the present invention, the second unsaturated copolymer is formed from an α-olefin having 2 to 12 carbon atoms and a conjugated diene monomer represented by the above formula (Ib). (A) In the copolymer, a 1,2 adduct (including a 3,4 adduct) derived from the conjugated diene monomer (Ib) is a copolymer And the 1,4 adduct has a double bond in the main chain of the copolymer, and has a side chain derived from the 1,2 adduct. Of the main chain derived from the double bond and the 1,4 adduct
Heavy bond ratio (side chain double bond derived from 1,2 adduct /
Main chain double bond derived from 1,4 adduct) is 5/95 to 9
It is preferably 9/1.

In a preferred embodiment of the present invention, the second unsaturated copolymer comprises an α-olefin having 2 to 12 carbon atoms and a conjugated diene monomer represented by the above formula (Ib) And (a) a copolymer derived from the conjugated diene monomer (Ib) in the copolymer.
The diadduct (including the 3,4 adduct) forms a double bond in the side chain of the copolymer, and the 1,4 adduct has a double bond in the main chain of the copolymer. And the ratio of the double bond of the side chain derived from the 1,2 adduct to the double bond of the main chain derived from the 1,4 adduct (side chain 2 derived from the 1,2 adduct)
Heavy bond / 1,4-adduct-derived main chain double bond) is 5 /
(B) having a five-membered ring in the main chain of the copolymer, and (c) a ratio of the double bond to the five-membered ring of all the adducts (total of all adducts). (Double bond / 5-membered ring) is 20 / 80-
It is desirably 90/10.

In the second unsaturated copolymer,
Desirably, the conjugated diene monomer is isoprene. In the present invention, the α-olefin is ethylene alone, or ethylene and C 3 to C 1.
2, in which case ethylene / α-olefin having 3 to 12 carbon atoms (molar ratio)
Is preferably from 99/1 to 40/60.

In the second unsaturated copolymer,
It is desirable that the main chain of the copolymer further has a cyclopropane ring. In the second unsaturated copolymer, the total number of constituent units derived from the conjugated diene monomer is from 0.01 to 0.01.
Desirably, it is contained in an amount of 30 mol%.

In a preferred embodiment of the present invention, the second unsaturated copolymer has an iodine value of 1 to 50 g / 100.
the intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.01 to 10 dl / g, and DS
It is desirable that the glass transition temperature Tg measured at C is 25 ° C. or less.

The second unsaturated copolymer elastomer composition according to the present invention comprises (a) the second unsaturated copolymer (copolymer) described above, (b) a crosslinking agent and / or Alternatively, it is characterized by containing a filler.

In the present invention, the second unsaturated copolymer is obtained by combining an α-olefin having 2 to 12 carbon atoms with at least one conjugated diene monomer represented by the above formula (Ib). When producing by co-polymerizing with the body in the presence of a catalyst,
It is characterized by using the same catalyst system as described above.

The third unsaturated copolymer (unsaturated random copolymer) according to the present invention comprises an α-olefin having 2 to 12 carbon atoms, an aromatic vinyl compound, and a conjugated diene monomer. It is characterized by consisting of.

In a preferred embodiment of the present invention, the third unsaturated copolymer comprises an α-olefin having 2 to 12 carbon atoms, an aromatic vinyl compound and a conjugated diene unit represented by the following formula (I). And (a) a 1,2 adduct (including a 3,4 adduct) derived from the conjugated diene monomer (I) in the copolymer. The double bond is formed in the side chain in the polymer, and the 1,4 adduct forms a double bond in the main chain in the copolymer and is derived from the above 1,2 adduct. The ratio of the double bond of the side chain to the double bond of the main chain derived from the 1,4 adduct (side chain double bond derived from the 1,2 adduct / main chain 2 derived from the 1,4 adduct) (Heavy bond) is preferably from 10/90 to 99/1.

[0038]

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[In the formula (I), R ¹ and R ² are each independently a hydrogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms, and at least one of R ¹ and R ² is hydrogen. . ]. In a preferred embodiment of the present invention, the third unsaturated copolymer comprises an α-olefin having 2 to 12 carbon atoms, an aromatic vinyl compound, and a conjugated diene monomer represented by the above formula (I). (A) In the copolymer, 1,2 adducts (including 3,4 adducts) derived from the conjugated diene monomer (I) are contained in the copolymer. Has a double bond in the side chain of
Forming a double bond in the main chain of the copolymer,
The ratio of the double bond of the side chain derived from the 2 adduct to the double bond of the main chain derived from the 1,4 adduct (side chain double bond derived from the 1,2 adduct / 1,4 adduct) Main-chain double bond derived from
Is 10/90 to 99/1, (b) a 5-membered ring is present in the main chain of the copolymer, and (c) a double bond and 5
Ratio (total double bond of all adducts / 5-membered ring) to 20-membered ring
/ 80 to 90/10, and preferably contains the structural unit derived from the aromatic vinyl compound in an amount of 0.1 to 60 mol%.

In the present invention, the third unsaturated copolymer (copolymer) contains structural units derived from a conjugated diene monomer in a total amount of 0.01 to 30 mol%. Is desirable.

In the third unsaturated copolymer, the conjugated diene monomer is desirably 1,3-butadiene or isoprene. In the third unsaturated copolymer, the α-olefin is ethylene alone or a combination of ethylene and an α-olefin having 3 to 12 carbon atoms. Α-olefin (molar ratio) of from 99/1 to 4
It is preferably 0/60.

In the third unsaturated copolymer, the aromatic vinyl compound is preferably styrene.
In the third unsaturated copolymer, it is desirable to further have a cyclopropane ring in the main chain of the copolymer.

In the third unsaturated copolymer, the iodine value of the copolymer is 1 to 50 g / 100 g, and 135
C. The intrinsic viscosity [η] measured in decalin at 0.01 ° C. is 0.01
And the glass transition temperature Tg is 2
It is desirable that the temperature is 5 ° C. or less.

In the third unsaturated copolymer, DSC
It is desirable that the peak of the melting point (Tm) measured at 120 ° C. is 120 ° C. or less. The third modified copolymer according to the present invention is:
The third unsaturated copolymer is graft-modified with at least one compound selected from the group consisting of an unsaturated carboxylic acid or a derivative thereof and an aromatic vinyl compound, and the graft amount is 0.01%. -30% by weight.

The third unsaturated copolymer-containing elastomer composition according to the present invention contains (A) the third unsaturated copolymer described above and (B) a crosslinking agent and / or a filler. It is characterized by doing.

In the present invention, the third unsaturated copolymer is a copolymer of an α-olefin having 2 to 12 carbon atoms, an aromatic vinyl compound and a conjugated diene monomer represented by the above formula (I). In producing the compound by copolymerizing the compound with a catalyst in the presence of a catalyst, the same catalyst system as described above is used.

The crosslinked product according to the present invention is characterized in that the composition described above is crosslinked. In the present invention, the crosslinking agent in the composition is preferably an organic peroxide.

The film or sheet according to the present invention is characterized by comprising the above-mentioned crosslinked product. The unsaturated copolymer according to the present invention has excellent weather resistance, heat resistance, cold resistance, compatibility, oil resistance, etc., a low glass transition temperature, excellent cold resistance, and excellent crosslinking efficiency and modification efficiency, and It is also economical.

According to the method for producing an unsaturated copolymer according to the present invention, a copolymer having the above-mentioned various excellent properties can be produced efficiently and industrially. Further, the modified unsaturated copolymer according to the present invention has good compatibility with other elastomers or resins.

[0050]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the first, second, and third embodiments according to the present invention will be described.
And the third unsaturated copolymer (these are collectively referred to simply as “unsaturated copolymer”) will be specifically described.

[Unsaturated Copolymer] The first unsaturated copolymer according to the present invention (also simply referred to as “copolymer”).
Is at least one α-olefin having 2 to 12 carbon atoms and at least one conjugated diene monomer (I-
a) a copolymer comprising:

The second unsaturated copolymer according to the present invention comprises:
A copolymer comprising an α-olefin having 2 to 12 carbon atoms and at least one conjugated diene monomer (Ib) described below.

The third unsaturated copolymer (unsaturated random copolymer) according to the present invention comprises an α-olefin having 2 to 12 carbon atoms, an aromatic vinyl monomer and at least one And a conjugated diene monomer (I). This conjugated diene monomer (I) is the conjugated diene monomer (Ia) and / or (Ib).

The α-olefin used for preparing such an unsaturated copolymer has 2 to 1 carbon atoms.
It is not particularly limited as long as it is within the range of 2, even if it is linear,
It may have a branch.

Specific examples of such α-olefin include ethylene, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-heptene, 1-
Octene, 1-nonene, 1-decene, 1-undecene,
1-dodecene, 3-methyl-1-butene, 3-methyl-
1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene,
4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene and the like can be mentioned. These α-olefins can be used alone or in combination of two or more.

In particular, when one kind of the above-mentioned α-olefin is used alone, those having 2 to 5 carbon atoms are preferable, and ethylene is particularly preferable. When two or more of the above α-olefins are used in combination, a combination of ethylene and another α-olefin is preferred, and the molar ratio (ethylene / α-olefin having 3 or more carbon atoms) is 99/1 to 99/1. 4
The molar ratio is preferably 90/10 to 60/40 in consideration of the fact that the glass transition temperature Tg of the obtained copolymer can be lowered. Is preferably 85/15 to 70/30. When the obtained copolymer is used as an elastomer, particularly, the molar ratio is 80/20 to 5
5/45 is desirable.

In the present invention, the conjugated diene monomer includes
What is represented by the following formula (I) is used.

[0058]

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[In the formula (I), R ¹ and R ² are each independently a hydrogen atom, an alkyl group or an aryl group having 1 to 8 carbon atoms, and at least ^one of R ¹ and R ² is hydrogen. is there. The conjugated diene monomer (I) may be either aromatic or aliphatic, and is not particularly limited.

Examples of the conjugated diene monomer (I) include, for example, 1,3-butadiene, 1,3
-Pentadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 1-phenyl-1,
3-butadiene, 1-phenyl-2,4-pentadiene, isoprene, 2-ethyl-1,3-butadiene, 2
-Propyl-1,3-butadiene, 2-butyl-1,3
-Butadiene, 2-pentyl-1,3-butadiene, 2
-Hexyl-1,3-butadiene, 2-heptyl-1,
3-butadiene, 2-octyl-1,3-butadiene,
2-phenyl-1,3-butadiene and the like. The conjugated diene monomers can be used alone or in combination of two or more.

In particular, in the first unsaturated copolymer, a conjugated diene monomer represented by the following formula (Ia) is used.

[0062]

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[In the formula (Ia), R ² is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group. The conjugated diene monomer (Ia) may be either aromatic or aliphatic, and is not particularly limited.

Examples of such a conjugated diene monomer (Ia) include, for example, 1, 1
3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 1-phenyl-1,3-butadiene, 1-phenyl-2,4-pentadiene, and the like. Can be Among these, 1,3-butadiene is particularly preferred because of its excellent copolymerizability and crosslinking efficiency.

In particular, in the case of the second unsaturated copolymer,
As the conjugated diene monomer, those represented by the following formula (Ib) are used.

[0066]

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[In the formula (Ib), R ¹ is a group having 1 to 8 carbon atoms.
Is an alkyl group or an aryl group. The conjugated diene monomer (Ib) may be any of an aromatic type and an aliphatic type, and is not particularly limited.

Specific examples of the conjugated diene monomer (Ib) include, among the above examples, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1, 3-butadiene, 2-butyl-1,3-butadiene, 2-pentyl-1,3-butadiene, 2-hexyl-1,3-butadiene, 2-heptyl-1,3-butadiene, 2-octyl-1, Examples thereof include 3-butadiene and 2-phenyl-1,3-butadiene. Of these, isoprene is particularly preferred because of its excellent copolymerizability and crosslinking efficiency.

In the third unsaturated copolymer, the conjugated diene monomer (I) as described above can be used. In the above examples, 1,3-butadiene and isoprene are copolymerized. It is particularly preferable in terms of excellent properties.

The aromatic vinyl compound optionally used is a compound having only one carbon-carbon double bond (C = C) per one substituent bonded to an aromatic ring. As the compound, specifically, for example, styrene; o-methylstyrene, m-methylstyrene,
mono- or polyalkylstyrenes such as p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene; methoxystyrene,
Functional group-containing styrene derivatives such as ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene; 3-phenylpropylene, 4-phenylbutene, α -Methylstyrene and the like. Of these, styrene or 4-methoxystyrene is preferred.

These aromatic monomers can be used alone or in combination of two or more.

The first and second unsaturated copolymers (α-olefin / conjugated diene copolymer) according to the present invention are usually composed of a raw material α-olefin-derived structural unit; Adducts (including 3,4 adducts) and 1,4 adduct structural units; and preferably further have a 5-membered ring (cyclopentane ring) structural unit formed in the main chain. doing.

The third unsaturated copolymer (unsaturated terpolymer, α-olefin / aromatic vinyl compound / conjugated diene copolymer) according to the present invention is usually Α- of the same raw material as in the case of the first and second unsaturated copolymers
A olefin-derived structural unit; a conjugated diene-derived 1,2 adduct (including a 3,4 adduct) and a 1,4 adduct structural unit; preferably a 5-member formed in the main chain Structural unit derived from an aromatic vinyl compound in addition to the ring (cyclopentane ring).

Such an unsaturated copolymer according to the present invention may have a cyclopropane structural unit in addition to the above structure. In this specification, the 1,2 adduct and the 3,4 adduct are collectively referred to simply as 1,2 adduct. (A) In the copolymer of the present invention, the 1,2 adduct derived from the conjugated diene monomer forms a double bond in a side chain in the copolymer, and The adduct forms a cis or trans double bond in the main chain in the copolymer.

In the first unsaturated copolymer (first copolymer) according to the present invention, the double bond of the side chain derived from the 1,2 adduct and the main bond derived from the 1,4 adduct are obtained. The double bond of the chain is defined as the molar ratio (double bond of side chain derived from 1,2 adduct /
Main chain double bond derived from 1,4 adduct)
It is desirably present in an amount such that it is 99/1, preferably 12/88 to 90/10.

In the second unsaturated copolymer (second copolymer) according to the present invention, the above molar ratio (double bond of side chain derived from 1,2 adduct / 1,4 addition) 2 of the main chain derived from the body
Heavy bond) is 5/95 to 99/1, preferably 10/9
0-99 / 1, more preferably 20 / 80-90 / 10
It is desirable that it be present in such an amount that

In the third unsaturated copolymer (third copolymer) according to the present invention, the above molar ratio (double bond of side chain derived from 1,2 adduct / 1,4 addition) 2 of the main chain derived from the body
Heavy bond) is 5/95 to 99/1 (molar ratio), preferably 10/90 to 99/1. Further, for example, when R ¹ is a hydrogen atom and R ² is a hydrogen atom or an alkyl group as in butadiene, the above ratio is 12/88.
The ratio is more preferably from 20/80 to 90/10, for example, when R ¹ is an alkyl group and R ² is a hydrogen atom as in isoprene.

When the above-mentioned double bond (C = C) is present in each unsaturated copolymer at such a quantitative ratio, the weather resistance, heat resistance, cross-linking efficiency, and cold resistance of the copolymer are obtained. This is desirable because the denaturation efficiency is improved.

(B) A 5-membered ring (cyclopentane ring) exists in the main chain of the unsaturated copolymer according to the present invention. (C) In the copolymer, the double bond (2,3 derived from the 1,3-3,4- and 1,4-adducts)
The ratio (total double bond of all adducts / 5-membered ring) of the 5-membered ring to the 5-membered ring is 20/80 to 90/10 (molar ratio). Glass transition temperature T
Considering the balance between g and iodine value, 30/70 to 80 /
It is desirable that it be present in an amount such that it becomes 20 (molar ratio).

The five-membered ring present in the copolymer according to the present invention includes two types, cis and trans. Although the mechanism of the formation of the five-membered ring is not clear, for example,
An unsaturated copolymer of, for example, a copolymer of an α-olefin such as ethylene and a conjugated diene such as 1,3-butadiene will be described by way of example. The 1,3-butadiene of the conjugated diene is added to the oligomer or prepolymer chain (p) formed by 1,2, and then the ethylene of the α-olefin is added. It is thought that it will generate. (Cat) represents a catalyst,
(P) represents an oligomer chain or a prepolymer chain.

[0081]

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As shown in the above formula, the cyclopropane ring (3-membered ring) is formed by intramolecular cyclization after adding 1,2 a conjugated diene represented by butadiene to an oligomer chain or a prepolymer chain (P). It is estimated that. The 5-membered ring and the cyclopropane ring contribute to the improvement of the compatibility of the copolymer. Therefore, it has good compatibility with styrene-based elastomers such as SBR. The copolymer is excellent in processability.

The formed molar ratio of the cyclopropane ring to the 5-membered ring (cyclopropane ring / 5-membered ring) is 0.1 / 99.9.
~ 50/50, more preferably 0.1 / 1/50.
More preferably, it is 99.9-30 / 70.

Identification and quantification of these five-membered and cyclopropane rings (three-membered rings) can be performed by ¹³ C-NMR. More specifically, in the case of ethylene / 1,3-butadiene, a hexachlorobutadiene solvent, 110
The 1,4 adduct and the 5-membered ring structure were measured by Makr under the conditions of 100 ° C. and 100 MHz.
omol. Chem. 192, 2591-2601 (1991).

[0085] The identification and quantification of the 1,2 adduct ¹
H-NMR, ¹³ C-NMR and two-dimensional N of ¹ H and ¹³ C
It can be performed by MR.

[0086]

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The respective chemical shifts are shown in the following Table (1A).

[0088]

[Table 1]

Further, the following cyclopropane ring was also identified and quantified by ¹³ C-NMR, ¹ H-NMR and a C—H coupling constant specific to the cyclopropane ring in the same manner as described above.

[0090]

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The chemical shifts are shown in Table 2A below.

[0092]

[Table 2]

The ratio of each component and the quantitative ratio of the structure of the conjugated diene were determined from the area ratio of each peak of ¹³ C-NMR and / or ¹ H-NMR. In addition, a five-membered ring is also present in the second unsaturated copolymer, and the mechanism of formation of this five-membered ring is not clear, but in this second unsaturated copolymer, For example, 1,2- or 3,4-addition of isoprene, which is a conjugated diene, to an oligomer chain or a prepolymer chain formed by reaction of an α-olefin and a conjugated diene, followed by addition of ethylene and further intramolecular cyclization Is thought to generate a 5-membered ring.

The identification and quantification of the 5-membered ring can be performed by ¹³ C-NMR in the same manner as described above. Identification and quantification of the following 3,4 adducts were performed by ¹ H-NMR, ¹³ C
ＮＭＲ NMR and two-dimensional NMR of ¹ H and ¹³ C.

[0095]

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The respective chemical shifts are shown in the following Table (1B).

[0097]

[Table 3]

Further, the 1,2 adduct was identified and quantified based on the same chemical shift as the 3,4 adduct. The ratio of each component and the quantitative ratio of the structure of the conjugated diene are the same as those described above for ¹³ C-NMR and / or ¹ H-NM.
It was determined from the area ratio of each peak of R.

The same applies to the third unsaturated copolymer, for example, ethylene / styrene / 1,3-butadiene copolymer. Styrene, Makrom
ol. Chem. Phys. 197, 1071-1083 (1996) and Macromo.
lecules. 28, 4665-4667 (1995).

Incidentally, the ratio of each component and the quantitative ratio of the structure of the conjugated diene were determined by ¹³ C-NMR and / or ¹
It was determined from the area ratio of each peak of H-NMR. In the first unsaturated copolymer according to the present invention, a structural unit derived from a conjugated diene monomer, that is, a 1,2 adduct (including a 3,4 adduct; the same applies hereinafter), a 1,4 addition. , A 5-membered ring (cyclopentane structure), and a cyclopropane ring (3-membered ring) in total of 0.01 to 30 mol%, preferably 0.1 to 20 mol%.
Is preferably contained in an amount of The balance of the structural units is derived from α-olefin such as ethylene.

In the second unsaturated copolymer according to the present invention, structural units derived from conjugated diene monomers, ie, 1,2 adducts (including 3,4-adducts), 1,4 adducts Body, a 5-membered ring (cyclopentane structure) having a total of 0.01 to 30 mol%,
Preferably, it is contained in an amount of 0.1 to 15 mol%. The balance of the constituent units is derived from α-olefin such as ethylene.

In the third unsaturated copolymer according to the present invention, structural units derived from a conjugated diene monomer, ie, 1,2 adduct (including 3,4 adduct), 1,4 adduct Adduct,
It is preferable that a 5-membered ring (cyclopentane structure) and a cyclopropane ring (3-membered ring) are contained in a total amount of 0.01 to 30 mol%, preferably 0.1 to 15 mol%. The balance of the structural units is derived from α-olefins such as ethylene and aromatic vinyl compounds such as styrene.

In the third unsaturated copolymer, the constituent unit derived from the aromatic vinyl compound is 0.1 to 60 mol%, preferably 0.1 to 40 mol%, more preferably 0.5 to 40 mol%. -30% by mole. The constituent unit derived from an α-olefin represented by ethylene is contained in an amount of 10 to 99.89 mol%, preferably 45 to 99.8 mol%, more preferably 50 to 99.6 mol%. .

In each of the first, second, and third unsaturated copolymers, when each of the structural units is within the above range, the surface hardness, wear resistance, vibration-proofing properties, and damping properties are obtained. And good compatibility with other polar resins and fillers.

The iodine value of the unsaturated copolymer of the present invention is generally 1 to 50, preferably 3 to 50, more preferably 3 to 50.
It is desirable to be in the range of 40. When the iodine value of the copolymer is in the above range, when the copolymer is crosslinked and used for rubber or the like, the crosslinking speed of the copolymer is high, and the obtained crosslinked product has excellent low-temperature properties.

The unsaturated copolymer of the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C. of usually 0.01 to 0.01.
10.0 dl / g, wax, wax additive,
When used for release agents, lubricants, oil modifiers, etc.
It is preferable that the intrinsic viscosity [η] is 0.01 to 1.0 dl / g.
1 / g, more preferably in the range of 1.0 to 5.0 dl / g. Intrinsic viscosity [η] of the copolymer
However, when it is within the above range, a copolymer having excellent properties such as weather resistance, ozone resistance, heat aging resistance, low-temperature properties, and dynamic fatigue resistance will be obtained.

The unsaturated copolymer of the present invention has a single glass transition temperature and a glass transition temperature Tg measured by a differential scanning calorimeter (DSC) of usually 25 ° C. or less,
It is preferably in the range of 10 ° C. or less, more preferably 0 ° C. or less.

In particular, the glass transition temperature Tg is desirably -30 ° C. or lower, more preferably -35 ° C. or lower. On the other hand, the lower limit of Tg is usually -150 ° C. When the glass transition temperature Tg of the copolymer is within the above range,
Excellent cold resistance and low temperature characteristics.

In the case of the unsaturated copolymer having no aromatic vinyl compound unit, the glass transition temperature and the unsaturated copolymer are higher than those of the unsaturated copolymer having the aromatic vinyl compound unit.
It may be preferable in view of low-temperature characteristics.

Further, as the amount of ring structure in the copolymer increases, the glass transition temperature tends to increase, and the cis 1,4 adduct, 1,2 adduct (or 3,4 adduct), α -The glass transition temperature tends to decrease as the amount of each unit such as an olefin unit increases. Therefore, by limiting the range of the glass transition temperature, the ratio of each component in the copolymer is substantially limited.

In the present invention, when two or more types of α-olefins are used, the quantitative ratio (constituent ratio) of the α-olefins, the iodine value of the copolymer, the intrinsic viscosity [η], and the glass transition temperature Tg Among them, at least one is preferably in the above range, more preferably two or more is in the above range, and particularly, all of the constituent ratio of α-olefin, iodine value, intrinsic viscosity, and glass transition temperature are It is preferably within the above range.

The Mw / Mn (in terms of polystyrene) measured by GPC is preferably 3.0 or less.
Further, Tm (melting point) measured by DSC is 120 ° C. or less,
The temperature is preferably 110 ° C. or lower, more preferably 70 ° C. or lower, and particularly preferably 40 ° C. or lower for the elastomer.

For example, when used as an elastomer, the crystallinity measured by X-ray diffraction is preferably 15% or less, more preferably 10% or less. When used as a film or the like, Tm and crystallinity are not limited thereto.

(Oil Swelling Degree) In the case of the unsaturated copolymer of the present invention, in particular, an ethylene / C3-C12 α-olefin / conjugated diene copolymer having a melting point (Tm) of 40 ° C. or less. Is the same intrinsic viscosity [η], the same iodine value,
Identical ethylene content and 3-1 carbon atoms of the same type
Ethylene having 2 α-olefin units and having 3 to 3 carbon atoms
The oil swelling degree of the α-olefin / 5-ethylidene-2-norbornene copolymer (X) is preferably 90% or less, more preferably 85% or less.

Here, the same intrinsic viscosity [η], the same iodine value, and the same ethylene content refer to the intrinsic viscosity [η], iodine value, ethylene content of the unsaturated copolymer of the present invention. Indicates that the content is within plus / minus 10%. When the other monomer is copolymerized in the unsaturated copolymer of the present invention, the same type of monomer is copolymerized in the copolymer (X). Use something.

The degree of oil swelling of the unsaturated copolymer of the present invention or the copolymer (X) used as a reference was 70%.
Parts by weight, homopolypropylene (MFR at 230 ° C.)
Is 10 to 20 g / min. ), 0.1 part by weight of divinylbenzene, 2,5-dimethyl-
Olefin heat obtained by uniformly mixing 2,5- (tert-butylperoxyhexane) at a rate of 0.15 parts by weight and kneading at a temperature of 200 ° C. for 5 minutes using a Labo Plastomill manufactured by Toyo Seiki Seisaku-sho Measure for plastic elastomer.

[Production of Unsaturated Copolymer] The first unsaturated copolymer according to the present invention contains at least one kind of carbon having 2 carbon atoms.
To 12 and an at least one conjugated diene monomer represented by the above formula (Ia) in the presence of an olefin polymerization catalyst, preferably a metallocene catalyst shown below, It is preferably obtained by random copolymerization.

The second unsaturated copolymer according to the present invention comprises:
At least one α-olefin having 2 to 12 carbon atoms,
Obtained by copolymerizing at least one conjugated diene monomer represented by the above formula (Ib) in the presence of an olefin polymerization catalyst, preferably a metallocene catalyst shown below, preferably a random copolymerization. Can be

Further, the third unsaturated copolymer (unsaturated ternary copolymer) according to the present invention has the carbon number of 2 to 12 described above.
Α-olefin, an aromatic vinyl compound and a conjugated diene monomer represented by the above formula (I) (in other words, the conjugated diene monomer (Ia) and / or (Ib))
Are copolymerized, preferably randomly copolymerized, in the presence of an olefin polymerization catalyst, preferably a metallocene catalyst shown below.

As such a metallocene catalyst, a transition metal complex (a) represented by the following formula (II) or (III):

[0121]

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[In the formulas (II) and (III), M is Ti, Z
r, Hf, Nd, Sm or Ru, wherein Cp1 and Cp2 are a cyclopentadienyl group which is π-bonded to M,
X ¹ and X ² are an anionic ligand or a neutral Lewis base ligand, and Y is a nitrogen atom, an oxygen atom, a phosphorus atom, or a sulfur atom. And Z is a C, O, B, S, Ge, Si or Sn atom or a group containing these atoms. And one or more compounds selected from the following components (b), (c) and (d). (B): a compound which reacts with the transition metal M in the component (a) to form an ionic complex. (C): an organoaluminum compound. (D): an alumoxane.

First, the transition metal complex (a) represented by the following formula (II) used in the present invention will be described.

[0124]

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In the formula (II), M is a transition metal of Group 4 of the periodic table or a lanthanide series, and specifically, Ti, Z
r, Hf, Nd, Sm, Ru, preferably T
i, Zr, Hf, Cp1 is a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative thereof bonded to M by π, X ¹ and X ² are an anionic ligand or Y is a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom, or a sulfur atom, and Z is carbon, oxygen, sulfur, boron or an element of group 14 of the periodic table. (For example, silicon, germanium or tin), preferably any of carbon, oxygen and silicon, and Z may have a substituent,
Z and Y may form a condensed ring.

More specifically, Cp1 is a ligand coordinating to a transition metal and is a ligand having a cyclopentadienyl skeleton such as a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative group thereof. The ligand having a cyclopentadienyl skeleton may have a substituent such as an alkyl group, a cycloalkyl group, a trialkylsilyl group, and a halogen atom.

Z is C, O, B, S, Ge, Si,
It is an atom selected from Sn, and Z may have a substituent such as an alkyl group or an alkoxy group, and the substituents of Z may combine with each other to form a ring.

X ¹ and X ² are anionic ligands or neutral Lewis base ligands, which may be the same or different from each other, and are each a hydrogen atom or a halogen atom;
Or a hydrocarbon, silyl or germyl group containing up to 20 carbon, silicon or germanium atoms.

Specific examples of the compound represented by the formula (II) include (dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silylene) titanium dichloride [Example A1 to be described later. Used), ((t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl) titanium dichloride, (dimethyl (phenylamide) (tetramethyl-η ⁵ -cyclopentadienyl) (Silylene) titanium dichloride, (dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silylene) titanium dimethyl, (dimethyl (4
-Methylphenylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silylene) titanium dichloride, (dimethyl (t-butylamide) (η ⁵ -cyclopentadienyl)
(Silylene) titanium dichloride, (tetramethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) disilylene) titanium dichloride, and the like.

In the present invention, a transition metal compound represented by the following formula (III) can also be used.

[0131]

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[In the formula (III), M is Ti, Zr, Hf,
Nd, a Sm or Ru, preferably Ti, Zr or Hf, Cp1 and Cp2 are cyclopentadienyl groups, indenyl group, fluorenyl group or their derivative groups attached M and [pi, X ¹ And X ²
An anionic ligand or a neutral Lewis base ligand,
Z is a C, O, B, S, Ge, Si or Sn atom or a group containing these atoms. ]

In the formula (III), the bonding group Z is preferably C, O,
It is preferably one atom selected from B, S, Ge, Si, and Sn, and this atom may have a substituent such as an alkyl group or an alkoxy group, and the substituents of Z are mutually bonded. To form a ring.

Cp1 and Cp2 are ligands which coordinate to the transition metal, and include cyclopentadienyl group, indenyl group, 4,5,
A ligand having a cyclopentadienyl skeleton such as a 6,7-tetrahydroindenyl group or a fluorenyl group, and the ligand having a cyclopentadienyl skeleton includes an alkyl group, a cycloalkyl group, and a trialkylsilyl group. And a substituent such as a halogen atom.

X ¹ and X ² are anionic ligands or neutral Lewis base ligands, and specifically include a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, and a sulfone group. acid-containing group (-SO ₃ Ra, where, Ra is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, an aryl group substituted with substituted aryl group or an alkyl group with a halogen atom.), Examples include a halogen atom and a hydrogen atom.

The following are examples of metallocene compounds in which M is zirconium and contains two ligands having a cyclopentadienyl skeleton. Cyclohexylidene-bis (indenyl) dimethyl zirconium, cyclohexylidene-bis (indenyl) zirconium dichloride, isopropylidene-bis (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylene-bis ( Indenyl) zirconium dichloride, methylphenylsilylene-bis (indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-
1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (4,7-dimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,7-trimethyl-1-indenyl) zirconium dichloride, rac
-Dimethylsilylene-bis (2,4,6-trimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (α -Naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (β-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-methyl-4- (1-anthryl) -1-indenyl) zirconium dichloride and the like.

In addition, metallocene compounds in which zirconium metal is replaced with titanium metal or hafnium metal in the above compounds can also be exemplified. The metallocene compounds as described above can be used alone or in combination of two or more.

The metallocene compound as described above can be used by being supported on a particulate carrier. Such particulate supports include SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ , M
gO, ZrO ₂ , CaO, TiO ₂ , ZnO, SnO ₂ ,
Inorganic carriers such as BaO and ThO, polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene,
An organic carrier such as a styrene-divinylbenzene copolymer can be used. These particulate carriers can be used alone or in combination of two or more.

Next, a metallocene-based catalyst is formed (b): a compound which reacts with the transition metal M in the component (a) to form an ionic complex, that is, an ionized ionic compound, (c): an organoaluminum The compound and (d): alumoxane (aluminum oxy compound) will be described.

<(B) Ionized Ionic Compound> The ionized ionic compound is a compound which reacts with the transition metal M in the transition metal complex component (a) to form an ionic complex. Examples of the acidic compound include a Lewis acid, an ionic compound, a borane compound, and a carborane compound.

As the Lewis acid, a compound represented by BR ₃ (where R is a fluorine atom, a phenyl group which may have a substituent such as a methyl group or a trifluoromethyl group or a fluorine atom). For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl)
Boron, tris (4-fluoromethylphenyl) boron,
Tris (pentafluorophenyl) boron, tris (p-
And tris (o-tolyl) boron and tris (3,5-dimethylphenyl) boron.

Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts. Specifically, the trialkyl-substituted ammonium salts include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) boron.
And ammonium tetra (phenyl) boron. Examples of the dialkyl ammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron. Further, examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, and ferrocenium tetra (pentafluorophenyl) borate.

As a borane compound, decaborane (1
4), bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III)
And salts of metal borane anions.

As the carborane compound, 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) Salts of metal carborane anions such as nickelate (IV) are exemplified.

The ionized ionic compound as described above is
They can be used alone or in combination of two or more.
The organic aluminum oxy compound or the ionized ionic compound can be used by being supported on the above-mentioned particulate carrier.

In forming the catalyst, the following organic aluminum compound (c) may be used together with the organic aluminum oxy compound and / or the ionized ionic compound.

<(C) Organoaluminum Compound> As the organoaluminum compound, a compound having at least one Al-carbon bond in a molecule can be used. Examples of such a compound include an organoaluminum compound represented by the following general formula.

(R ¹ ) m Al (O (R ² )) nHpXq (wherein R ¹ and R ² may be the same or different, and usually have 1 to 15 carbon atoms, preferably 1 to 1 carbon atoms.
X is a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, and q is 0
≦ q <3, and m + n + p + q
= 3. <(D) Organoaluminum oxy compound (alumoxane)> The (d) organoaluminum oxy compound may be a conventionally known aluminoxane.
It may be a benzene-insoluble organic aluminum oxy compound as exemplified in JP-A-8687.

Conventionally known aluminoxanes (alumoxanes) are specifically represented by the following general formula.

[0150]

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In the formula, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group, preferably a methyl group, an ethyl group, and particularly preferably a methyl group. m is an integer of 2 or more, preferably 5 to 40.

Here, the aluminoxane has the formula (OAl (R
¹⁾ represented alkyloxy aluminum units and formula (OAl (R ²⁾ represented alkyloxy aluminum units (where they are in) is in), R ¹ and R ² are the same hydrocarbon group as R, R ¹ And R ² represent different groups.).

The organoaluminum oxy compound may contain a small amount of an organic compound component of a metal other than aluminum. In the present invention, as the olefin polymerization catalyst, the metallocene catalyst as described above is preferably used.In some cases, other than the metallocene catalyst, a conventionally known solid titanium catalyst component and an organoaluminum compound are used. And a vanadium catalyst composed of a soluble vanadium compound and an organoaluminum compound.

In the present invention, (i) an α-olefin, (ii) a conjugated diene, and if necessary, (iii) an aromatic vinyl compound are usually copolymerized in a liquid phase in the presence of a metallocene catalyst as described above. . At this time, a hydrocarbon solvent is generally used, but an α-olefin may be used as the solvent. The copolymerization can be carried out by either a batch method or a continuous method.

When the copolymerization is carried out by a batch method using a metallocene catalyst, the concentration of the metallocene compound in the polymerization system is usually 0.00005 per liter of polymerization volume.
-1 mmol, preferably 0.0001-0.5 mmol.

The organic aluminum oxy compound has a molar ratio (Al / M) of aluminum atom (Al) to transition metal atom (M) in the metallocene compound of 1 to 1000.
It is used in such an amount that it becomes 0, preferably 10-5000.

The ionized ionic compound has a molar ratio of the ionized ionic compound to the metallocene compound (ionized ionic compound / metallocene compound) of 0.5-2.
It is used in an amount such that it becomes 0, preferably 1 to 10.

When an organoaluminum compound is used, it is used in an amount of usually about 0 to 5 mmol, preferably about 0 to 2 mmol, per liter of polymerization volume.

In the copolymerization reaction, the temperature is usually -20 to 15
0 ° C, preferably 0 to 120 ° C, more preferably 0 to
In the range of 100 ° C., the pressure is over 0 to 80 kg / cm
² , preferably above 0 and up to 50 kg / cm ² .

The reaction time (average residence time when the copolymerization is carried out by a continuous method) varies depending on conditions such as the catalyst concentration and the polymerization temperature, but is usually 5 minutes to 3 hours, preferably 10 minutes to 10 minutes. 1.5 hours.

(I) α-olefin, (ii) conjugated diene, and optionally (iii) aromatic vinyl compound are used in such an amount as to obtain the above-mentioned unsaturated copolymer having a specific composition. It is supplied to the polymerization system. Further, upon copolymerization, a molecular weight regulator such as hydrogen may be used.

As described above, (i) an α-olefin,
When (ii) a conjugated diene and, if necessary, (iii) an aromatic vinyl compound are copolymerized, an unsaturated copolymer is usually obtained as a polymerization solution containing the same. This polymerization solution is treated by a conventional method to obtain an unsaturated copolymer.

In the present invention, the unsaturated copolymer can be variously modified by having a double bond in the main chain and the side chain. By the peroxide modification, the double bond can be epoxidized, and a highly reactive epoxy group can be introduced into the copolymer.

Thus, it can be used as a thermosetting resin or as a reactive resin. Further, a double bond can be used for a Diels-Alder reaction, a Michael addition reaction, and the like. In addition, heat resistance and ozone resistance are further improved by selectively hydrogenating and saturating the double bond of the main chain.

In the present invention, part or all of the unsaturated copolymer may be modified with an unsaturated carboxylic acid, a derivative thereof, or an aromatic vinyl compound, and the amount of the modification may be 0.01 to 30% by weight. % Is preferable.

Particularly, in the unsaturated copolymer, since a highly reactive double bond exists in the side chain, the radical initiator used in the modification can be reduced. On the other hand, in a resin having no side chain double bond, a radical generated by a hydrogen abstraction reaction is used as a starting point. Large amounts of initiator are required because not all initiators trigger the hydrogen abstraction reaction. In addition, the molecular weight is generally reduced due to the simultaneous occurrence of a decomposition reaction.

On the other hand, in the unsaturated copolymer according to the present invention, since a highly reactive terminal double bond is present in the side chain, the amount of the radical initiator used can be reduced, and at the same time, Since the radical generated during the modification mainly reacts with the double bond in the side chain, the main chain decomposition reaction is suppressed, and the decrease in the molecular weight is also suppressed.

Examples of the monomer used for the modification (hereinafter, referred to as “graft monomer”) include unsaturated carboxylic acids, derivatives thereof, and aromatic vinyl compounds. Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid. Examples of the unsaturated carboxylic acid derivatives include acid anhydrides, esters, amides, imides, and metal salts, and specifically, maleic anhydride, citraconic anhydride, itaconic anhydride, methyl acrylate, and methacrylic acid. Methyl, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, monoethyl maleate, diethyl maleate, monomethyl fumarate, dimethyl fumarate,
Itaconic acid monomethyl ester, itaconic acid diethyl ester, acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N, N-diethylamide, maleic acid-N-monobutylamide, Maleic acid-N, N-dibutylamide, fumaric acid monoamide, fumaric acid diamide, fumaric acid-N-monoethylamide, fumaric acid-N, N-diethylamide, fumaric acid-N-monobutylamide, fumaric acid-N, N-
Dibutylamide, maleimide, N-butylmaleimide, N-
Examples include phenylmaleimide, sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate and the like. It is preferable to use maleic anhydride among these graft monomers.

Specific examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene. Mono or polyalkyl styrene such as styrene, methoxy styrene, ethoxy styrene, vinyl benzoic acid, vinyl benzoate methyl, vinyl benzyl acetate, hydroxy styrene,
Functional group-containing styrene derivatives such as o-chlorostyrene, p-chlorostyrene, and divinylbenzene, 3-phenylpropylene, 4-phenylbutene, α-methylstyrene, and the like are included. Of these, styrene or 4-methoxystyrene is preferred.

In order to produce a modified copolymer by graft copolymerizing a graft monomer with an unsaturated copolymer, various known methods can be employed. For example, there is a method in which graft copolymerization is performed by heating an unsaturated copolymer and a graft monomer at a high temperature with or without a radical initiator in the presence or absence of a solvent. In the reaction, another vinyl monomer such as styrene may be allowed to coexist.

In order to produce a partially or completely modified graft-modified unsaturated copolymer having a graft ratio of 0.01 to 30% by weight, from the viewpoint of industrial production, a graft-modified unsaturated copolymer having a higher graft ratio is required. Preparing an unsaturated copolymer,
Next, a method of adjusting the graft ratio by mixing the graft-modified unsaturated copolymer with the unmodified unsaturated copolymer (the product obtained by this method is referred to as "partially modified graft-modified unsaturated copolymer"). This is a preferable method because the concentration of the graft monomer in the composition can be appropriately adjusted. Further, a predetermined amount of a graft monomer may be blended with the unsaturated copolymer from the beginning and grafting may be performed (the product obtained by this method is referred to as “a completely modified graft-modified unsaturated copolymer”). .).

The amount of modification of the unsaturated copolymer with the graft monomer is such that the graft ratio in the whole resin composition as described above is 0.01 to 30% by weight, particularly 0.05 to 10% by weight.
Preferably it is in the range of weight%.

The modified unsaturated copolymer obtained here (hereinafter sometimes referred to as a modified copolymer) was added with ethylene / α
-An olefin copolymer and / or an ethylene / vinyl acetate copolymer can be blended and used as a modified unsaturated copolymer-containing composition.

The modified unsaturated copolymer was ethylene / α
-By blending an olefin copolymer or an ethylene / vinyl acetate copolymer or both, it is possible to lower the melt viscosity of the obtained composition, improve the moldability, and further improve the adhesiveness after the retort treatment. Can be improved. Further, the adhesiveness to the polyolefin can be improved.

In the ethylene / α-olefin copolymer as described above, ethylene and α-olefin are copolymerized at random and have an ethylene content of 45 to 95 mol%, preferably 45 to 90 mol%. Ethylene-α-olefin copolymer is used.

This ethylene / α-olefin copolymer is generally used in a melt flow rate (ASTM D12
38, the condition E) is from 0.1 to 50 g / 10 min, preferably from 0.3 to 30 g / 10 min, and the density is usually from 0.850 to 10 g / 10 min.
0.900 g / cm ³ , preferably 0.850 to 0.8
90 g / cm ³ , and the crystallinity by X-rays is generally 3
It is less than 0%, preferably less than 25%.

The α-olefin constituting the ethylene / α-olefin copolymer has 3 to 2 carbon atoms.
Α-olefin of 0 is used, specifically, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-
Octene, 1-decene, 1-tetradecene, 1-octadecene and the like are used, and these α-olefins are used alone or as a mixture of two or more.

The ethylene / α-olefin copolymer has a melting point (ASTM D 3418) of usually 10
0 ° C. or less. The ethylene / vinyl acetate copolymer as described above preferably has a vinyl acetate content of 5 to 40% by weight, preferably 10 to 35% by weight. The ethylene / vinyl acetate copolymer generally has a melt flow rate (ASTM D1238, condition E) of 0.1 to 50 g / 10 min, preferably 0.3 to 30 g / 10 min.
Minutes.

Further, in addition to the above-mentioned modified unsaturated copolymer, ethylene / α-olefin copolymer and ethylene / vinyl acetate copolymer, the composition containing the modified unsaturated copolymer may have a crystalline property. An ethylene-based polymer, a crystalline propylene-based polymer and modified products thereof, and a tackifier can be blended.

Such a crystalline ethylene polymer is a homopolymer of ethylene or a copolymer of ethylene and a small amount of α-olefin, and has an ethylene content of more than 90 mol% and not more than 100 mol%, preferably Is in the range of 95-100 mol%.

This crystalline ethylene polymer is generally
Melt flow rate (ASTM D1238, condition E)
Is 0.1 to 50 g / 10 min, preferably 0.3 to 30 g / min.
10 minutes, density is usually 0.900 to 0.980 g / c
m ³ , preferably 0.920 to 0.970 g / cm ³ .

The α-olefin used for producing the crystalline ethylene polymer has 3 carbon atoms.
And α-olefins of, for example, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-tetradecene, and 1-octadecene. These α-olefins can be used alone or in combination of two or more.

Such a crystalline ethylene polymer may be modified with an unsaturated carboxylic acid, a derivative thereof or an aromatic vinyl compound. And the same. Further, in order to produce the modified ethylene polymer, various known methods can be employed.

Such a resin composition has excellent adhesive strength. The crystalline propylene-based polymer is a homopolymer of propylene or a copolymer of propylene and an α-olefin, and has a propylene content of more than 55 mol% and 1
It is not more than 00 mol%, preferably in the range of 80 to 100 mol%.

The crystalline propylene polymer generally has a melt flow rate (ASTMD 1238, condition E) of 0.1 to 50 g / 10 min, preferably 0.3 to 30 g / 10 min.
g / 10 min, and the melting point (Tm) is 110-165 ° C, preferably 120-165 ° C.

As the α-olefin used in producing the crystalline propylene polymer, ethylene and α-olefins having 4 to 20 carbon atoms are used.
Specifically, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene and the like, and these α-olefins alone or Two or more kinds can be used in combination.

Such a crystalline propylene-based polymer is
The unsaturated carboxylic acid, its derivative or the aromatic vinyl compound may be modified with an unsaturated carboxylic acid, a derivative thereof or an aromatic vinyl compound. In order to produce the modified propylene-based polymer, various known methods can be employed.

Such a resin composition has excellent adhesive strength. The tackifier is added to adjust the viscosity of the modified unsaturated copolymer-containing composition at the time of melting, and to improve hot tack and wettability. Specific examples of the tackifier include an alicyclic hydrogenated tackifier, rosin, modified rosin or an ester thereof, an aliphatic petroleum resin, an alicyclic petroleum resin, an aromatic petroleum resin, and an aliphatic component. Examples of suitable tackifiers include copolymerized petroleum resins of styrene and aromatic components, low molecular weight styrene resins, isoprene resins, alkyd resins, phenol resins, terpene resins, and cumarone / indene resins. These tackifiers can be used alone or in combination of two or more.

The composition containing the modified unsaturated copolymer (also referred to as “resin composition”) is composed of the above-mentioned graft-modified unsaturated copolymer (also referred to as “modified copolymer”) 1-1.
00 parts by weight, preferably 1 to 80, more preferably 10
-80 parts by weight and 99 to 0 parts by weight, preferably 99 to 20 parts by weight, more preferably 90 to 20 parts by weight of the soft polymer (however, the total amount of the modified copolymer and the soft polymer) Is 100 parts by weight.)

Examples of the soft polymer include the above-mentioned ethylene / α-olefin copolymer, ethylene / vinyl acetate copolymer and a mixture thereof. As a preferred embodiment of the resin composition, 10 to 80 parts by weight of the modified copolymer, ethylene / α-olefin copolymer and / or ethylene / vinyl acetate copolymer 90
To 20 parts by weight (however, the total amount is 100 parts by weight).

Specifically, the modified copolymer is 10 to 80 parts by weight, preferably 30 to 80 parts by weight, and the ethylene / α-olefin copolymer is 90 to 20 parts by weight, preferably 70 to 80 parts by weight.
20 parts by weight (however, the total amount is 100 parts by weight), 10 to 80 parts by weight, preferably 3 parts by weight of the modified copolymer.
0 to 80 parts by weight, and ethylene / vinyl acetate copolymer 90
To 20 parts by weight, preferably 70 to 20 parts by weight (however, the total amount is 100 parts by weight), 10 to 80 parts by weight, preferably 30 to 80 parts by weight of the modified copolymer, and ethylene / α -5 to 60 parts by weight, preferably 10 to 50 parts by weight, of the olefin copolymer and 5 to 40 parts by weight, preferably 10 to 30 parts by weight of the ethylene / vinyl acetate copolymer (however, the total amount is 100 parts by weight). And the like.

The modified unsaturated copolymer-containing composition according to the present invention may contain, in addition to the above-mentioned modified copolymer, ethylene / α-olefin copolymer and ethylene / vinyl acetate copolymer, Further, an ethylene polymer or a modified product thereof, a propylene polymer or a modified product thereof, a tackifier, and the like may be added.

When an ethylene-based polymer or a modified product thereof is added, 0 parts by weight is added to 100 parts by weight of the total of the modified copolymer, the ethylene / α-olefin copolymer and the ethylene / vinyl acetate copolymer. It is used in an amount of 1 to 50 parts by weight, preferably 1 to 30 parts by weight.

When a propylene-based polymer or a modified product thereof is added, 0 parts by weight based on 100 parts by weight of the total of the modified copolymer, ethylene / α-olefin copolymer and ethylene / vinyl acetate copolymer is added. It is used in an amount of 1 to 50 parts by weight, preferably 1 to 30 parts by weight.

When a tackifier is added, 0.5 to 25 parts by weight based on 100 parts by weight of the total of the modified copolymer, the ethylene / α-olefin copolymer and the ethylene / vinyl acetate copolymer is used. It is used in an amount of 5 parts by weight, preferably 5 to 15 parts by weight.

As described above, the composition containing a modified unsaturated copolymer (also referred to as a composition containing a modified copolymer) contains a graft-modified unsaturated copolymer as an essential component. Graft ratio is generally 0.01-30.
%, Preferably 0.05 to 10% by weight, MF
R is 0.1 to 50 g / 10 min, preferably 0.2 to 40 g
/ 10 min and the degree of crystallinity is less than 35%.

In the composition containing the modified unsaturated copolymer as described above, each component can be prepared by various known methods within the ranges described above.
For example, a method of mixing with a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, or the like, or a method of mixing and kneading with a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, or the like, followed by granulation or pulverization is adopted. Can be manufactured.

This modified copolymer-containing composition contains, in addition to the above components, a heat stabilizer, a weather stabilizer, an antistatic agent, a pigment, a dye, a rust inhibitor and the like, which impair the object of the present invention. It can be blended in a range that does not exist.

The composition containing the modified copolymer has excellent adhesiveness to polyester resins, polycarbonate resins, saponified olefin / vinyl acetate copolymers, polyolefins, and the like, and is suitable as an adhesive between these resins. Used.

Using such a modified copolymer-containing composition, a polycarbonate layer or a polyester resin layer
By bonding the ethylene / vinyl acetate saponified layer to form a laminate, a laminate having excellent gas permeability resistance and not causing delamination during high-temperature filling or retorting can be obtained. Since the present laminate also has low gas permeability for oxygen and the like, it has extremely excellent properties as a packaging material for retorts and a packaging material for hot fill.

When the above unsaturated copolymer (also referred to as an α-olefin / conjugated diene polymer, unsaturated terpolymer, etc.) is used as an elastomer,
The unsaturated copolymer-containing elastomer composition (A) may contain at least one compounding agent selected from the group consisting of a crosslinking agent (B) and a filler (C), if necessary. Hereinafter, it may be referred to as an elastomer composition).
Further, an ethylene / α-olefin copolymer or the like may be blended.

Examples of the crosslinking agent (B) include sulfur, sulfur compounds and organic peroxides. Specific examples of the sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, and insoluble sulfur.

Specific examples of the sulfur compound include sulfur chloride, sulfur dichloride, polymer polysulfide and the like.
Also, sulfur compounds that release active sulfur at the crosslinking temperature to crosslink, for example, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide,
Selenium dimethyldithiocarbamate and the like can also be used. When sulfur or a sulfur compound is used as the crosslinking agent, it is preferable to use a crosslinking accelerator together.

Specific examples of the organic peroxide include dicumyl peroxide (DCP), di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, and t-butyl cumene. Luperoxide, di-t-amyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane , 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, alkyl such as t-butylhydroperoxide Peroxides: t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxypivalate, t-butylperoxymaleic acid, t-butylperoxyneodecanoate, t-butylperoxide Oxybenzoate, di-t-butyl Peroxyesters such as luperoxyphthalate; ketone peroxides such as dicyclohexanone peroxide. These organic peroxides can be used alone or in combination of two or more.

Of these, the one-minute half-life temperature was 13
Organic peroxides at 0 ° C. to 200 ° C. are preferred, specifically, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butyl Cumyl peroxide, di-t-amyl peroxide, t-butyl hydroperoxide and the like are preferred. In addition, when using an organic peroxide as a crosslinking agent, it is preferable to use a crosslinking assistant together.

Of the various cross-linking agents described above, sulfur or a sulfur-based compound, particularly sulfur, is preferred because a crosslinked product having excellent properties can be obtained. However, organic peroxides are particularly excellent in crosslinking efficiency. Is more preferable.

The unsaturated copolymer of the present invention can be prepared by adding sulfur,
It is very economical because peroxides can be crosslinked. In particular, in the copolymer containing the component unit derived from the formula (Ib), crosslinking by sulfur and peroxide occurs efficiently.

When the crosslinking agent (B) is sulfur or a sulfur-based compound, the amount of (A) the unsaturated copolymer is 10%.
It is used in a proportion of usually 0.5 to 10 parts by weight, preferably 1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 0 parts by weight. When it is an organic peroxide, (A)
For 100 grams of the unsaturated copolymer, 0.00
005 to 0.1 mol, preferably 0.0005 to 0.05
It is used in molar amounts.

(C) The filler includes a filler having a reinforcing property and a filler having no reinforcing property. Reinforcing fillers
It has the effect of increasing mechanical properties such as tensile strength, tear strength, and abrasion resistance of the bridge. Specific examples of such a filler include SRF, GPF, FEF, MAF, HAF,
Examples include carbon blacks such as ISAF, SAF, FT, and MT; those obtained by surface-treating these carbon blacks with a silane coupling agent; silica; activated calcium carbonate; and finely divided talc. When carbon black is used as the filler, any type of carbon black can be used as long as it is a carbon black generally used for rubber.

The filler having no reinforcing property can increase the hardness of a rubber product without significantly affecting the physical properties,
Used to reduce costs. As such a filler, specifically, talc, clay,
Calcium carbonate and the like.

The filler (C) is usually 300 parts by weight or less, preferably 10 to 300 parts by weight, more preferably 10 to 2 parts by weight, based on 100 parts by weight of the unsaturated copolymer (A).
It is used in a ratio of 00 parts by weight.

The unsaturated copolymer-containing elastomer composition comprises (A) an unsaturated copolymer and at least one compound selected from other components such as (B) a crosslinking agent and (C) a filler. And a rubber compounding agent, and kneading by a conventionally known method such as a mixing method using an internal mixer such as a Banbury mixer, a kneader, or an intermix.

The unsaturated copolymer-containing elastomer composition according to the present invention can be used as it is without being crosslinked, but when it is used as a crosslinked product, its properties can be exhibited most. That is, (A) the unsaturated copolymer includes:
It functions to improve the crosslinking speed of the crosslinked product and to improve the strength properties of the crosslinked product.

(C) In order to produce a crosslinked product from a composition containing no crosslinking agent, an unsaturated copolymer-containing elastomer composition is once prepared in the same manner as in ordinary crosslinking of a general rubber. After the elastomer composition is formed into a desired shape, crosslinking may be performed. A method of irradiating an electron beam is employed as a crosslinking method.

(C) In order to prepare a crosslinked product from an unsaturated copolymer-containing elastomer composition containing a crosslinking agent, the unsaturated copolymer-containing elastomer composition is usually prepared in the same manner as in the case of crosslinking a general rubber. The product may be prepared once, and then the elastomer composition may be molded into a desired shape and then subjected to crosslinking by heating or the like.

In the present invention, in addition to the unsaturated copolymer (A), the crosslinking agent (B) and the filler (C), a crosslinking accelerator and a crosslinking aid are added to the uncrosslinked compounded rubber. , Softeners, tackifiers, anti-aging agents, foaming agents, processing aids, adhesion promoters, heat stabilizers, weather stabilizers, antistatic agents, coloring agents, lubricants, flame retardants, anti-blooming rubbers A compounding agent can be compounded within a range that does not impair the purpose of the present invention.

Specific examples of the crosslinking accelerator include N-cyclohexyl-2-benzothiazolesulfenamide (CB
Z), N-oxydiethylene-2-benzothiazolesulfenamide, N, N-diisopropyl-2-benzothiazolesulfenamide, 2-mercaptobenzothiazole, 2-
Thiazole compounds such as (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole, dibenzothiazyldisulfide; diphenylguanidine (DPG), triphenylguanidine, diphenylguanidine Guanidine compounds such as orthonitrile guanidine, orthonitrile biguanide, diphenylguanidine phthalate; aldehyde amine or aldehyde-ammonia compounds such as acetaldehyde-aniline reactant, butyraldehyde-aniline condensate, hexamethylenetetramine, acetaldehyde ammonia; Imidazoline compounds such as mercaptoimidazoline; thiourea compounds such as thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, and diorthotolylthiourea Compounds; tetramethyl thiuram monosulfide, tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, thiuram-based compounds such as pentamethylene thiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, di -n
Dithioate compounds such as zinc-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate and tellurium dimethyldithiocarbamate; xanthate compounds such as zinc dibutylxanthate; Compounds such as zinc white can be cited. These crosslinking accelerators are
(A) 1-2 parts per 100 parts by weight of the unsaturated copolymer
It is used in an amount of 0 parts by weight, preferably 2 to 10 parts by weight.

Specific examples of the crosslinking assistant include sulfur; quinone dioxime compounds such as p-quinone dioxime, and polyfunctional monomers such as (meth) acrylates such as trimethylolpropane triacrylate and polyethylene glycol dimethacrylate. Allyl compounds such as diallyl phthalate and triallyl cyanurate; maleimide compounds such as m-phenylene bismaleimide; and divinylbenzene. It is preferable that the crosslinking assistant is used in an amount of 0.5 to 2 mol, preferably approximately equimolar to 1 mol of the organic peroxide.

As the softening agent, a softening agent conventionally compounded in rubber is widely used, and specifically, a petroleum softening agent such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, petrolatum; tar,
Coal tar softeners such as coal tar pitch; fatty oil softeners such as castor oil, linseed oil, rapeseed oil, and coconut oil; tall oil; sub; waxes such as beeswax, carnauba wax, and lanolin; ricinoleic acid, palmitin Fatty acids and fatty acid salts such as acids, barium stearate, calcium stearate, and zinc laurate; and synthetic high molecular substances such as petroleum resins, atactic polypropylene, and coumarone indene resins. Among them, a petroleum softener is preferably used, and particularly, a process oil is preferably used. The softener is (A) the unsaturated copolymer 100
200 parts by weight or less, preferably 5 to 2 parts by weight,
It is used in an amount of 00 parts by weight, more preferably 10 to 150 parts by weight, even more preferably 10 to 100 parts by weight.

As the foaming agent, foaming agents generally used for foaming rubber can be widely used.
Specifically, inorganic foaming agents such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite, N, N'-dimethyl-N, N'-dinitrosoterephthalamide, N, N'-di Nitroso compounds such as nitrosopentamethylenetetramine, azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, azo compounds such as barium azodicarboxylate, benzenesulfonylhydrazide, toluenesulfonylhydrazide, p, p ' -Oxybis (benzenesulfonylhydrazide), sulfonylhydrazide compounds such as diphenylsulfone-3,3'-disulfonylhydrazide, and azide compounds such as calcium azide, 4,4-diphenyldisulfonylazide, and p-toluenesulfonylazide. Can be Of these,
Nitroso compounds, azo compounds and azide compounds are preferred. The foaming agent is used in an amount of 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the unsaturated copolymer (A). From the elastomer composition of the unsaturated copolymer containing the foaming agent in such an amount, a foam having an apparent specific gravity of 0.03 to 0.8 g / cm ³ can be produced.

A foaming aid can be used together with the foaming agent. When the foaming aid is used in combination, there are effects such as lowering the decomposition temperature of the foaming agent, accelerating the decomposition, and making the bubbles uniform. Examples of such a foaming aid include organic acids such as salicylic acid, phthalic acid, stearic acid and oxalic acid, urea and derivatives thereof. The foaming aid is used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the unsaturated copolymer (A).

As the processing aid, those generally blended with rubber as processing aids can be widely used.
Specifically, ricinoleic acid, stearic acid, palmitic acid, higher fatty acids such as lauric acid, salts of these higher fatty acids such as barium stearate, zinc stearate,
Examples include calcium stearate or esters. The processing aid is appropriately used in an amount of 10 parts by weight or less, preferably 5 parts by weight or less based on 100 parts by weight of the unsaturated copolymer (A).

The adhesion-imparting agent improves the adhesion between the crosslinked product and a decorative layer such as a coating film. For example, an organotin compound, a tertiary amine compound, a hydroxyl group-containing (co) polymer, a metal Hydroxide and the like.

Examples of the organic tin compound include dialkyltin dicarboxylates such as dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin dilaurate, and dioctyltin dilaurate; dibutyltin dimethyl maleate, dibutyltin dioctyl maleate;
Dialkyltin maleates such as dibutyltin dioleyl maleate, dibutyltin dimethoxymethyl maleate and dibutyltin laurate methyl maleate; dialkyltin dithioglycolates such as dibutyltin dioctylthioglycolate and dioctyltin dioctylthioglycolate; dibutyltin dilauryl Mercaptide,
Dialkyltin dimercaptides such as dioctyltin dilaurylmercaptide; dialkyltin dithiocarboxylates such as dibutyltin dithioacetate, dibutyltin dithiooctanoate, dibutyltin dithiolaurate, dioctyltin dithiolaurate; dibutyltin dimercaptopropionate Dialkyltin dimercaptocarboxylates; dialkylhydroxytin chlorides such as dibutylhydroxytin chloride;
Alkyltin trilaurates such as butyltin trilaurate and octyltin trilaurate; alkyltin trimaleates such as butyltin trimethylmaleate and butyltin trioctylmaleate; alkylhydroxytin dichlorides such as butylhydroxytin dichloride; Examples thereof include triaralkyl tin maleates such as tribenzyl tin octyl maleate and tribenzyl tin methyl maleate, and dialkyl tin maleate polymers such as dioctyl tin maleate polymer. The organotin compound is used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the unsaturated copolymer (A).
It is used in a proportion of up to 5 parts by weight.

Specific examples of the tertiary amine compound include monoamines such as triethylamine, dimethylpropylamine, diethylpropylamine and N, N-dimethylcyclohexane; triethylenediamine, N, N, N ', N'-tetramethyl Ethylenediamine, N, N, N ', N'-tetramethylpropane
-1,3-diamine, N, N, N ', N'-tetramethylhexane-1,6-
Diamines such as diamines; N, N, N ', N', N ", N" -hexamethyldiethylenetriamine, N, N, N ', N', N ", N" -hexamethyldipropylenetriamine, tetramethyl Triamines such as guanidine; N, N'-dimethylpiperazine, N-methyl-N '-(2-dimethylamino) -ethylpiperazine, N-methylmorpholine, N- (N', N'-dimethylaminoethyl)-
Morpholine, 1,2-dimethylimidazole, 1,4-diazabicyclo- [2.2.2] -octane, 1,8-diazabicyclo- [5.4.
0] -7- Cyclic amines such as undecene; dimethylaminoethanol, methylaminodiethanol, dimethylaminoethoxyethanol, N, N, N'-trimethylaminoethylethanolamine, N-methyl-N '-(2-hydroxyethyl ) -Piperazine, alcoholamines such as N- (2-hydroxyethyl) morpholine; tris (dimethylamino)
Phenolamines such as methylphenol; etheramines such as bis (2-dimethylaminoethyl) ether and ethylene glycol bis (3-dimethyl) -aminopropyl ether; 2- (dimethylamino) ethyl acrylate and 2- (diethylamino) Ethyl acrylate, 2- (dimethylamino) ethyl methacrylate, 2- (diethylamino) ethyl methacrylate, 2- (dibutylamino) ethyl acrylate, 2- (dibutylamino) ethyl methacrylate, 2- (dimethylamino) propylacrylamide, 2- ( Low molecular weight compounds such as tertiary amino group-containing unsaturated compounds such as dimethylamino) propyl methacrylamide.

Further, as the tertiary amine compound, a high molecular compound such as a tertiary amino group-containing olefin (co) polymer can be exemplified. The tertiary amino group-containing olefin (co) polymer has a structure in which a tertiary amino group-containing unsaturated compound is copolymerized irregularly or regularly in a branched or linear carbon atom chain, or It has a structure in which a side chain having a tertiary amine structure is grafted, and the amount of the tertiary amino group-containing unsaturated compound is 0.1 to 50% by weight. Such tertiary amino group-containing olefin (co)
The polymer can be produced by a known method of copolymerizing using a tertiary amino group-containing unsaturated compound or graft-polymerizing a polyolefin. Third as above
1,4-diazabicyclo- [2.2.2]-
Octane is preferably used. The tertiary amine compound is based on 100 parts by weight of the unsaturated copolymer (A).
It is used in a proportion of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight.

Specific examples of the hydroxyl group-containing (co) polymer include saponified ethylene / vinyl acetate copolymers; hydroxyl groups at the molecular terminals such as polybutadiene having a hydroxyl group at the molecular terminal and polyisoprene having a hydroxyl group at the molecular terminal. Hydrogenated conjugated diene polymer having a hydroxyl group at the molecular end, such as hydrogenated polybutadiene having a hydroxyl group at the molecular end and hydrogenated polyisoprene having a hydroxyl group at the molecular end; ethylene / hydroxy Copolymer of ethylene and a hydroxyl group-containing unsaturated compound such as ethyl acrylate copolymer, ethylene / hydroxyethyl methacrylate copolymer, ethylene / hydroxyoctyl acrylate copolymer, ethylene / hydroxyoctyl methacrylate copolymer; hydroxyethyl Acrylate, hydroxyethyl methacrylate Graft-modified olefins (co) such as polyethylene, polypropylene, ethylene / α-olefin copolymer, ethylene / α-olefin / polyene copolymer, etc., grafted with hydroxyl group-containing unsaturated compounds such as hydroxyoctyl acrylate and hydroxyoctyl methacrylate. Polymers. Of these, hydrogenated polybutadiene having a hydroxyl group at the molecular terminal and hydrogenated polyisoprene having a hydroxyl group at the molecular terminal are preferable. When a hydroxyl group-containing (co) polymer is blended, the adhesion between the crosslinked product and the urethane resin-based coating film can be improved. The hydroxyl group-containing (co) polymer is added in an amount of 0.5 to 100 parts by weight of the unsaturated copolymer (A).
To 20 parts by weight, preferably 1 to 15 parts by weight.

Specific examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, calcium hydroxide,
Examples include iron hydroxide and nickel hydroxide. Among them,
Aluminum hydroxide and magnesium hydroxide are preferred,
Particularly, magnesium hydroxide is preferable. Metal hydroxide is
With respect to 100 parts by weight of the unsaturated copolymer (A), 2
0 to 200 parts by weight, preferably 20 to 150 parts by weight, more preferably 50 to 150 parts by weight.

The method for producing a crosslinked product from the unsaturated copolymer-containing elastomer composition according to the present invention is not particularly limited, but specifically, for example, the following method is employed.

That is, using a mixer such as a Banbury mixer, the unsaturated copolymer (A), the filler (C), the liquid softener, and other rubber compounding agents, if necessary, are added at 80 to 170 ° C. After kneading at a temperature of 3 to 10 minutes, using a roll such as an open roll, (B) a crosslinking agent and, if necessary, a crosslinking accelerator are further mixed, and the roll temperature is 40 to 8
After kneading at 0 ° C. for 5 to 30 minutes, the mixture is dispensed to prepare a ribbon-shaped or sheet-shaped unvulcanized compound rubber. When the kneading temperature in the above internal mixers is low,
A crosslinking agent (B), a crosslinking accelerator, a foaming agent and the like can be simultaneously kneaded.

The uncrosslinked compounded rubber thus prepared is molded into a desired shape by an extruder, a calender roll, or a press.
The molded product is heated at a temperature of 150 ° C. for 1 to 30 minutes or heated at a temperature of 150 to 270 ° C. for 1 to 30 minutes to obtain a crosslinked product. Crosslinking may be performed in a mold or without a mold. When a mold is not used, the steps of molding and crosslinking are usually performed continuously. As a heating method in the crosslinking tank, a heating tank such as hot air, a fluidized bed of glass beads, UHF (ultra-high frequency electromagnetic wave), or steam can be used.

When a method of irradiating with an electron beam is adopted as a crosslinking method, a mixer such as a Banbury mixer is used, and (A) an unsaturated copolymer, if necessary, (C) a filler, and other rubber compounding agents. 3 ~ at a temperature of 80 ~ 170 ° C
After kneading for 10 minutes, using a roll such as an open roll, kneading at a roll temperature of 40 to 80 ° C. for 5 to 30 minutes, and then dispensing to prepare a ribbon-shaped or sheet-shaped uncrosslinked compounded rubber. The uncrosslinked compounded rubber thus prepared is molded into a desired shape by an extruder, a calender roll, or a press, and irradiated with an electron beam to obtain a crosslinked product. Irradiation of electron beam is 0.1-10Me
V (mega electron volts), preferably 0.3 to 2
An electron having an energy of MeV is absorbed in an amount of 0.5
~ 35 Mrad (Megarad), preferably 0.5 ~ 1
It is desirable to carry out so as to be 0 Mrad.

The unsaturated copolymer of the present invention has a crosslinking density,
Particularly, it is excellent in that the crosslink density when crosslinked with an organic peroxide is high. The crosslinked product thus obtained is widely used for applications such as automobile parts, general industrial parts, and parts for civil engineering and construction materials. In particular, applications requiring oil resistance and dynamic fatigue resistance, such as tire treads,
Tire tread modifiers, parts around automobile engines, anti-vibration rubber, rubber rolls, heat-resistant belts, hoses, wiper blades, electric wires, various packings, anode caps, electric insulating materials such as grommets, building gaskets, civil engineering sheets, etc. It can be used for applications such as civil engineering building materials and rubberized cloth. In particular, it is used for an engine mount insulator of an automobile, a center bearing insulator, an insulator of a rack and pinion type steering device, and the like. Such a crosslinked product has good tear resistance and the like.

Further, a foam can be produced from the unsaturated copolymer-containing elastomer composition according to the present invention. In the case of producing a foam, a foaming agent usually used for rubber, and It can be produced by blending a foaming aid according to the above and foaming. These blowing agents are used in an amount of 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the unsaturated copolymer (A). The apparent specific gravity of the obtained foam is usually in the range of 0.03 to 0.7. The obtained foam is heat insulating material, cushion material,
It can be used for applications such as sealing materials and hoses.

Further, from the unsaturated copolymer-containing elastomer composition according to the present invention (including a compounded rubber, an uncrosslinked product, and a crosslinked product), a crosslinked product having a surface decorative layer is produced. Can also. This can be obtained by coating the surface of the crosslinked material as described above, or by bonding another member such as metal or resin using an adhesive to form a decorative layer. Also, after forming the decorative layer on uncrosslinked compounded rubber,
By crosslinking the compounded rubber, a crosslinked product having a surface decoration layer can be obtained.

Such an unsaturated copolymer-containing elastomer composition is a third unsaturated copolymer-containing elastomer composition, for example, an α-olefin / aromatic vinyl compound / conjugated diene copolymer-containing elastomer. When the composition is a composition, the aromatic vinyl compound is contained in an amount of 0.1 to 40 mol%, preferably 0.5 to 40 mol%, based on the copolymer.
When it is 30 mol%, the coatability is excellent.

For coating of a crosslinked or uncrosslinked compounded rubber,
Generally used paints such as acrylic resin paints, epoxy resin paints, polyester resin paints, urethane resin paints, alkyd resin paints, melamine resin paints, and silicone resin paints can be used.

The acrylic resin-based paint is obtained by homopolymerizing or copolymerizing a monomer (main raw material) selected from acrylic acid, methacrylic acid and esters thereof and, if necessary, other comonomers by a solution polymerization method or an emulsion polymerization method. A paint that is polymerized to prepare a varnish and, if desired, used as a clear to which a diluent, a second resin or other additives are added, or as an enamel to which the clear is further added with a pigment.

The polyester resin paint is a resin which is cured by allowing a vinyl compound or the like to act on an unsaturated polyester obtained by polycondensation of a polyhydric alcohol and a polybasic acid. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, and propylene glycol.Examples of the polybasic acid include phthalic anhydride, maleic anhydride, fumaric acid, and adipic acid. Methacrylic acid or the like is used. Of these, propylene glycol, phthalic anhydride and styrene are most frequently used.

The urethane resin-based coating is generally a coating which forms a coating film by a reaction between a polyisocyanate and a polyol compound, and is classified into a one-pack type and a two-pack type, and a powder coating using a block type isocyanate. .

The melamine resin paint is a thermosetting paint obtained by combining a butylated melamine resin etherified with butanol, a phthalic acid resin, a butylated urea resin and the like. As the phthalic acid resin, one modified with a non-drying oil such as castor oil or coconut oil or a semi-drying oil is used.

The silicone resin-based paint is a paint using a curable silicone resin or a curable silicone resin modified with alkyd, epoxy, phenol, acrylic, melamine, urethane, or the like.

When acrylic resin-based paint, melamine resin-based paint, polyester resin-based paint, urethane resin-based paint, and silicone resin-based paint are used, the adhesion of the coating film is excellent, and particularly, urethane resin-based paint and silicone resin-based paint are used. Paints are preferred because of the excellent adhesion of the coating film.

As a means for applying the paint as described above, any method such as spraying with a spray, brushing, or applying with a roller may be employed. The thickness of the coating is
It can be changed according to the purpose of use of the molded article, and is not particularly limited, but is usually about 1 to 500 μm.

The cross-linked molded article having such a surface decoration layer is used for automotive industrial parts such as weather strips, door glass run channels, and window frames, and construction materials such as glazing gaskets, joint gaskets, and airtight gaskets. Can be used.

In particular, when the above crosslinked product is used for a weatherstrip sponge, it is preferable to use two types of olefins in the unsaturated copolymer, ethylene and an α-olefin having 3 or more carbon atoms. At this time, the molar ratio of ethylene / α-olefin is 80/20 to 6
It is preferably 0/40 (total 100 mol).

In particular, when the above-mentioned crosslinked molded article using the third unsaturated copolymer is used for a weatherstrip sponge, the third unsaturated copolymer (unsaturated ternary copolymer) is used. As the olefin in the polymer), it is preferable to use two kinds of ethylene and an α-olefin having 3 or more carbon atoms in the same molar ratio as described above. When styrene is copolymerized as the aromatic vinyl compound, 1
It is further preferred that the amount is from 7 to 7 mol%, preferably from 2 to 6 mol%.

In addition, the intrinsic viscosity [η] of the unsaturated copolymer of the present invention used for a weatherstrip sponge.
Is preferably 2.5 to 4.5 dl / g. As the crosslinking type, sulfur crosslinking is preferable. The molar ratio of ethylene / α-olefin, intrinsic viscosity [η],
The crosslinking type described above is preferable because it is excellent in tear strength, flexibility, compression set and the like.

The larger the melt viscosity η ^* in the low frequency range, the smaller the permanent compression set, which is preferable. For example, those having a long chain branch and those containing a high molecular weight component are more preferable.

In particular, when the above crosslinked product is used for door glass run channels, it is preferable to use two types of olefins in the unsaturated copolymer, ethylene and α-olefin having 3 or more carbon atoms. At this time, the molar ratio of ethylene / α-olefin is 90/10 to 7
It is preferably 5/25 (total 100 mol). Further, the intrinsic viscosity [η] is preferably 2.5 to 4.5 dl / g. Further, the iodine value is preferably 20 to 50. When the molar ratio of ethylene / α-olefin, intrinsic viscosity [η], and iodine value are as described above, the strength,
It is preferable because elongation, hardness and the like increase and compression set decreases.

Particularly, the above-mentioned crosslinked product molded product, especially the above-mentioned crosslinked product molded product using the third unsaturated copolymer, is preferably used for a tire tread. In the present invention, when the crosslinked product is used for a tire tread, ethylene and ethylene having 3 or more carbon atoms are used as olefins in the unsaturated copolymer (particularly preferably, the unsaturated ternary copolymer). It is preferable to use two types of α-olefin, and in this case, each structural unit (ethylene / α-olefin)
Is from 99/1 to 75/25, preferably 85/1
5 to 75/25, more preferably 85/15 to 80/2
It is preferably 0. Further, when styrene is copolymerized as the aromatic vinyl compound used as required, the amount of the constituent unit is preferably 5 to 20 mol%, more preferably 7 to 15 mol%. Also t
Preferably, the value of an δ (0 ° C.) tends to increase, and the value of tan δ (50 ° C.) tends to decrease.

When the unsaturated copolymer of the present invention has the following composition, it can be used as a shrink film. That is, in the unsaturated copolymer constituting the film, units derived from ethylene are 99.89.
The content of a structural unit derived from an α-olefin having 3 to 12 carbon atoms is 0 to 30 mol%, and the content of a structural unit derived from an aromatic vinyl compound used as required is 0.1 to 0.5 mol%.
1 to 12 mol%, a structural unit comprising a conjugated diene, particularly butadiene or isoprene, is contained in an amount of 0.01 to 10 mol%, and the intrinsic viscosity [η] of the copolymer is 0.1 to 0.1 mol%.
1 to 10 dl / g, melting point of 60 to 125 ° C.,
Moreover, when the film is stretched in at least one direction, it can be suitably used as a shrink film.

The resin for a film contains a tackifier in an amount of 1 to 50 parts by weight based on 100 parts by weight of the unsaturated copolymer.
It is preferable that the film is blended in parts by weight, the film is more preferably biaxially stretched, and the shrinkage at 80 ° C. is even more preferably 20% or more.

A composition obtained by mixing 0.5 to 100 parts by weight of an antifogging agent and 0.5 to 10 parts by weight of a nucleating agent as required with respect to 100 parts by weight of the unsaturated copolymer is It is useful as a film, a sheet, a tube, or a hose, and specific examples thereof include agricultural films, stretch films, wrap films, and sheets for packaging.

Examples of the tube include a shrink tube, a piping tube, a medical tube and the like. When the unsaturated copolymer is used for these applications, it is more preferable that the melting point measured by DSC is in the range of 70 to 125 ° C.

In the above-mentioned applications, the unsaturated copolymer has 99.89 to 83% by mole of a structural unit derived from ethylene and 0 to 10% of a structural unit derived from an α-olefin having 3 or more carbon atoms. Preferably it is mol%. The structural unit derived from the aromatic vinyl compound used as necessary is preferably contained in an amount of 0.1 to 7 mol%. In the above-mentioned application, the copolymer preferably contains the butadiene or isoprene constituent unit in an amount of 0.01 to 5 mol%. <Hot melt adhesive> The unsaturated copolymer according to the present invention, in particular, the third unsaturated copolymer (unsaturated terpolymer, α-olefin / aromatic vinyl compound / conjugated diene copolymer) Can also be used as a composition shown below in a hot melt adhesive or the like.

Such a hot-melt adhesive comprises (A)
It is formed from a base polymer, (B) a tackifier and (C) an unsaturated copolymer as described above, and if necessary (D) a low molecular weight polyolefin.

The components (A) base polymer, (B) tackifier and (D) low molecular weight polyolefin will be described below. (A) Base Polymer The base polymer used in the present invention is not particularly limited as long as it is a polymer usually used for a hot melt adhesive. For example, (a-1) a polyolefin, (a-2)
Examples thereof include a polar group-containing polymer and (a-3) an aromatic vinyl compound / conjugated diene copolymer.

(A-1) Polyolefin (a-1) As the polyolefin, polyethylene (HD)
PE, LDPE, LLDPE, etc.), polypropylene (atactic polypropylene, syndiotactic polypropylene, etc.), ethylene / propylene copolymer and the like.

(A-2) Polar Group-Containing Polymer Examples of the (a-2) polar group-containing polymer include the following polymers. (1) Ethylene / vinyl acetate copolymer (EVA) (2) Modified E such as saponified EVA and graft-modified EVA
VA polymer (3) Ethylene ethyl (meth) acrylate (EE
An ethylene / (meth) acrylate copolymer such as A) (4) An ionomer resin obtained by partially neutralizing an ethylene / (meth) acrylic acid copolymer. Using these as specific examples,
Products marketed by Mitsui-Dupont Polychemicals Co., Ltd. under the trade name "Himilan" are listed. (5) Terpolymer of ethylene / propylene / (meth) acrylic acid (6) Polyamide: a reaction product of a dibasic acid and a diamine, for example, a dimer of a fatty acid such as soybean oil, tung oil, and tall oil Reaction products of dimer acid with alkyl diamines such as ethylene diamine and diethylene triamine, and nylons such as nylon 12. Specific examples thereof include those marketed under trade names such as Daiamide (Daicel Chemical Industries), Brachicon (Toa Gosei Chemical Industry), and Amilan (Toray). (7) Polyester: Examples thereof include those marketed under the trade names of ester resins 200 and 300 (Toyobo), Vita1200 and 300 (Goodyear) and the like. (8) vinyl acetate copolymer, vinyl acetate / crotonic acid copolymer, vinyl acetate / phthalic anhydride copolymer, vinyl acetate / vinyl pyrrolidone polymer, cellulose derivative polymer, polymethyl methacrylate polymer, Polyvinyl ether polymer, polyurethane polymer, thermosetting resin polymer, etc.

(A-3) Aromatic vinyl compound / conjugated diene copolymer (a-3) Aromatic vinyl compound / conjugated diene copolymer
A copolymer comprising an aromatic vinyl compound and a conjugated diene compound and a hydrogenated product thereof, specifically, styrene.
Butadiene random copolymer, styrene / isoprene random copolymer, butadiene / polystyrene block copolymer, polystyrene / polyisoprene block copolymer, polystyrene / polyisoprene / polystyrene triblock copolymer (SIS), polystyrene / polybutadiene Polystyrene triblock copolymer (SB
S), poly (α-methylstyrene) polybutadiene
Poly (α-methylstyrene) triblock copolymers and hydrogenated products thereof can be exemplified. These polymers can be obtained as commercial products, and hydrogenated products are also commercially available. For example, Califlexx TR-11
01, TR-1107, TR-4113 (Shell Chemical Co., Ltd.), Clayton G-6500, G-6521, G-1
Products marketed under trade names such as 650, G-1652, G-1657 (Shell Chemical Co., Ltd.), Sorprene, and hydrogenated Sorprene (Philips) are exemplified.

In this hot melt adhesive, these base polymers can be used alone or in combination of two or more. Among these base polymers, an aromatic vinyl compound / conjugated diene copolymer or a hydrogenated product thereof is preferable, and an aromatic vinyl compound / conjugated diene copolymer is particularly preferable.

(B) Tackifier The (B) tackifier used in this hot melt adhesive adjusts the viscosity of the base polymer (A) at the time of melting,
It is blended in order to improve hot tack and wettability. The (B) adhesive is not particularly limited as long as it can be blended with the (A) base polymer and can improve hot tack and wetting of the (A) base polymer when heated. Is used as described above.

(D) Low molecular weight polyolefin The (D) low molecular weight polyolefin used as required in this hot melt adhesive includes (i) a single α-olefin having 2 to 12 carbon atoms. A polyolefin having a limiting viscosity [η] in the range of 0.01 to 0.6 dl / g; and (ii) a limiting viscosity [η] of 0.01 to 0.6 dl. / G of saturated, linear or saturated, side-chain hydrocarbons.

Examples of the α-olefin having 2 to 12 carbon atoms in the polyolefin (i) include those described above. The production of the polyolefin (i) can be performed according to a known method. For example, it can be produced by a polymerization method such as a high pressure radical polymerization method or a medium / low pressure polymerization method carried out in the presence of various transition metal compound catalysts such as a Ziegler catalyst.

The polyolefin (i) was obtained by producing a high molecular weight homopolymer or copolymer by the above polymerization method.
The high molecular weight homopolymer or copolymer can be produced by a thermal decomposition method in which the molecular weight is reduced by a thermal degradation or a radical degradation method using a peroxide.

Examples of the hydrocarbon (ii) include linear hydrocarbons (paraffin wax and sasol wax) and hydrocarbons having a side chain (microwax). These waxes are publicly known and available on the market. Among them, examples of the method for producing sasol wax are shown below.

For example, coal is gasified using steam and oxygen to obtain a synthesis gas mainly composed of carbon monoxide and hydrogen.
Among the reactants obtained by passing this synthesis gas through a fixed-bed catalytic reactor known as a reactor of the ARGE process, substances heavier than diesel engine oil are subjected to a first distillation using a vacuum distillation method. Distillate (C18 to C2
3), it is separated into a second fraction (components C22 to C36) and a third fraction (C33 or higher). The third fraction is hydrogenated to remove all unsaturated hydrocarbons and oxygenates. The wax thus obtained is sasol wax.

The hot-melt adhesive comprises (A) the base polymer, (B) a tackifier, and (C) an unsaturated copolymer (particularly preferably an α-olefin / aromatic vinyl compound). / (Conjugated diene copolymer, that is, unsaturated ternary copolymer), and (B) 10 to 300 parts by weight of (B) a tackifier based on 100 parts by weight of base polymer; Preferably 50-2
00 parts by weight and the unsaturated copolymer (C) in an amount of 10 to 400 parts by weight, preferably 30 to 300 parts by weight.

This hot melt adhesive composition includes:
(D) The low molecular weight polyolefin can be blended in an amount of 1 to 100 parts by weight, preferably 10 to 80 parts by weight, based on 100 parts by weight of the base polymer (A). (D)
When a low molecular weight polyolefin is blended, the melt viscosity of the hot melt adhesive composition can be reduced, and the workability can be further improved. In addition, when (D) low molecular weight polyolefin is blended, the intrinsic viscosity [η] of the unsaturated copolymer (C) is preferably in the range of more than 0.6 dl / g and 10 dl / g or less. .

This hot melt adhesive composition needs not only the above (A) base polymer, (B) tackifier, (C) unsaturated copolymer and (D) low molecular weight polyolefin, but also Various additives such as a softening agent, a stabilizer, a filler, and an antioxidant can be added to the extent that the purpose of the hot melt adhesive is not impaired.

The hot melt adhesive composition can be produced by a conventionally known method, and includes (A) the base polymer, (B) the tackifier, (C) the unsaturated copolymer, If necessary, the (D) low-molecular-weight polyolefin and various compounding agents are supplied to a mixer such as Brabender at a predetermined compounding ratio, and are heated and melt-mixed, and the mixture is mixed into a desired shape, for example, granular or flake. It can be performed by forming into a shape, a rod shape, or the like.

The hot melt adhesive composition is heated and melted, and applied to a coated body such as cloth, kraft paper, metal foil such as aluminum foil, and resin molded article such as polyester film by a usual method. To form an adhesive layer for use. This hot melt adhesive composition exhibits excellent adhesive performance even when bonding a styrene polymer and a polyolefin.

<Latex composition> The unsaturated copolymer according to the present invention can also be used as a latex composition.
Such a latex composition comprises the above (A) 100 parts by weight of an unsaturated copolymer, and (B) a low molecular weight polyethylene, a low molecular weight ethylene / α-olefin copolymer, an unsaturated carboxylic acid compound-modified low molecular weight. Polyethylene and unsaturated carboxylic acid compound modified low molecular weight ethylene / α
2 to 50 parts by weight of at least one low molecular weight polymer selected from the group consisting of -olefin copolymers can be uniformly dispersed in an aqueous medium in the presence of a surfactant.

The latex composition desirably has an average solid particle diameter of 0.1 to 3.0 μm.
Further, it is preferable that the solid content has a cross-linking bond and the content of the insoluble matter in hot toluene is 30% by weight or more.

As the low molecular weight polymer, any of a waxy polymer at room temperature and a liquid at room temperature can be used. Examples of the low molecular weight polyethylene include polyethylene wax. The low molecular weight polyethylene preferably has an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.01 to 0.3 dl / g.

The low molecular weight ethylene / α-olefin copolymer includes, for example, ethylene / propylene copolymer,
Examples include ethylene / α-olefin copolymers such as ethylene / 1-butene copolymer. Low molecular weight ethylene / α-
The olefin copolymer preferably has an intrinsic viscosity [η] measured at 135 ° C. in decalin in the range of 0.01 to 0.3 dl / g.

The unsaturated carboxylic acid compound-modified low molecular weight polyethylene and the unsaturated or carboxylic acid compound-modified low molecular weight ethylene / α-olefin copolymer may contain an unsaturated carboxylic acid compound as a comonomer, or may contain an unsaturated carboxylic acid compound. The low molecular weight polyethylene and the low molecular weight ethylene / α-olefin copolymer graft-modified with a compound.

Examples of the unsaturated carboxylic acid compounds include unsaturated carboxylic acids having 3 to 20 carbon atoms and anhydrides, amides, imides, esters and the like. Specific examples thereof include acrylic acid and methacrylic acid. Unsaturated carboxylic acids such as, maleic acid, fumaric acid, itaconic acid, citraconic acid, norbornene dicarboxylic acid, tetrahydrophthalic acid, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic acid; maleic anhydride, Unsaturated carboxylic anhydrides such as itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride; maleic monoamide, maleic diamide, Unsaturated carboxylic acid amides or imides such as maleimide; methyl acrylate, methyl methacrylate, dimethyl maleate, mono-maleic acid Chill, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconic acid, tetrahydrophthalic acid dimethyl,
And unsaturated carboxylic acid esters such as dimethyl bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylate and glycidyl (meth) acrylate.

Of these, maleic acid, maleic anhydride, maleic monoamide, maleic diamide,
Maleimide, monomethyl maleate, diethyl maleate, and glycidyl (meth) acrylate are preferred.

Low-molecular-weight polyethylene, low-molecular-weight ethylene / α-olefin copolymer copolymerized with the unsaturated carboxylic acid compound, low-molecular-weight polyethylene graft-modified with the unsaturated carboxylic compound, low-molecular-weight ethylene In the α-olefin copolymer, the structural unit derived from the unsaturated carboxylic acid-based compound is 0.2 to 50.
%, Preferably in the range of 0.2 to 30% by weight.

Also, low-molecular-weight polyethylene copolymerized with the unsaturated carboxylic acid compound, low-molecular-weight ethylene
α-olefin copolymer, and low-molecular-weight polyethylene graft-modified with the unsaturated carboxylic acid-based compound,
The low molecular weight ethylene / α-olefin copolymer is 135
℃, intrinsic viscosity [η] measured in decalin is 0.01 to
It is preferably in the range of 0.3 dl / g.

These low molecular weight polymers (B) can be used alone or in combination of two or more. The low molecular weight polymer (B) has a function of miniaturizing the unsaturated copolymer (A) when producing a copolymer latex composition (hereinafter, also simply referred to as “latex composition”).

Such a copolymer latex composition comprises:
It contains the above unsaturated copolymer (A) as a solid content. In the present invention, the copolymer latex composition is
(B) It may contain a low molecular weight polymer. It is desirable that the low molecular weight polymer (B) is contained in an amount of 2 to 50 parts by weight, preferably 5 to 40 parts by weight, per 100 parts by weight of the unsaturated copolymer (A). Low molecular weight polymer (B)
When the amount is within the above range, the solid content can be finely divided, and the obtained copolymer latex composition has excellent storage stability, and has an impact resistance when used as a resin modifier. Excellent reforming effect.

[0285] Such a copolymer latex composition comprises
It can be produced by uniformly dispersing (A) an unsaturated copolymer and (B) a low molecular weight polymer in an aqueous solvent in the presence of a surfactant. More specifically, for example, (A) an unsaturated copolymer, a hydrocarbon solvent such as hexane, and if necessary, (B) a low molecular weight polymer are mixed,
Stir to obtain a homogeneous solution. Next, the homogeneous solution is added to an aqueous medium in which a surfactant is dispersed, and the mixture is stirred and mixed to obtain an emulsion. Further, the emulsion is heated at 50 to 100 ° C. to volatilize and remove the organic solvent to obtain a copolymer latex composition.

Here, the aqueous medium is used in such an amount that the concentration of solids in the obtained copolymer latex composition is in the range of 5 to 65% by weight. When the aqueous medium is used in such an amount, the copolymer latex composition obtained has good handleability.

The surfactant is not particularly limited, and an anionic surfactant, a cationic surfactant, a nonionic surfactant and the like can be used. In the present invention,
Anionic surfactants are preferred, and metal salts of fatty acids such as fatty acid sodium and fatty acid potassium are particularly preferably used. The amount of the surfactant used depends on the type of the polymer component used.
Usually 0.2 to 20 parts by weight, preferably 0.5 to 0.5 parts by weight
It is used in an amount of from 10 to 10 parts by weight.

Further, such a copolymer latex composition is produced by a method of phase inversion under high shear using a twin screw extruder as described in JP-A-61-123664. You can also.

The average particle size of the solid content of the copolymer latex composition thus obtained is 0.1 to 3.0 μm.
Is desirably within the range. In the present invention, the copolymer latex composition obtained as described above may be subjected to a crosslinking treatment. The crosslinking treatment can be performed using a known method such as ionizing radiation crosslinking or organic peroxide crosslinking.

The ionizing radiation used for the ionizing radiation crosslinking includes α-ray, β-ray, γ-ray, electron beam, X-ray and the like. The irradiation dose of the ionizing radiation is 1 to 50 Mra.
It is preferably in the range of d. When performing ionizing radiation crosslinking, a polyfunctional monomer may be allocated to the copolymer latex composition, and as the polyfunctional monomer,
For example, a monomer having two or more ethylenically unsaturated groups, particularly a vinyl group, is preferably used. In particular,
Examples thereof include divinylbenzene, tetramethylene diacrylate, glyceryl triacrylate, ethylene glycol dimethacrylate, 1,2,4-trivinylcyclohexane, and tetraallyloxyethane. The polyfunctional monomer is used in an amount of usually 0.1 to 20 parts by weight, preferably 0.3 to 5 parts by weight, per 100 parts by weight of the unsaturated copolymer (A).

The organic peroxide crosslinking is carried out by uniformly dispersing the organic peroxide in the copolymer latex composition and then heating it to a temperature not lower than the decomposition temperature of the organic peroxide. Organic peroxide has a 10-hour half-life temperature of 0 ° C
Organic peroxide having a temperature of 100 ° C. is preferred, and specifically, 1,1-bis (t-butylperoxy) cyclohexane,
t-butyl peroxypivalate, t-butyl peroxy-2
-Ethylhexanoate, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, p- Chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, isobutyl peroxide, diisobutylperoxydicarbonate, di (2-ethylhexyl)
Peroxycarbonate and the like can be mentioned. These organic peroxides can be used alone or in combination of two or more. The organic peroxide is used in an amount of usually 0.3 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the unsaturated copolymer (A).

In carrying out the organic peroxide crosslinking, a polyfunctional monomer may be allocated to the copolymer latex composition, and examples of the polyfunctional monomer include the same as those described above. The polyfunctional monomer is used in an amount of usually 0.1 to 20 parts by weight, preferably 0.3 to 5 parts by weight, per 100 parts by weight of the unsaturated copolymer (A).

The organic peroxide crosslinking may be carried out under normal pressure or under pressure. The solid content of the hot toluene-insoluble component is 30% by weight or more, preferably 50% by weight or more, more preferably 60% by weight or more. % Is desirable. Specifically, it is preferable that the heating time is usually 5 to 7 times the half life. The hot toluene insoluble content of the solid content indicates the degree of crosslinking, and when the hot toluene insoluble content is in the above range, when the crosslinked copolymer latex composition is used as a resin modifier, Excellent in impact resistance modification effect.

The crosslinked copolymer latex composition thus obtained has an average solid particle diameter of 0.1 to 3.0.
It is desirable to be in the range of μm. The crosslinked copolymer latex composition according to the present invention has excellent storage stability and, when used as a resin modifier, has excellent effects of modifying impact resistance and surface gloss.

The crosslinked copolymer latex composition according to the present invention may contain a pigment, a thickener, a plasticizer, a preservative, an antifoaming agent, a pH adjuster, an antioxidant, an antioxidant, etc., depending on its use. Can be blended in a conventionally known blending amount. These compounding agents may be compounded in the copolymer latex composition before crosslinking.

The (crosslinked) copolymer latex composition according to the present invention comprises an acrylonitrile / styrene copolymer (AS).
Resin) and a modified resin of thermoplastic resin such as modified polyphenylene oxide (modified PPO resin). In this case, the (crosslinked) copolymer latex composition is dried and used. In addition, acrylonitrile or the like may be subjected to emulsion graft polymerization in the presence of a (crosslinked) copolymer latex composition to be used as a resin modifier.

The AS resin and the modified PPO resin modified by the (crosslinked) copolymer latex composition according to the present invention are excellent in weather resistance, solvent resistance, impact resistance, surface gloss, and housing for home electric appliances. , Automotive interior parts such as instrument panels,
Used for automotive exterior parts such as front grills.

Further, the crosslinked product of the present invention, particularly the crosslinked product obtained by crosslinking with an organic peroxide, is particularly useful as a film or sheet, and has an excellent balance of transparency, scratch resistance, heat resistance and flexibility. ing. When used for this purpose, a copolymer obtained by copolymerizing at least one selected from ethylene, a conjugated diene and, if necessary, an α-olefin having 3 or more carbon atoms and an aromatic vinyl compound is preferable.
This copolymer is the above-mentioned copolymer, and particularly, DSC
Having a melting point of 40 ° C. or higher, preferably 70 ° C.
It is desirable to use those described above from the viewpoint of heat resistance. These films and sheets can be used, for example, for decorative films, table cloths, book covers, and the like. There is no particular limitation on the thickness of such a film or sheet,
Usually, the thickness is 1 μm to 110 mm. Further, it is more preferable that the film and the sheet are transparent. The haze value of the crosslinked product of the present invention is 0 to 50%, preferably 0 to 30% (1 m
m thickness).

In particular, when the unsaturated copolymer of the present invention is a third unsaturated copolymer containing an aromatic vinyl compound unit, it may be in the form of a film or a sheet, and may be a cold storage bag, a decorative film, It is suitably used for tablecloths, book covers, and in the form of tubes, and is suitably used for medical devices. In addition, food containers, stationery, daily necessities (eg, vacuum cleaner covers, cutting mats, bathtubs, infusion sets),
It is suitably used for the same applications as so-called soft vinyl chloride, such as automotive interior materials.

[0300]

According to the present invention, excellent weather resistance, heat resistance, oil resistance, economy, etc., low glass transition temperature, excellent cold resistance, and excellent crosslinking efficiency and modification efficiency, especially organic peroxides The present invention provides an unsaturated copolymer which is excellent in crosslinking efficiency and modification efficiency when sulfur is used, is capable of sulfur crosslinking, is inexpensive, is economically efficient, and can be industrially produced.

Further, according to the present invention, there is provided a method capable of industrially efficiently producing an unsaturated copolymer having the above-mentioned various excellent properties.

[0302]

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

The physical property test conditions and the like will be described below. [Ozone resistance test] The ozone resistance test was performed in an ozone test tank, under the conditions that the ozone concentration was 80 ppm, the elongation rate was 80%,
This is a static test in which the temperature is 40 ° C. and the time is 96 hours. The evaluation of ozone resistance is based on JIS K630
Perform according to criteria 1. The evaluation criteria for the surface state are as follows, for example, displayed as “C-5”.

Number of cracks A: small number of cracks B: many cracks C: countless number of cracks Size and depth of cracks 1: not visible to the naked eye, but can be confirmed with a magnifying glass of 10 times magnification 2: visible to the naked eye 3. The crack is deep and relatively large (less than 1 mm) 4 ... The crack is deep and large (1 mm or more and less than 3 mm) 5 ... The crack or cut that is likely to cause 3 mm or more [Tearing test] A Teflon sheet having a width of 20 mm is sandwiched between unvulcanized rubber sheets. After press vulcanization, a portion where the Teflon sheet is sandwiched is pulled with a chuck, and the peel strength is measured. [Oil resistance test] The oil resistance test is performed in accordance with the immersion test defined in JIS K6301, and the volume change rate (ΔV (%)) of the test piece is determined. The test oil was JI
It is carried out at 100 ° C. for 72 hours using S3 oil. [Tensile test] Tensile strength (TB), elongation at break (EB) and permanent elongation (PS) are measured according to JIS K6301. [Hardness test] JIS A according to JIS K 6301
The hardness (HS) is measured. [Compression set] Compression set (C which is an index of crosslink density)
S) (Compression conditions 150 ° C, 22 hours) is based on JIS K
6301. [Rubber properties] Rubber properties are evaluated by the following test methods. That is, the strength characteristics are determined by tensile strength (TB), the wear resistance is determined by the method of Lambourn, and the braking performance (wet skid) on a wet road surface is measured at 0 ° C. by a spectrometer.
The rolling resistance is evaluated by tan δ, and the rolling resistance is evaluated by tan δ at 50 ° C. using a spectrometer. [Melting Point (Tm) and Glass Transition Temperature (Tg)] DSC
, And the temperature at the maximum peak position is defined as Tm.

For the measurement, the sample was packed in an aluminum pan and 10 ° C.
/ Min at 200 ° C for 5 minutes, then decrease to -150 ° C at 20 ° C / min.
It was determined from an endothermic curve when the temperature was raised at ° C / min.

From the endothermic peak at the time of DSC measurement, the heat of fusion per unit weight is obtained, and this is divided by the heat of fusion of the polyethylene crystal of 70 cal / g to obtain
The crystallinity (%) can be determined. [Intrinsic viscosity [η]] Measured in decalin at 135 ° C. [Mw / Mn] GPC (gel permeation chromatography) using an orthodichlorobenzene solvent,
It was measured at 140 ° C. <Test Method> (1) Tensile strength (TB) is measured according to JIS K6301. (2) Lambourn abrasion is measured using a Lambourn abrasion tester manufactured by Iwamoto Seisakusho under the following conditions.

[0307] (3) tan δ is measured using a dynamic spectrometer manufactured by Rheometrics Inc. under the following conditions.

Measurement conditions: shear strain rate 0.5%, frequency 1
5Hz

[0309]

Example A1 (Pre-Activation of Catalyst) In a glass vessel sufficiently purged with nitrogen, (dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane) was synthesized by a known method. 5.5 mg of titanium dichloride was weighed, and a 1.0 mmol / ml toluene solution of triisobutylaluminum (hereinafter abbreviated as TIBA) was added to a 0.7 mmol / l aluminum atom.
0.75 ml was added to give 5 mmol, and 1
Ultrasonic irradiation was performed for 5 minutes to prepare a catalyst solution.

(Synthesis of Ethylene / Butadiene Copolymer)
At room temperature, 288 ml of toluene and 0.075 ml of the catalyst solution prepared in the step of pre-activating the catalyst were added to a 2 L autoclave which had been dried under reduced pressure and purged with nitrogen. After pressurizing to ² G, the pressure was released, and this pressure depressurizing operation was repeated three times. Thereafter, under normal pressure of ethylene, 1,3-butadiene was inserted as a gas corresponding to 7 g, and the temperature was raised to 50 ° C. Thereafter, the system was pressurized with ethylene to a pressure of 6 kg / cm ² G, and a toluene solution of triphenylcarbenium tetra (pentafluorophenyl) borate (0.0
02 mM / ml), and 1.5 ml of ethylene and 1,3
-Copolymerization with butadiene was started. The catalyst concentration at this time was 0.005 mmol / L of (dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane) dichloride titanium and triphenylcarbenium tetra (penta (Fluorophenyl) borate was 0.01 mmol / L. During the polymerization, the internal pressure was increased to 6 kg / cm by continuously supplying ethylene.
It was held on the ² G. After 5 minutes, the polymerization reaction was stopped by adding methyl alcohol.

After depressurizing, the polymer solution was taken out and 1 L of water
The mixture was washed with an aqueous solution to which 5 ml of concentrated hydrochloric acid was added and at a ratio of 1: 1 to transfer a catalyst residue to an aqueous phase. After the contact mixed solution was allowed to stand, the aqueous phase was separated and removed, and further washed twice with distilled water to separate the polymerization liquid phase from oil and water. Next, the polymer liquid phase separated from the oil and water was brought into contact with a three-fold amount of acetone under vigorous stirring to precipitate a polymer, and then thoroughly washed with acetone, and a solid part (copolymer) was collected by filtration. It dried at 130 degreeC and 350 mmHg for 12 hours under nitrogen flow.
The yield of the ethylene-butadiene copolymer obtained as described above was 13 g, the intrinsic viscosity [η] measured in decalin at 135 ° C. was 3.5 dl / g, and the glass transition temperature Tg was −
39 ° C., iodine value 31 g / 100 g, ethylene content 96 mol%, 5-membered ring structure 2.4 mol%, 3-membered ring structure 0.1
Mol%, 1,2 addition structure is 0.4 mol%, 1,4 addition structure is 1.1 mol%, activity is 104 kg / mmol Zr ·
hr.

Table 4 also shows the results.

[0313]

Example A2 The same operation as in Example A1 was carried out except that the amount of 1,3-butadiene was changed to 10 g. The yield of the obtained ethylene-butadiene copolymer was 14 g, the intrinsic viscosity [η] measured in decalin at 135 ° C. was 4.0 dl / g, and the glass transition temperature Tg was −38.
° C, the iodine value was 40 g / 100 g, the ethylene content was 91 mol%, the 5-membered ring structure was 6.8 mol%, the cyclopropane ring structure was 0.1 mol%, the 1,2 addition structure was 0.6 mol%, 1,
The 4-addition structure was 1.5 mol%, and the activity was 112 kg / mmol Zr · hr.

The results are shown in Table 4.

[0315]

Example A3 The same operation as in Example A1 was carried out except that the amount of 1,3-butadiene was changed to 4 g. The yield of the obtained ethylene / butadiene copolymer was 15 g, the intrinsic viscosity [η] measured in decalin at 135 ° C.
Is 4.2 dl / g, the glass transition temperature Tg is -40 ° C., the iodine value is 21 g / 100 g, the ethylene content is 97 mol%, the 5-membered ring structure is 1.9 mol%, and the cyclopropane ring structure is 0.1 mol%.
1 mol%, 1,2 addition structure 0.4 mol%, 1,4 addition structure 0.6 mol%, activity 120 kg / mmol Zr
Hr.

Table 4 also shows the results.

[0317]

Example A4 In Example A1, propylene was added at 55%.
Add 00 ml (25 ° C, 1 atm) and add 1,3-butadiene to 4
g, the same operation as in Example A1 was performed, except that the reaction temperature was changed to 20 ° C. The obtained ethylene propylene
The yield of the butadiene copolymer was 1.7 g, the intrinsic viscosity [η] measured in decalin at 135 ° C was 1.7 dl / g, the glass transition temperature Tg was -45 ° C, and the iodine value was (18.1) g / 1.
00g, ethylene content 67.5 mol%, propylene content 24.9 mol%, 5-membered ring structure 5.0 mol%, cyclopropane ring structure 0.1 mol%, 1,2 addition structure 0.1 mol%. 5
Mol%, 2.0 mol% for 1,4 addition structure, activity 13 kg
/ Mmol Zr · hr.

Table 4 also shows the results.

[0319]

[Table 4]

[0320]

Example A5 A 200 ml glass autoclave was sufficiently replaced with nitrogen, and 38 ml of toluene was mixed with the ethylene / propylene / 1,3-butadiene copolymer 6 obtained in Example A4.
g, and the temperature was raised to 140 ° C. while stirring. In a separate container, add 1.06 g of maleic anhydride and 0.1
A solution was prepared by dissolving 8 g of dicumyl peroxide in 8 ml of toluene. The prepared solution was dropped into the autoclave at a constant speed over 3.5 hours, and then stirred for another 30 minutes. During this dropping, the temperature was gradually raised to 160 ° C. After completion of the reaction, the mixture was cooled to 70 ° C., and the reaction solution was added to 200 ml of methanol to precipitate a polymer. The precipitated polymer is further treated with acetone 200
The resultant was washed with ml and vacuum-dried at 130 ° C. for 12 hours to obtain a graft-modified ethylene / propylene / 1,3-butadiene copolymer. The resulting modified product had a maleic anhydride content of 3.5.
% By weight. The intrinsic viscosity [η] of the modified product measured at 135 ° C. in decalin was 1.8 dl / g.

[0321]

Example A6 <Production of vulcanized rubber> The copolymer produced in Example A4, zinc white, stearic acid, HAF carbon black (HAF Asahi # 70TM (manufactured by Asahi Carbon Co., Ltd.)), dicumyl peroxide ( DCP-40C) were added in the following amounts, respectively, and an open roll (front roll / rear roll: 5) was added.
(0/60 ° C., 16/18 rpm) to obtain an unvulcanized compounded rubber. (Blending composition) Copolymer produced in Example A4: 100 parts by weight Zinc flower: 5 parts by weight Stearic acid: 1 part by weight HAF carbon black: 50 parts by weight Dicumyl peroxide (DCP-40C): 7 parts by weight The unvulcanized compounded rubber thus obtained is heated to 170 ° C.
Was heated by a press heated for 15 minutes to produce a vulcanized sheet, and a tensile test, a hardness test, and a compression set test were performed under the conditions described above.

The tensile strength TB (MPa) was 18, elongation EB (%) was 200, and hardness HS (JIS A)
Was 72, and the compression set CS (%) was 13.
The results are shown in Table 5.

[0323]

Comparative Example A1 In Example A6, an ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (ethylene / propylene) was used without using the copolymer (in Table 4) obtained in Example A4. = 73/27 (molar ratio), iodine value 18 g / 100 g, [η] 1.85), except that Example A6 was used.

The tensile strength TB (MPa) was 18, elongation EB (%) was 230, and hardness HS (JIS A)
Was 69 and the compression set CS (%) was 20.
The results are shown in Table 5.

[0325]

[Table 5]

[0326]

Example A7 4400 ml of propylene (25 ° C., 1
Atmospheric pressure), 1,3-butadiene to 7 g, catalyst solution to 0.045 ml, reaction time 15 minutes, reaction temperature 2
The same operation as in Example A1 was performed except that the temperature was changed to 0 ° C. The yield of the obtained ethylene-propylene-butadiene copolymer was 2.9 g, the intrinsic viscosity [η] measured in decalin at 135 ° C was 2.5 dl / g, the glass transition temperature Tg was -43 ° C, and the iodine value (I V) is 25.1 g / 100 g,
The ethylene content is 71.4 mol% and the propylene content is 2
0.1 mol%, 5-ring structure is 5.3 mol%, cyclopropane ring structure is 0.2 mol%, 1,2 addition structure is 0.7 mol%, 1,4 addition structure is 2.3 mol%. The activity is 13kg /
Mmol Zr · hr.

[0327]

Example A8 (Production of vulcanized rubber) The copolymer produced in Example A7, zinc white, stearic acid, HAF carbon black (HAF Asahi # 70 ^™ (manufactured by Asahi Carbon Co., Ltd.)), dicumyl peroxide (DCP-40C) was added in the following amount and an open roll (front roll / rear roll: 50/60)
At 16/18 rpm) to obtain an unvulcanized compounded rubber.

Copolymer: 100 parts by weight Zinc white flower: 5 parts by weight Stearic acid: 1 part by weight HAF carbon black: 50 parts by weight DCP-40C: 7 parts by weight Unvulcanized compounded rubber obtained as described above 170 ° C
Was heated by a press heated for 15 minutes to produce a vulcanized sheet, and the following test was conducted.

Table 6 shows the results. This sheet is suitable for use as a glass run channel. Further, the unvulcanized rubber was separated by adjusting the roll gap to 1 mm, and 2
Crosslinking was performed for 10 minutes in an oven heated to 20 ° C., and the surface was solid. Table 6 shows the results.

[0330]

[Table 6]

[0331]

Example A9 70 parts by weight of the unsaturated copolymer rubber produced in Example A4 and polypropylene (PP, trade name "J
700 "(manufactured by Mitsui Chemicals, Inc.) in a nitrogen atmosphere at 180 ° C. for 5 minutes using a Banbury mixer.
After kneading for a minute, the kneaded material was passed through a roll to form a sheet, and then cut with a sheet cutter to produce square pellets.

With respect to 100 parts by weight of the square pellets, 0.1 of divinylbenzene (hereinafter, also referred to as “DVB”).
Parts by weight and 0.15 parts by weight of 2.5-dimethyl-2.5- (tert-butylperoxy) hexane (hereinafter also referred to as “POX”) were mixed and stirred and mixed with a Henschel mixer.

Next, the mixture was subjected to a Labo Plastomill (Model 20R200, manufactured by Toyo Seiki Seisaku-sho, Ltd.)
200 ° C., 5 minutes, nitrogen atmosphere, rotation speed 100 rpm
To obtain an olefin-based thermoplastic elastomer composition.

The obtained olefinic thermoplastic elastomer composition was molded by a press heated to 200 ° C. to obtain a square plate of 2 × 80 × 80 mm. (Oil resistance test) A test piece of 2 × 10 × 10 mm was punched out of the obtained square plate, and the initial volume (V0) was obtained by using a volume measuring instrument of a dipping type in water.

The test piece was heated to 70 ° C. according to JIS-1
After immersion in No. oil for 3 days, the temperature was returned to room temperature, and the volume (V) after swelling was determined in the same manner. From these values, the following formula:
The degree of swelling (ΔV) was measured by “{V (%) = {(V−V0) / V0} × 100”.

As a result, the degree of swelling (ΔV) was 98 (%).
It became.

[0337]

Comparative Example A2 A composition ratio of ethylene / propylene / ENB (ethylidene norbornene) was 68.3 / 29.3 /
2.4 (mol), and the intrinsic viscosity [η] is 1.8 dl / g.
The same evaluation as in Example A9 was performed using an ENB-EPT copolymer (ethylene-propylene-ethylidene norbornene copolymer) having an iodine value of 18 g / 100 g.

As a result, the degree of swelling (ΔV) was 121
(%).

[0339]

Example B1 (Pre-Activation of Catalyst) 16.0 mg of isopropylidenebisindenyl zirconium dichloride synthesized by a known method was weighed into a glass container sufficiently purged with nitrogen.
A 1.484 mmol / ml solution of methylalumoxane in toluene (hereinafter abbreviated as MAO) was treated with 2 aluminum atoms.
15.2 ml was added to a concentration of 2.57 mmol, and ultrasonic irradiation was performed at 23 ° C. for 15 minutes to prepare a catalyst solution.

(Synthesis of Ethylene / Isoprene Copolymer)
At a room temperature, 177.2 ml of toluene and isoprene 1 were placed in a 2 liter autoclave dried under reduced pressure and purged with nitrogen.
17.5 ml were added, followed by 0.3 ml of a toluene solution of 1.0 mmol / ml of triisobutylaluminum (hereinafter abbreviated as MAO), and ethylene was fed under stirring to give 6 kg.
/ Cm ² G and then depressurized.
Repeated times. Then, it was made to reach 30 degreeC under ethylene normal pressure. Thereafter, the inside of the system was pressurized with ethylene to 6 kg / cm ² G, and 1.52 ml of the catalyst solution prepared in the catalyst pre-activation step was added to start copolymerization of ethylene and isoprene. The catalyst concentration at this time was 0.0123 mmol / L of isopropylidenebisindenyl zirconium dichloride and 7.5 mmol / L of MAO based on the whole system. During the polymerization, the internal pressure was maintained at 6 kg / cm ² G by continuously supplying ethylene. 30 minutes later,
The polymerization reaction was stopped by adding methyl alcohol.

After depressurization, the polymer solution was taken out and washed with an aqueous solution obtained by adding 5 ml of concentrated hydrochloric acid to 1 liter of water at a ratio of 1: 1 to transfer a catalyst residue to an aqueous phase. After allowing this contact mixed solution to stand, the aqueous phase is separated and removed.
Further, the resultant was washed with distilled water twice, and the polymerization liquid phase was separated into oil and water.

Next, the polymer liquid phase separated from the oil and water was brought into contact with 3 times the volume of acetone under vigorous stirring to precipitate a polymer, which was thoroughly washed with acetone, and a solid portion (copolymer) was collected by filtration. did. 130 ° C, 350mmHg under nitrogen flow
For 12 hours. The yield of the ethylene / isoprene copolymer obtained as described above was 47 g, the intrinsic viscosity [η] measured in decalin at 135 ° C. was 1.5 dl / g, the glass transition temperature Tg was −30 ° C., and the iodine value was 27g / 100
g, ethylene content: 97 mol%, ring structure: 1.5 mol%, 1,2 addition structure: 0.04 mol%, 3,4 addition structure: 0.96 mol%, 1,4 addition structure: 0.4 mol%. The activity was 5 kg%, and the activity was 26 kg / mmol Zr · hr.

The results are shown in Table 7.

[0344]

Example B2 In Example B1, propylene was added at 55%.
Add 00ml (25 ° C, 1 atm) and add 60ml of isoprene
Then, the same operation as in Example B1 was performed except that the reaction temperature was changed to 20 ° C. The yield of the obtained ethylene / propylene / isoprene copolymer was 18.8 g, the intrinsic viscosity [η] measured in decalin at 135 ° C. was 1.4 dl / g, the glass transition temperature Tg was −40 ° C., and the iodine value was 15 g. / 100g,
The ethylene content is 68.8 mol% and the propylene content is 25.
7 mol%, the ring structure is 3.5 mol%, the 1,2 addition structure is 0.1 mol%.
05 mol%, 3,4 addition structure is 1.25 mol%, 1,4
The additional structure is 0.7 mol% and the activity is 10 kg / mmol Zr.
Hr.

The results are shown in Table 7.

[0346]

Example B3 A 200 ml glass autoclave was sufficiently substituted with nitrogen, 38 ml of toluene and 6 g of the ethylene / propylene / isoprene copolymer obtained in Example B2 were charged, and the temperature was raised to 140 ° C. while stirring. . In a separate container, a solution was prepared by dissolving 1.06 g of maleic anhydride and 0.18 g of dicumyl peroxide in 8 ml of toluene. Place the prepared solution in an autoclave for 3.
The solution was added dropwise at a constant speed over 5 hours, and the mixture was further stirred for 30 minutes. During this dropping, the temperature was gradually raised to 160 ° C. After completion of the reaction, the mixture was cooled to 70 ° C., and the reaction solution was added to 200 ml of methanol to precipitate a polymer. The precipitated polymer was further washed with 200 ml of acetone and vacuum-dried at 130 ° C. for 12 hours to obtain a graft-modified ethylene / propylene / isoprene copolymer. The resulting modified product had been modified with maleic anhydride at 3.5% by weight.
The intrinsic viscosity [η] of the denatured product measured at 135 ° C. in decalin was 1.4 dl / g.

[0347]

[Table 7]

[0348]

Example B4 (Production of vulcanized rubber) The copolymer produced in Example B2, zinc white, stearic acid, HAF carbon black (HAF Asahi # 70TM (manufactured by Asahi Carbon Co., Ltd.)), and a vulcanization accelerator MBT (Suncellar MBT (manufactured by Sanshin Chemical Co., Ltd.)), vulcanization accelerator TMTD (Suncellar TT (manufactured by Sanshin Chemical Co., Ltd.)) and sulfur were added in the following amounts and an open roll (front roll / rear roll: 50) was added. / 60 ° C, 16/18 rpm) to obtain an unvulcanized compounded rubber.

Copolymer of Example B2: 100 parts by weight Zinc white flower: 5 parts by weight Stearic acid: 1 part by weight HAF carbon black: 50 parts by weight Vulcanization accelerator MBT: 0.5 part by weight Vulcanization accelerator TMTD: 1.0 parts by weight Sulfur: 1.5 parts by weight The unvulcanized compounded rubber obtained as described above is heated to 160 ° C.
Was heated for 20 minutes by a press heated to produce a vulcanized sheet, and a tensile test, a hardness test, and a compression set test were performed under the conditions described above.

The tensile strength TB (MPa) is 20, elongation EB (%) is 270, and hardness HS (JIS A)
Was 76. Table 8 also shows the results.

[0351]

Comparative Example B1 In Example B4, ethylene-propylene / 5- was used without using the copolymer produced in Example B2.
Vinyl-2-norbornene copolymer rubber (ethylene / propylene = 71/29 (molar ratio), iodine value 9 g / 100 g,
Example B4 except that [η] 2.12 dl / g) was used.
As a result, vulcanization was not possible, and physical properties could not be measured.

The results are shown in Table 8.

[0353]

[Table 8]

[0354]

Example B5 The oil resistance was tested in the same manner as in Example A9, except that the rubber of Example B2 was used.

As a result, ΔV (%) was 102%.

[0356]

Comparative Example B2 In Example B5, the composition ratio of ethylene / propylene / ENB was 70.2 / 27.9 / 1.9.
(Molar ratio), using an ENB-EPT copolymer (formal name: ethylene-propylene-ethylidene norbornene copolymer) having an intrinsic viscosity [η] of 1.5 dl / g and an iodine value of 15 g / 100 g, Oil resistance was tested in the same manner as in Example B5.

As a result, ΔV (%) was 125%.

[0358]

Example B6 40 g of the ethylene / isoprene copolymer obtained in Example B1 was sampled, and 2.5-dimethyl-2,2
0.04 g of 5-ditertbutylperoxyhexane
Mix and mix at 100 rpm and 200 ° C.
Kneaded for minutes and allowed to crosslink.

The crosslinked product had a HAZE of 12%, a temperature as an index of heat resistance of 115 ° C., and a Young's modulus (YM) of 98M.
Pa and Martens hardness were 10.6 mm ^-1 . In the case of the ethylene / isoprene copolymer before crosslinking, its HAZE is 10%, and the temperature as an index of heat resistance is 112%.
° C, YM is 94MPa, Martens hardness is 9.6mm
^-1 .

The methods for measuring these physical properties are as follows. HAZE (%): Formed into a sheet having a thickness of 1.0 mm, and measured using a digital turbidimeter DH-20D manufactured by Nippon Denshoku Industries.

Martens hardness (/ mm): The film was torn by a Martens tear hardness tester, and the reciprocal of the tear width was read. Heat resistance test: 2 m in accordance with "JIS K 7196"
a load of ² kg / cm ^{2 on} a sample thickness of m
The temperature is raised at a rate of 5 ° C./min, and TMA (thermomechan
ical analysis) The penetration temperature was determined from the curve and used as an index of heat resistance.

Young's modulus (MPa): A dumbbell of JIS No. 3 was set at a distance of 30 mm between chucks, and measured at room temperature (23 ° C.) at a tensile speed of 30 mm / min.

[0363]

Example C1 (Pre-activation of catalyst) (Dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane) synthesized by a known method in a glass container sufficiently purged with nitrogen. Weigh 13.5 mg of titanium dichloride,
A catalyst solution was prepared by adding 22.86 ml of a toluene solution of methylalumoxane (hereinafter abbreviated as MAO) at a concentration of 22.86 mmol of aluminum atoms at 23 ° C. for 15 minutes at 23 ° C.

(Synthesis of Ethylene-Butadiene-Styrene Copolymer) To a 2-liter autoclave which had been dried under reduced pressure and purged with nitrogen, 440.6 ml of toluene and 30 ml of styrene were added at room temperature, and then 6 kg / ethylene was stirred.
After pressurization to cm ² G, the pressure was released, and this pressure release operation was repeated three times. Thereafter, 18 ml of 1,3-butadiene (25 ° C., 1 atm) was added under ethylene normal pressure to reach 30 ° C. After that, the inside of the system was pressurized with ethylene to 6 kg / cm ² G, 3.11 ml of the catalyst solution prepared in the above pre-activation step of the catalyst was added, and the copolymerization of ethylene, styrene and 1,3-butadiene was started. I let it. The catalyst concentration at this time was (dimethyl (t-butylamide) (tetramethyl-
η ⁵ -cyclopentadienyl) silane) dichloride titanium was 0.01 mmol / L, and MAO was 6.0 mmol / L. During the polymerization, the internal pressure was maintained at 6 kg / cm ² G by continuously supplying ethylene. After 15 minutes, the polymerization reaction was stopped by adding methyl alcohol. After depressurization, the polymer solution was taken out and used in a 1: 1 ratio with an aqueous solution obtained by adding 5 ml of concentrated hydrochloric acid to 1 liter of water.
And washed, and the catalyst residue was transferred to the aqueous phase.

After allowing the contact mixed solution to stand, the aqueous phase was separated and removed, and further washed twice with distilled water, and the polymerization liquid phase was separated into oil and water. Next, the polymer liquid phase separated from the oil and water was brought into contact with a three-fold amount of acetone under vigorous stirring to precipitate a polymer, which was thoroughly washed with acetone, and a solid part (copolymer) was collected by filtration. 130 ° C, 350mmH under nitrogen flow
g for 12 hours. The yield of the ethylene / styrene / 1,3-butadiene copolymer obtained as described above is 13
g, intrinsic viscosity [η] measured in decalin at 135 ° C. is 2.0 dl / g, glass transition temperature Tg is −30 ° C., iodine value is 22 g / 100 g, ethylene content is 86.7 mol%,
Styrene 4.0 mol%, 5-membered ring structure 5.9 mol%, cyclopropane ring structure 0.2 mol%, 1,2 addition structure 0.7 mol%, 1,4 addition structure 2.5 Mol%, activity 1
It was 0.4 kg / mmol Zr · hr.

Table 9 also shows the results.

[0367]

Example C2 4400 ml of propylene (25 ° C., 1 atm) were added, 13-ml of 1,3-butadiene and 5 ml of styrene were added.
The same operation as in Example C1 was performed except that the reaction temperature was changed to 20 ° C. to 0 ml. The obtained ethylene / propylene /
The yield of styrene / 1,3-butadiene copolymer is 9 g, 13
The intrinsic viscosity [η] measured in decalin at 5 ° C. is 2.1 dl /
g, the glass transition temperature Tg is -44 ° C, and the iodine value is 17.5.
g / 100 g, ethylene content 63.6 mol%, propylene content 23.7 mol%, styrene content 5.4 mol%,
The 5-membered ring structure is 4.8 mol%, and the cyclopropane ring structure is 0.8 mol%.
1 mol%, 1,2 addition structure 0.5 mol%, 1,4 addition structure 1.9 mol%, activity 7.2 kg / mmol Zr · h
r.

Table 9 also shows the results.

[0369]

Example C3 A 200 ml glass autoclave was sufficiently substituted with nitrogen, and 38 ml of toluene and 6 g of the ethylene / propylene / styrene / 1,3-butadiene copolymer obtained in Example C2 were charged and stirred. The temperature was raised to 140 ° C. In a separate container, add 1.06 g of maleic anhydride and
A solution was prepared by dissolving 18 g of dicumyl peroxide in 8 ml of toluene. The prepared solution was dropped into the autoclave at a constant speed over 3.5 hours, and then stirred for another 30 minutes. During this dropping, the temperature was gradually raised to 160 ° C. After the reaction is completed, cool to 70 ° C and
The reaction solution was added to methanol to precipitate a polymer. The precipitated polymer was further washed with 200 ml of acetone and vacuum-dried at 130 ° C. for 12 hours to obtain a graft-modified ethylene / propylene / styrene / 1,3-butadiene copolymer. The resulting modified product had a maleic anhydride content of 3.
It had been modified by 5% by weight. The intrinsic viscosity [η] of the denatured product measured in decalin at 135 ° C. was 2.0 dl / g.

[0370]

[Table 9]

[0371]

Example C4 <Production of vulcanized rubber> The copolymer produced in Example C2, zinc white, stearic acid, HAF carbon black (HAF Asahi # 70TM (manufactured by Asahi Carbon Co., Ltd.)), dicumyl peroxide ( DCP-40C) were added in the following amounts, respectively, and an open roll (front roll / rear roll: 5) was added.
(0/60 ° C., 16/18 rpm) to obtain an unvulcanized compounded rubber. (Blending composition) Copolymer produced in Example C2: 100 parts by weight Zinc flower: 5 parts by weight Stearic acid: 1 part by weight HAF carbon black: 50 parts by weight Dicumyl peroxide (DCP-40C): 7 parts by weight The unvulcanized compounded rubber thus obtained is heated to 170 ° C.
Was heated by a press heated for 15 minutes to produce a vulcanized sheet, and a tensile test, a hardness test, and a compression set test were performed under the conditions described above.

The tensile strength TB (MPa) was 21, elongation EB (%) was 210, and hardness HS (JIS A)
Was 72, and the compression set CS (%) was 14.
Table 10 also shows the results.

[0373]

Comparative Example C1 In Example C4, an ethylene / propylene / styrene / 5-ethylidene-2-norbornene copolymer rubber (ethylene copolymer) was used without using the copolymer obtained in Example C2 (in Table 9). / Propylene = 74/26 (molar ratio), styrene content = 4.6 mol%, iodine value 18 g /
100 g, [η] 1.45), except that 100 g of [η] was used.

The tensile strength TB (MPa) was 20, elongation EB (%) was 260, and hardness HS (JIS A)
Was 70 and the compression set CS (%) was 22.
Table 10 also shows the results.

[0375]

[Table 10]

[0376]

Example C5 <Synthesis of ethylene / propylene / styrene / 1,3-butadiene copolymer> 3900 ml of propylene (25 ° C., 1
Atmospheric pressure), the same operation as in Example C1 was performed, except that the catalyst solution was changed to 1.56 ml and the reaction temperature was changed to 20 ° C.

The yield of the obtained ethylene / propylene / styrene / 1,3-butadiene copolymer was 4.2 g, 135 ° C.
The intrinsic viscosity [η] measured in decalin is 2.5 dl /
g, the glass transition temperature Tg is -42 ° C, and the iodine value is 21 g /
100 g, ethylene content 67.8 mol%, propylene content 18.9 mol%, styrene content 5.4 mol%,
The 5-membered ring structure is 4.8 mol%, the cyclopropane ring structure is 0.1 mol%, the 1,2 addition structure is 0.5 mol%,
The additional structure was 1.9 mol%, and the activity was 7.2 kg / mmol Zr · hr. <Production of vulcanized rubber> Ethylene / propylene / styrene / 1,3-butadiene copolymer produced as described above, zinc white, stearic acid, HAF carbon black (HAF
Asahi # 70TM (manufactured by Asahi Carbon Co., Ltd.) and dicumyl peroxide (DCP-40C) are added in the following amounts and an open roll (front roll / rear roll: 50/60 ° C, 16
/ 18 rpm) to obtain an unvulcanized compounded rubber.

Ethylene / propylene / styrene / 1,3-butadiene copolymer: 100 parts by weight Zinc white flower: 5 parts by weight Stearic acid: 1 part by weight HAF carbon black: 50 parts by weight DCP-40C: 7 parts by weight As described above. The unvulcanized compounded rubber obtained at 170 ° C
The mixture was heated by a press heated for 15 minutes to produce a vulcanized sheet. The tensile strength TB (MPa) of this sheet is 2
3, the elongation EB (%) is 230, and the hardness HS
(JIS A) was 76, compression set CS (%) was 12, and there was no surface solid.

This sheet is suitable for use as a glass run channel.

Further, the unvulcanized rubber was separated by adjusting the roll gap to 1 mm, and crosslinked in an oven heated to 220 ° C. for 10 minutes.

Table 11 also shows the results.

[0382]

[Table 11]

[0383]

Example C6 An ethylene / styrene / butadiene copolymer was prepared in the same manner as in Example C1, except that the catalyst was changed to isopropylidene-bis (indenyl) zirconium dichloride synthesized by a known method. Obtained.

The yield of the obtained ethylene / styrene / butadiene copolymer was 2.5 g, the intrinsic viscosity [η] measured in decalin at 135 ° C. was 1.1 dl / g, the glass transition temperature Tg was -25 ° C., and iodine was used. The value is 15 g / 100 g, the ethylene content is 88.0 mol%, the styrene content is 4.5 mol%,
The 5-membered ring structure is 4.8 mol%, the cyclopropane ring structure is 0.2 mol%, the 1,2 addition structure is 0.6 mol%, 1,4
1.9 mol% additional structure, activity 2 kg / mmol Zr
Hr.

[0385]

Example C7 The oil resistance was tested in the same manner as in Example A9, except that the rubber of Example C2 was used.

As a result, ΔV (%) was 91%.

[0387]

Comparative Example C2 In Example C7, the composition ratio of ethylene / propylene / styrene / ENB was 65.7 / 26.
ENB-E having a molar ratio of 7 / 5.3 / 2.3, an intrinsic viscosity [η] of 2.0 dl / g, and an iodine value of 18 g / 100 g.
The oil resistance was tested in the same manner as in Example C7, using a PT copolymer (official name: ethylene / propylene / ethylidene norbornene copolymer).

As a result, ΔV (%) was 112%.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08F 255/02 C08F 255/02 C08K 3/00 C08K 3/00 5/00 5/00 C08L 23/02 C08L 23/02 // (C08F 210/00 236: 04) (C08F 210/00 236: 04 212: 04) (C08F 210/02 236: 04) (C08F 210/02 236: 04 212: 04) (C08F 210/16 236: 04) ) (C08F 210/16 236: 04 212: 04)

Claims (33)

[Claims] 1. A copolymer comprising an α-olefin having 2 to 12 carbon atoms and a conjugated diene monomer represented by the following formula (Ia): (a) In the above, the conjugated diene monomer (I
The 1,2 adduct (including the 3,4 adduct) derived from -a) forms a double bond in the side chain in the copolymer, and the 1,4 adduct is a copolymer A double bond is formed in the main chain, and the ratio of the double bond of the side chain derived from the 1,2 adduct to the double bond of the main chain derived from the 1,4 adduct (1, Side chain double bond derived from 2-adduct / 1 main chain derived from 1,4-adduct
(B) has a five-membered ring in the main chain of the copolymer, and (c) a ratio of the double bond to the five-membered ring in all the adducts. (Total double bond / 5-membered ring of all adducts) 20/80 to 90/10; unsaturated copolymer; [In the formula (Ia), R ² is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group. ]. 2. The unsaturated copolymer according to claim 1, wherein the conjugated diene monomer is 1,3-butadiene. 3. The α-olefin is ethylene alone or a combination of ethylene and an α-olefin having 3 to 12 carbon atoms, and in this case, ethylene / α-olefin having 3 to 12 carbon atoms (molar Ratio) is 99/1 to 4
The unsaturated copolymer according to claim 1, wherein the ratio is 0/60. 4. The copolymer according to claim 1, wherein the copolymer contains structural units derived from a conjugated diene monomer in a total amount of 0.01 to 30 mol%. Saturable copolymer. 5. The copolymer has an iodine value of 1 to 50 g / 1.
2. The intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.01 to 10 dl / g, and the glass transition temperature Tg is 25 ° C. or lower. The unsaturated copolymer according to the above. 6. The copolymer according to any one of claims 1 to 5, wherein (i) an unsaturated carboxylic acid or a derivative thereof;
Graft-modified with at least one compound selected from the group consisting of aromatic vinyl compounds, and the amount of the unsaturated carboxylic acid or derivative thereof is 0.01
A modified unsaturated copolymer in the range of .about.30% by weight. 7. An unsaturated copolymer-based elastomer comprising (a) the copolymer according to claim 1 and (b) a crosslinking agent and / or a filler. Composition. 8. An unsaturated copolymer according to any one of claims 1 to 5, comprising an α-olefin having 2 to 12 carbon atoms and a compound represented by the formula (Ia)
When producing by copolymerizing at least one conjugated diene monomer represented by the following in the presence of a catalyst, the following components (a), (b), (c) and ( d) a method for producing an unsaturated copolymer, characterized by using at least one catalyst system comprising at least one compound selected from the group consisting of: (a): the following formula (II) or the following formula: Transition metal complex represented by (III) [In the formulas (II) and (III), M is Ti, Zr, Hf, N
d, Sm or Ru, and Cp1 and Cp2 are a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative group thereof bonded to M by π, and X
¹ and X ² are anionic ligands or neutral Lewis base ligands, Y is a ligand containing a nitrogen, oxygen, phosphorus, or sulfur atom, and Z is C, O ,
It is a B, S, Ge, Si or Sn atom or a group containing these atoms. (B): a compound that reacts with the transition metal M in the component (a) to form an ionic complex (c): an organoaluminum compound (d): alumoxane. 9. An unsaturated copolymer comprising an α-olefin having 2 to 12 carbon atoms and a conjugated diene monomer represented by the following formula (Ib): [In the formula (Ib), R ¹ is an alkyl group or an aryl group having 1 to 8 carbon atoms. ] 10. A copolymer comprising an α-olefin having 2 to 12 carbon atoms and a conjugated diene monomer represented by the above formula (Ib), wherein (a) the copolymer In the above, the conjugated diene monomer (I
The 1,2 adduct (including the 3,4 adduct) derived from -b) forms a double bond in the side chain in the copolymer, and the 1,4 adduct is a copolymer A double bond is formed in the main chain, and the ratio of the double bond of the side chain derived from the 1,2 adduct to the double bond of the main chain derived from the 1,4 adduct (1, Side chain double bond derived from 2-adduct / 1 main chain derived from 1,4-adduct
An unsaturated copolymer having a (heavy bond) ratio of 5/95 to 99/1. 11. A copolymer comprising an α-olefin having 2 to 12 carbon atoms and a conjugated diene monomer represented by the above formula (Ib), wherein (a) the copolymer In the above, the conjugated diene monomer (I
The 1,2 adduct (including the 3,4 adduct) derived from -b) forms a double bond in the side chain in the copolymer, and the 1,4 adduct is a copolymer A double bond is formed in the main chain, and the ratio of the double bond of the side chain derived from the 1,2 adduct to the double bond of the main chain derived from the 1,4 adduct (1, Side chain double bond derived from 2-adduct / 1 main chain derived from 1,4-adduct
(B) has a 5-membered ring in the main chain of the copolymer, and (c) a ratio of the double bond to the 5-membered ring of the above all adduct. (Total double bond of all adducts / 5-membered ring)
Is 20/80 to 90/10. 12. The unsaturated copolymer according to claim 9, wherein the conjugated diene monomer is isoprene. 13. The α-olefin is ethylene alone or a combination of ethylene and an α-olefin having 3 to 12 carbon atoms, in which case the ethylene / α-olefin having 3 to 12 carbon atoms (molar Ratio) is 99/1 ~
The unsaturated copolymer according to any one of claims 9 to 12, wherein the ratio is 40/60. 14. The copolymer according to claim 9, wherein the copolymer contains structural units derived from a conjugated diene monomer in a total amount of 0.01 to 30 mol%. Or an unsaturated copolymer described in the above. 15. An iodine value of the copolymer is 1 to 50 g / g.
100 g, the intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.01 to 10 dl / g,
The unsaturated copolymer according to any one of claims 9 to 14, wherein the glass transition temperature Tg measured by DSC is 25 ° C or lower. 16. An unsaturated copolymer elastomer comprising: (a) the copolymer according to any one of claims 9 to 15; and (b) a crosslinking agent and / or a filler. Composition. 17. The unsaturated copolymer according to claim 9, wherein the unsaturated copolymer is an α-olefin having 2 to 12 carbon atoms and the above formula (Ib)
When producing by copolymerizing at least one conjugated diene monomer represented by the following in the presence of a catalyst, the following components (a), (b), (c) and ( d) a method for producing an unsaturated copolymer, characterized by using at least one catalyst system comprising at least one compound selected from the group consisting of: (a): the following formula (II) or the following formula: Transition metal complex represented by (III) [In the formulas (II) and (III), M is Ti, Zr, Hf, N
d, Sm or Ru, and Cp1 and Cp2 are a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative group thereof bonded to M by π, and X
¹ and X ² are anionic ligands or neutral Lewis base ligands, Y is a ligand containing a nitrogen, oxygen, phosphorus, or sulfur atom, and Z is C, O ,
It is a B, S, Ge, Si or Sn atom or a group containing these atoms. (B): a compound that reacts with the transition metal M in the component (a) to form an ionic complex (c): an organoaluminum compound (d): alumoxane. 18. An unsaturated random copolymer comprising an α-olefin having 2 to 12 carbon atoms, an aromatic vinyl compound and a conjugated diene monomer. 19. A copolymer comprising an α-olefin having 2 to 12 carbon atoms, an aromatic vinyl compound and a conjugated diene monomer represented by the following formula (I), wherein (a) the copolymer: In the coalescence, 1,1 derived from the conjugated diene monomer (I)
The diadduct (including the 3,4 adduct) forms a double bond in the side chain of the copolymer, and the 1,4 adduct has a double bond in the main chain of the copolymer. And the ratio of the double bond of the side chain derived from the 1,2 adduct to the double bond of the main chain derived from the 1,4 adduct (the side chain 2 derived from the 1,2 adduct) Main chain 2 derived from heavy bond / 1,4 adduct
An unsaturated copolymer having a (heavy bond) of from 10/90 to 99/1; [In the formula (I), R ¹ and R ² each independently represent a hydrogen atom,
An alkyl group or an aryl group having 1 to 8 carbon atoms,
At least one of R ¹ and R ² is hydrogen. ]. 20. A copolymer comprising an α-olefin having 2 to 12 carbon atoms, an aromatic vinyl compound and a conjugated diene monomer represented by the above formula (I), wherein (a) the copolymer In the coalescence, 1,1 derived from the conjugated diene monomer (I)
The diadduct (including the 3,4 adduct) forms a double bond in the side chain of the copolymer, and the 1,4 adduct has a double bond in the main chain of the copolymer. And the ratio of the double bond of the side chain derived from the 1,2 adduct to the double bond of the main chain derived from the 1,4 adduct (the side chain 2 derived from the 1,2 adduct) Main chain 2 derived from heavy bond / 1,4 adduct
(B) has a five-membered ring in the main chain of the copolymer, and (c) a ratio of the double bond to the five-membered ring in all the adducts. (Total double bond / 5-membered ring of all adducts) is 20/80 to 90/10, and (d) a structural unit derived from an aromatic vinyl compound is contained in an amount of 0.1 to 60 mol%. An unsaturated copolymer, characterized in that: 21. The method according to claim 18, wherein the copolymer contains structural units derived from a conjugated diene monomer in a total amount of 0.01 to 30 mol%. Unsaturated copolymer. 22. The unsaturated copolymer according to claim 18, wherein the conjugated diene monomer is 1,3-butadiene. 23. The unsaturated copolymer according to claim 18, wherein the conjugated diene monomer is isoprene. 24. The α-olefin is ethylene alone or a combination of ethylene and an α-olefin having 3 to 12 carbon atoms.
When the α-olefin having 3 to 12 carbon atoms (molar ratio) is 99 /
24. The method according to claim 23, wherein the ratio is 1 to 40/60.
The unsaturated copolymer according to any one of the above. 25. The unsaturated copolymer according to claim 18, wherein the aromatic vinyl compound is styrene. (26) The copolymer has an iodine value of 1 to 50 g /
100 g, the intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.01 to 10 dl / g,
The unsaturated copolymer according to any one of claims 18 to 25, wherein the glass transition temperature Tg is 25 ° C or less. 27. The method according to claim 18, wherein the peak of the melting point (Tm) measured by DSC is 120 ° C. or lower.
7. The unsaturated copolymer according to any one of 6. 28. The unsaturated copolymer according to claim 18, grafted with at least one compound selected from the group consisting of unsaturated carboxylic acids or derivatives thereof and aromatic vinyl compounds. A modified copolymer which is modified and has a graft amount in the range of 0.01 to 30% by weight. 29. An unsaturated copolymer comprising: (a) the unsaturated copolymer according to any one of claims 18 to 27; and (b) a crosslinking agent and / or a filler. A polymer-containing elastomer composition. 30. The unsaturated copolymer according to claim 18, wherein the unsaturated copolymer is an α-olefin having 2 to 12 carbon atoms, an aromatic vinyl compound and the above formula (I). When producing by copolymerizing at least one conjugated diene monomer in the presence of a catalyst, the following components (a) and (b), (c) and (d) are used as the catalyst. A method for producing an unsaturated copolymer, characterized by using at least one catalyst system consisting of at least one compound selected from the group consisting of: (a) a compound represented by the following formula (II) or (III): Transition metal complex represented [In the formulas (II) and (III), M is Ti, Zr, Hf, N
d, Sm or Ru, and Cp1 and Cp2 are a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative group thereof bonded to M by π, and X
¹ and X ² are anionic ligands or neutral Lewis base ligands, Y is a ligand containing a nitrogen, oxygen, phosphorus, or sulfur atom, and Z is C, O ,
It is a B, S, Ge, Si or Sn atom or a group containing these atoms. (B): a compound that reacts with the transition metal M in the component (a) to form an ionic complex (c): an organoaluminum compound (d): alumoxane. 31. A crosslinked product obtained by crosslinking the composition according to any one of claims 7, 16 and 29. 32. The crosslinked product according to claim 31, wherein the crosslinking agent is an organic peroxide. 33. A film or sheet comprising the crosslinked product according to claim 31.