JPH10264325A - Molded product of vulcanized material having surface decorating layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable attainment of excellent adhesion to a surface decorating layer without conducting surface treatment, by providing the decorating layer on the surface of a vulcanized material of an unsaturated olefin copolymer constituted of ethylene, a specific aromatic vinyl compound, a non-conjugated polyene and α-olefin which is added as occasion demands. SOLUTION: An unsaturated olefin copolymer used for a molded body of a vulcanized material is a random copolymer of ethylene, an aromatic vinyl compound expressed by the formula (where R<1> , R<2> and R<3> denote alkyl groups which may be identical or different from one another and of which the number of hydrogen or carbon atoms is 1-8, or 1-3 preferably, and (n) denotes an integer of 0-5, or 0-3 preferably) and a non-conjugated polyene, or a random copolymer of ethylene, the aromatic vinyl compound expressed by the formula, the non- conjugated polyene and α-olefin of which the number of carbon atoms 3-20. As for a decorating layer, a coat of acrylic resin or the like can be mentioned.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vulcanizate molded article having a surface decorative layer, and more particularly, to excellent adhesion to a surface decorative layer such as a coating film and mechanical strength. The present invention relates to a vulcanized product having a surface decoration layer.

[0002]

BACKGROUND OF THE INVENTION Ethylene propylene copolymer rubber (EPR) and ethylene propylene diene copolymer rubber (EPDM) are widely used because they have no unsaturated bonds in the main chain of their molecular structure. Compared to conjugated diene rubbers, it has excellent heat resistance, weather resistance, and ozone resistance, and is widely used in applications such as automotive parts, electric wire materials, electric and electronic parts, building civil engineering materials, and industrial material parts. And in these applications, in order to improve the slidability of the design or the surface, it is necessary to apply urethane coating on the surface of the molded body or to bond other members such as metal and resin using an adhesive. is there. However, since EPR and EPDM do not contain a polar group in the molecule, they do not have a sufficient affinity for other resins, and are not suitable for applying surface decoration such as painting or bonding to other members on the surface of a molded product. For this purpose, it is necessary to improve the affinity of the surface of the molded body with other resins by performing pretreatments such as roughening, cleaning of the surface with an organic solvent, and primer treatment. Performing such pretreatment involves the problem of increasing equipment costs for the processing equipment, complicating the steps in the production of rubber products, and increasing the production cost because a considerable amount of time is required for the pretreatment. Also, rough surface processing is difficult for products having complicated shapes.

[0003] As means for solving the above problems,
For example, JP-A-6-306223 proposes to blend a polar resin-based tackifier as an adhesive (adhesion) improving agent for a surface decorative layer in an ethylene-propylene rubber compound. . However, when such a tackifier is incorporated into the ethylene / propylene rubber compound, there is a problem that the strength of the obtained vulcanized rubber is reduced.

[0004] Therefore, even when surface treatment such as surface roughening, surface cleaning with an organic solvent, and primer treatment is not performed, a rubber molded article having excellent adhesion to the surface decorative layer and excellent mechanical strength. The emergence of is desired.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art as described above, and in the case where surface treatment such as roughening, surface cleaning with an organic solvent, and primer treatment is not performed. It is an object of the present invention to provide a vulcanizate molded article having a surface decorative layer having excellent adhesion to a surface decorative layer and excellent mechanical strength.

[0006]

SUMMARY OF THE INVENTION A vulcanizate molded article having a surface decorative layer according to the present invention comprises (i) ethylene, (ii) an aromatic vinyl compound represented by the following formula (I), and (iii) non- A decorative layer is provided on the surface of a vulcanized product of (A) an unsaturated olefin copolymer obtained from a conjugated polyene and, if necessary, (iv) an α-olefin having 3 to 20 carbon atoms. It is characterized by becoming.

[0007]

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(Wherein R ¹ , R ² and R ³ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and n is an integer of 0 to 5) The vulcanized product is (A) the unsaturated olefin-based copolymer, (B) a vulcanizing agent, (C) a reinforcing material, and (D)
It may be a vulcanizate of an unsaturated olefin copolymer composition comprising at least one compounding agent selected from liquid softeners.

In the present invention, (iii) the non-conjugated polyene is represented by the following general formula (II-a), and the structural unit derived from the non-conjugated polyene is represented by the following general formula (II-b) A compound represented by the following general formula (III-a):
In addition, at least one kind of non-conjugated triene or tetraene whose structural unit derived from the non-conjugated polyene is selected from compounds represented by the following general formula (III-b) can be given.

[0010]

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(Wherein p and q may be the same or different and are 0 or 1 (provided that p and q are not simultaneously 0), and f is an integer of 0 to 5 (provided that ,
g is an integer of 1 to 6; R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different even if p and q are both 1; May represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁸ represents an alkyl group having 1 to 5 carbon atoms, R ⁹ represents a hydrogen atom or 1 to 5 carbon atoms. An alkyl group or-(C
^{_{H 2) n -CR 10 = CR}} 11 group represented by R ¹² (wherein, n
Is an integer of 1 to 5, R ¹⁰ and R ¹¹ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ¹² has 1 to 5 carbon atoms. 5
(Where p and q are both 1, R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). )

[0012]

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(Where p, q, f, g, R ^{1 to} R ⁹ are
It has the same meaning as in the case of the general formula (II-a). )

[0014]

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(Where p, q, f, g, R ^{1 to} R ⁹ are
It has the same meaning as in the case of the general formula (II-a). )

[0016]

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(Where p, q, f, g, R ^{1 to} R ⁹ are
It has the same meaning as in the case of the general formula (II-a). The non-conjugated triene or tetraene represented by the general formula (II-a) is represented by the following general formula (IV-a), and a structural unit derived from the non-conjugated triene or tetraene is represented by the following general formula (IV-a). Preferably, the non-conjugated triene or tetraene represented by the general formula (III-a) is represented by the following general formula (V-a). Is preferably a compound represented by the following general formula (V-b).

[0018]

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Wherein f is an integer of 0 to 5, and g is 1
R ¹ , R ² , R ⁵ , R ⁶ and R
⁷ may be the same or different, and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R ⁸ represents an alkyl group having 1 to 5 carbon atoms; R ⁹ represents a hydrogen atom; An alkyl group having 1 to 5 carbon atoms or-(C
^{_{H 2) n -CR 10 = CR}} 11 group represented by R ¹² (wherein, n
Is an integer of 1 to 5, R ¹⁰ and R ¹¹ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ¹² has 1 to 5 carbon atoms. 5
Represents an alkyl group). )

[0020]

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(Where f, g, R ¹ , R ² , R ⁵ -R ⁹
Has the same meaning as in the above formula (IV-a). )

[0022]

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Wherein f, g, R ¹ , R ² , R ⁵ -R ⁹
Has the same meaning as in the above formula (IV-a). )

[0024]

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Where f, g, R ¹ , R ² , R ⁵ -R ⁹
Has the same meaning as in the above formula (IV-a). In the present invention, the (iii) non-conjugated polyene is represented by the general formula (II-a) and the structural unit derived from the non-conjugated polyene is a compound represented by the general formula (II-b) It is preferably at least one selected from non-conjugated trienes and tetraenes. Particularly, the structural unit represented by the general formula (IV-a) and derived from the non-conjugated polyene is represented by the general formula (IV-b). It is preferably at least one non-conjugated triene or tetraene selected from the compounds to be prepared.

The unsaturated olefin copolymer has a constitutional unit derived from ethylene (i) and a carbon number of 3 to 3.
The molar ratio (ethylene / α-olefin) to the structural unit derived from α-olefin (iv) is 100/0 to 4
Α / olefin (iv) having a constitutional unit derived from ethylene (i) and having 3 to 20 carbon atoms, which is in the range of 0/60.
And the molar ratio of the structural unit derived from the aromatic vinyl compound (ii) to the total amount of the structural unit derived from
α-olefin / aromatic vinyl compound) is 99.5 /
It is preferably in the range of 0.5 to 60/40.

The unsaturated olefin-based copolymer preferably has an intrinsic viscosity [η] measured at 135 ° C. in decalin in the range of 0.8 to 5.0 dl / g.
In the present invention, as the decorative layer, an acrylic resin-based paint,
A coating film obtained from one kind of paint selected from the group consisting of an epoxy resin paint, a polyester resin paint, a urethane resin paint, and an alkyd resin paint is exemplified.

[0028]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a vulcanized product having a surface decorative layer according to the present invention will be specifically described.

The vulcanizate molded article having a surface decorative layer according to the present invention is a molded article comprising a vulcanizate of a specific unsaturated olefin copolymer (A) and a decorative layer provided on the surface. Alternatively, an unsaturated resin comprising a specific (A) unsaturated olefin copolymer and at least one compounding agent selected from (B) a vulcanizing agent, (C) a reinforcing material, and (D) a liquid softener. This is a molded article in which a decorative layer is provided on the surface of a vulcanized product of the olefin copolymer composition. First, each component used in the vulcanized product having the surface decorative layer according to the present invention will be described.

(A) Unsaturated olefin-based copolymer (A) Unsaturated olefin-based copolymer comprises (i) ethylene, (ii) an aromatic vinyl compound represented by the following formula (I), iii) a random copolymer with a non-conjugated polyene, or (i) ethylene and (ii) an aromatic vinyl compound represented by the following formula (I), (iii) a non-conjugated polyene and (iv) 3 carbon atoms. ~ 20 alpha-olefins.

(Ii) As the aromatic vinyl compound, specifically, a compound represented by the following general formula (I) is used.

[0032]

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In the formula, R ¹ , R ² and R ³ may be the same or different and represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Is an alkyl group.

N is an integer of 0 to 5, preferably 0 to 3. Examples of the aromatic vinyl compound as described above include styrene, methylstyrene, dimethylstyrene, mono- or polyalkylstyrene such as ethylstyrene,
Methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, chlorostyrene, functional group-containing styrene derivatives such as divinylbenzene, allylbenzene, 4-phenylbutene-1,3-phenylbutene- 1, 4- (4-
Methylphenyl) butene-1,4- (3-methylphenyl) butene-1,4- (2-methylphenyl) butene-1,4- (4-ethylphenyl) butene-1,4- (4-butylphenyl ) Butene
-1,5-phenylpentene-1,4-phenylpentene-1,3-
Phenylpentene-1,5- (4-methylphenyl) pentene
-1,4- (2-methylphenyl) pentene-1,3- (4-methylphenyl) pentene-1,6-phenylhexene-1,5-phenylhexene-1,4-phenylhexene-1,3- Phenylhexene-1,6- (4-methylphenyl) hexene-1,5- (2-
Methylphenyl) hexene-1,4- (4-methylphenyl)
Hexene-1,3- (2-methylphenyl) hexene-1,7-phenylheptene-1,6-phenylheptene-1,5-phenylheptene-1,4-phenylheptene-1,8- Phenyloctene-1, 7-phenyloctene-1, 6-phenyloctene-1,
Examples include phenyl-substituted alkenes such as 5-phenyloctene-1, 4-phenyloctene-1, 3-phenyloctene-1, and 10-phenyldecene-1.

Of these aromatic vinyl compounds, styrene, allylbenzene and 4-phenylbutene-1 are preferred, and styrene is particularly preferred. The aromatic vinyl compounds can be used alone or in combination of two or more.

(Iii) Non-conjugated polyenes include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene,
Diene compounds such as vinyl norbornene and 7-methyl-1,6-octadiene, non-conjugated triene or tetraene having one vinyl group per molecule, and 1 per molecule
Non-conjugated trienes or tetraenes having five 5-norbornen-2-yl groups. The total number of carbon atoms per non-conjugated triene or tetraene molecule (in the case of containing two or more non-conjugated trienes or tetraenes, the average number of carbon atoms is not particularly limited),
Preferably 9 to 30, more preferably 10 to 25,
Particularly preferably, the number is preferably 10 to 22. A non-conjugated triene or tetraene having a carbon atom number in such a range is advantageous because it is easy to handle such as purification. Here, "triene" means a hydrocarbon compound having three carbon-carbon double bonds (C = C) in one molecule, and "tetraene" means a carbon-carbon double bond in one molecule. Means a hydrocarbon compound having four. In addition,
The carbon-carbon double bond includes a carbon-carbon double bond of a vinyl group and a carbon-carbon double bond of a 5-norbornen-2-yl group.

The non-conjugated triene or tetraene includes three (in the case of a triene) or four (in the case of a tetraene) carbon-carbon double bond (C =) including a vinyl group or a 5-norbornen-2-yl group. C), but the total number of hydrogen atoms directly bonded to carbon atoms adjacent to all carbon-carbon double bonds contained in one molecule of this non-conjugated triene or tetraene is not particularly limited. But,
Preferably 9-33, more preferably 12-33,
Particularly preferably, the number is 14 to 33. It is preferable that the total number of hydrogen atoms be in such a range, since a copolymer having a high crosslinking reaction rate can be obtained. When the non-conjugated triene or tetraene used is a mixture of two or more, the number of hydrogen atoms is indicated by an average of the number of these hydrogen atoms.

In the present invention, among the non-conjugated triene or tetraene, a non-conjugated triene or tetraene in which a vinyl group or a 5-norbornen-2-yl group is bonded to a methylene group (-CH _2- ) is preferable.

Among such non-conjugated trienes or tetraenes, compounds represented by the following general formula (II-a) or the following general formula (III-a) are preferable.

[0040]

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In the formula, p and q may be the same or different and are 0 or 1 (provided that p and q are not simultaneously 0). f is an integer of 0 to 5, preferably an integer of 0 to 2 (however, when p and q are both 1, they are not 0).

G is an integer of 1 to 6, preferably 1 to 6.
It is an integer of 3. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶
And R ⁷ may be the same or different and represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms;
Preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, and R ⁷ is a hydrogen atom or a carbon atom number. Is an alkyl group of 1 to 3.

R ⁸ has a hydrogen atom or a carbon atom number of 1 to
5 represents an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

R ⁹ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a group represented by — (CH ₂ ) _n —CR ¹⁰ ＣＲCR ¹¹ R ¹² (where n is an integer of 1 to 5) in and, R ¹⁰ and R ¹¹ may be the same or different from each other, a hydrogen atom or a carbon atoms represents 1-5 alkyl group, R ¹²
Represents shown) an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom, or an alkyl group having a carbon number of 1 to 3 - represented by ^{_{(CH 2) n -CR 10 =}} CR 11 R 12 Wherein n is an integer of 1 to 3, R ¹⁰ and R
¹¹ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹² represents an alkyl group having 1 to 3 carbon atoms). However,
When both p and q are 1, R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0045]

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(Where p, q, f, g, R ^{1 to} R ⁹ are
It has the same meaning as in the case of the general formula (II-a). (Iii) the non-conjugated polyene has the general formula (II-a) or
When the non-conjugated triene or tetraene represented by (III-a) is used, the vulcanization rate is high and the obtained vulcanizate has excellent strength properties.

Specific examples of the non-conjugated triene or tetraene represented by the general formula (II-a) include the following compounds.

[0048]

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The non-conjugated triene or tetraene represented by the general formula (III-a) is specifically exemplified by the compound exemplified as the non-conjugated triene or tetraene represented by the general formula (II-a). Vinyl group is 5-norbornene
And compounds substituted with a 2-yl group.

Among the non-conjugated trienes or tetraenes represented by the general formula (II-a), the non-conjugated trienes or tetraenes represented by the following general formula (IV-a) are preferable.
This non-conjugated triene or tetraene is a compound in which p is 1 and q is 0 in the non-conjugated triene or tetraene represented by the general formula (II-a).

Further, among the non-conjugated triene or tetraene represented by the general formula (III-a), a non-conjugated triene or tetraene represented by the following general formula (V-a) is preferable. The non-conjugated triene or tetraene is a compound in which p is 1 and q is 0 in the non-conjugated triene or tetraene represented by the general formula (III-a).

[0052]

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In the formula, f is an integer of 0 to 5, preferably 0 to 2. g is an integer of 1 to 6,
Preferably it is an integer of 1-3. R ¹ , R ² , R ⁵ , R
⁶ and R ⁷ may be the same or different from each other,
The same as the general formula (II-a), preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably R ¹ , R ² , R ⁵ and R ⁶ are hydrogen atoms and R ⁷ Is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

R ⁸ is the same as in the above formula (II-a), and is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. is there.

R ⁹ is the same as in the above formula (II-a), and is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0056]

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(Where f, g, R ¹ , R ² , R ⁵ -R ⁹
Has the same meaning as in the above formula (IV-a). (Iii) the non-conjugated polyene has the general formula (IV-a) or
When the non-conjugated triene or tetraene represented by (Va) is used, the vulcanization rate is high, and the obtained vulcanizate has excellent strength properties.

Specific examples of the non-conjugated triene or tetraene represented by the general formula (IV-a) include the following compounds.

[0059]

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[0060]

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[0061]

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[0062]

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As the non-conjugated triene or tetraene represented by the general formula (V-a), specifically, the vinyl group of the compound exemplified as the non-conjugated triene or tetraene represented by the general formula (IV-a) With a 5-norbornen-2-yl group.

In the present invention, (iii) the non-conjugated polyene is
The compound represented by the general formula (II-a) is more preferable, and the compound represented by the general formula (IV-a) is particularly preferable.

(Iii) The non-conjugated polyene has the general formula (I
When the non-conjugated triene or tetraene represented by Ia) is used, the vulcanization rate is high and the obtained vulcanizate has excellent strength properties.

(Iii) The non-conjugated polyene has the general formula (I
When the non-conjugated triene or tetraene represented by Va) is used, the vulcanized product is particularly excellent in cold resistance, low-temperature properties, and vulcanization strength. The non-conjugated triene or tetraene may be a mixture of a trans form and a cis form, or may be a trans form alone or a cis form alone.

These (iii) non-conjugated polyenes can be used alone or in combination of two or more.
The non-conjugated triene or tetraene represented by the general formula (II-a) or (III-a) is, for example, EP0691
It can be prepared by a conventionally known method as described in 354A1 and WO96 / 20150.

(Iv) Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene and 3-methyl-1 -Pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene,
4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-
Dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl
-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-
Tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like, among which α-olefins having 4 or more carbon atoms are preferable, particularly 1-butene,
1-Hexene, 1-octene and 1-decene are preferred. These α-olefins can be used alone or in combination of two or more.

(A) The unsaturated olefin-based copolymer is
The structural unit derived from ethylene (i), the structural unit derived from the aromatic vinyl compound (ii), and the structural unit derived from the non-conjugated polyene (iii) are respectively randomly arranged and bonded, and (iii) The main chain has a branched structure derived from a conjugated polyene, and the main chain is derived from a copolymer having a substantially linear structure or a structural unit derived from ethylene (i) and an aromatic vinyl compound (ii). (Iii) a structural unit derived from the non-conjugated polyene (iii) and a structural unit derived from an α-olefin (3) having 3 to 20 carbon atoms are randomly arranged and bonded; A copolymer having a branched structure due to a non-conjugated polyene and having a substantially linear structure in the main chain. That this copolymer has a substantially linear structure and does not substantially contain a gel-like crosslinked polymer,
This can be confirmed by the fact that the copolymer is dissolved in an organic solvent and contains substantially no insoluble matter. For example, when the intrinsic viscosity [η] is measured, it can be confirmed by the fact that the copolymer is completely dissolved in decalin at 135 ° C.

(A) The unsaturated olefin-based copolymer is
The molar ratio (ethylene / α-olefin) of the structural unit derived from ethylene (i) to the structural unit derived from α-olefin having 3 to 20 carbon atoms (iv) is 100/0.
To 40/60, preferably 95/5 to 55/45, more preferably 90/10 to 60/40, even more preferably 80/20 to 60/40, and ethylene (i)
And the molar ratio of the structural unit derived from the aromatic vinyl compound (ii) to the total amount of the structural unit derived from the α-olefin (iv) having 3 to 20 carbon atoms and the structural unit derived from the aromatic vinyl compound (ii) -Olefin / aromatic vinyl compound)
Is 99.5 / 0.5-60 / 40, preferably 99/1
７０70/30, preferably 98 / 2２〜80 / 20.

A structural unit derived from ethylene (i),
Molar ratio with constituent units derived from α-olefin (iv) having 3 to 20 carbon atoms (ethylene / α-olefin)
Is in the range of 95/5 to 55/45, the resulting vulcanizate has excellent mechanical properties. Further, the vulcanizate obtained when the proportion of the structural unit derived from the aromatic vinyl compound (ii) is within the above range is excellent in coatability (coating film adhesion and the like), mechanical properties, and low-temperature properties.

In the unsaturated olefin copolymer (A), the content of the structural unit derived from the non-conjugated polyene (iii) is usually 0.01 to 30 mol%, preferably 0.05 to 25 mol%. , More preferably in the range of 0.1 to 20 mol%.

The iodine value of the unsaturated olefin copolymer (A) is usually from 5 to 35, preferably from 10 to 3
It is desirably within the range of 0, more preferably 10 to 25. (A) When the iodine value of the unsaturated olefin-based copolymer is within the above range, the vulcanization rate is high, and the obtained vulcanized product has poor coating properties, coating film adhesion strength, mechanical properties, and low-temperature properties. Excellent.

(A) The unsaturated olefin-based copolymer is
The intrinsic viscosity [η] measured in decalin at 135 ° C. is usually 0.1 to 6.0 dl / g, preferably 0.8 to 5.0 d.
1 / g, more preferably in the range of 1.5 to 4.0 dl / g. (A) When the intrinsic viscosity [η] of the unsaturated olefin-based copolymer is within the above range, the kneading property with the compounding agent is excellent.

In the present invention, (A) the unsaturated olefin-based copolymer preferably has at least one of the molar ratio of each structural unit, intrinsic viscosity [η] and iodine value within the above-mentioned range. It is more preferable that at least one of them is within the above range, and it is particularly preferable that all of the molar ratio, intrinsic viscosity [η] and iodine value of each structural unit are within the above range.

In the above (A) unsaturated olefin-based copolymer, (iii) the non-conjugated polyene has the general formula (I)
When represented by Ia), in the unsaturated olefin-based copolymer (A), the structural unit derived from the non-conjugated triene or tetraene has a structure represented by the following general formula (II-b) Have.

[0077]

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Wherein p, q, f, g, R ^{1 to} R ⁹ are
It has the same meaning as in the case of the general formula (II-a). Further, (iii) when the non-conjugated polyene is represented by the general formula (III-a), a structural unit derived from the non-conjugated triene or tetraene in the unsaturated olefin-based copolymer (A). Has a structure represented by the following general formula (III-b).

[0079]

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(Where p, q, f, g, R ^{1 to} R ⁹ are
It has the same meaning as in the case of the general formula (II-a). Further, (iii) the non-conjugated polyene has the general formula (IV-a)
When represented by the formula, in the unsaturated olefin-based copolymer (A), the structural unit derived from the non-conjugated triene or tetraene has a structure represented by the following general formula (IV-b) ing.

[0081]

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Where f, g, R ¹ , R ² , R ⁵ -R ⁹
Has the same meaning as in formula (IV-a). And (iii) when the non-conjugated polyene is represented by the general formula (V-a), in the unsaturated olefin-based copolymer (A), a structural unit derived from the non-conjugated triene or tetraene. Has a structure represented by the following general formula (V-b).

[0083]

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Where f, g, R ¹ , R ² , R ⁵ -R ⁹
Has the same meaning as in formula (IV-a). Note that (iii) the structural unit derived from the non-conjugated polyene is
The fact that the unsaturated olefin copolymer (A) has each of the above structures can be confirmed by measuring the ¹³ C-NMR spectrum of the copolymer.

Production of unsaturated olefin copolymer (A)
The unsaturated olefin copolymer (A) as described above is
(I) ethylene, (ii) an aromatic vinyl compound, and (ii)
It is obtained by copolymerizing i) a non-conjugated polyene and, if necessary, (iv) an α-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst.

Examples of such olefin polymerization catalysts include (a) a compound of a transition metal such as vanadium, zirconium and titanium, and (b) an organoaluminum compound (organoaluminum oxy compound) and / or an ionized ionic compound. Can be used.
Specifically, a titanium catalyst comprising a solid titanium catalyst component and an organoaluminum compound, a vanadium catalyst comprising a soluble vanadium compound and an organoaluminum compound, a transition metallocene compound selected from Group 4 of the periodic table, and And a metallocene catalyst comprising an organic aluminum oxy compound and / or an ionized ionic compound. Of these, a metallocene catalyst is particularly preferable.

The Periodic Table No. 4 for Forming Metallocene Catalysts
The transition metal metallocene compound selected from the group is specifically represented by the following formula (VI). M ¹ L ¹ _x (VI) In the formula, M is a transition metal selected from Group 4 of the periodic table, and is specifically zirconium, titanium or hafnium. x represents the valence of the transition metal M, and represents the number of ligands L coordinated to the transition metal.

L is a ligand coordinated to a transition metal, and at least one of the ligands L is a cyclopentadienyl group, an indenyl group, 4,5,6,7-tetrahydroindenyl Group, a ligand having a cyclopentadienyl skeleton such as a fluorenyl group, and the ligand having a cyclopentadienyl skeleton includes a substituent such as an alkyl group, a cycloalkyl group, a trialkylsilyl group, or a halogen atom. May be provided.

When the metallocene compound has two or more groups having a cyclopentadienyl skeleton as the ligand L, two of the groups having the cyclopentadienyl skeleton are an alkylene group or a substituted alkylene group. , A silylene group, a substituted silylene group or the like.

L other than the ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a sulfonic acid-containing group (—SO ₃ R ^a , ^Ra is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, an aryl group substituted with a halogen atom or an aryl group substituted with an alkyl group.), A halogen atom, a hydrogen atom, and the like.

The following is an example of a metallocene compound in which M is zirconium and contains two ligands having a cyclopentadienyl skeleton. Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (1-methyl-3-butylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (1, 3-dimethylcyclopentadienyl) zirconium dichloride, ethylene-bis (indenyl) dimethyl zirconium, ethylene-bis (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl
-Fluorenyl) zirconium dichloride, diphenylsilylene-bis (indenyl) zirconium dichloride, methylphenylsilylene-bis (indenyl) zirconium dichloride, rac-ethylene-bis (2-methyl-1-
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.

Further, metallocene compounds in which zirconium metal is replaced with titanium metal or hafnium metal in the above compounds can also be exemplified.

Further, as a bridge type metallocene compound, a metallocene compound represented by the following formula [A] can be mentioned. The metallocene has the formula [A]:

[0094]

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[A] [In the formula [A], M ¹ is a metal of Group IVB of the periodic table, and specifically, for example, titanium, zirconium,
Hafnium can be mentioned.

R ¹ and R ² may be the same or different from each other and include a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms;
~ 3 alkoxy groups, 6-10 carbon atoms, preferably 6 carbon atoms
To 8 aryl groups, having 6 to 10 carbon atoms, preferably 6 to
8 aryloxy groups, alkenyl groups having 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms; arylalkyl groups having 7 to 40 carbon atoms, preferably 7 to 10 carbon atoms; alkyls having 7 to 40 carbon atoms, preferably 7 to 12 carbon atoms Aryl group, 8 carbon atoms
-40, preferably 8-12 arylalkenyl groups, or halogen atoms, preferably chlorine atoms.

R ³ and R ⁴ may be the same as or different from each other, and may be a hydrogen atom, a halogen atom, preferably a fluorine atom, a chlorine atom or a bromine atom, an optionally halogenated carbon atom having 1 to 10 carbon atoms, 1-4 alkyl group, an aryl group having 6 to 10 carbon atoms, preferably _{^{6~8, -NR 10 2, -SR 10}} , -OSiR 10 3, -SiR 10
₃ or —PR ¹⁰ ₂ groups, wherein R ¹⁰ is a halogen atom, preferably a chlorine atom, or an alkyl group having 1 to 10, preferably 1 to 3 carbon atoms, or 6 to 10 carbon atoms.
Preferably, it is 6 to 8 aryl groups.

R ³ and R ⁴ are particularly preferably hydrogen atoms. R ⁵ and R ⁶ may be the same or different and are preferably the same, and have the meanings described for R ³ and R ⁴ , provided that R ⁵ and R ⁶ are not hydrogen atoms. R ⁵ and R ⁶ are preferably an optionally halogenated alkyl group having 1 to 4 carbon atoms,
Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a trifluoromethyl group, and a methyl group is preferable.

R ⁷ is as follows:

[0100]

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= BR ¹¹ , = AlR ¹¹ , -Ge-, -Sn
-, - O -, - S -, = SO, = SO 2, = NR 11, =
CO, = PR ¹¹ or = P (O) R ¹¹ , where R
¹¹ , R ¹² and R ¹³ may be the same or different from each other, and include a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, more preferably a methyl group, and a fluoro group having 1 to 10 carbon atoms. Alkyl group, preferably CF ₃
Group, an aryl group having 6 to 10 carbon atoms, preferably an aryl group having 6 to 8 carbon atoms, a fluoroaryl group having 6 to 10 carbon atoms, preferably a pentafluorophenyl group, an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms is particularly preferable. Is a methoxy group, an alkenyl group having 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, preferably 7 to 10 carbon atoms, and an arylalkenyl group having 8 to 40 carbon atoms, preferably 8 to 12 carbon atoms Or an alkylaryl group having 7 to 40 carbon atoms, preferably 7 to 12 carbon atoms;
^“11 and R ¹² ” or “R ¹¹ and R ¹³ ” may form a ring together with the atoms to which they are bonded.

M ² is silicon, germanium or tin, preferably silicon or germanium. R ⁷ is = CR
^{11 R 12, = SiR 11 R} 12, = GeR 11 R 12, -O -, -
S -, = SO, it is preferred that = PR ¹¹ or = P (O) R ^11.

R ⁸ and R ⁹ may be the same or different and have the same meaning as described for R ¹¹ . m and n may be the same or different and are 0, 1 or 2, preferably 0 or 1, and m + n is 0, 1 or 2, preferably 0 or 1.

Particularly preferable metallocenes satisfying the above conditions are shown in the following (i) to (iii).

[0105]

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[In the above formulas (i), (ii) and (iii), M ¹ is Zr or Hf, R ¹ and R ² are methyl groups or chlorine atoms, and R ⁵ and R ⁶ are methyl groups. , An ethyl group or a trifluoromethyl group, and R ⁸ , R ⁹ , R ¹⁰ and R ¹² have the above-mentioned meaning. Among the compounds represented by the formulas (i), (ii) and (iii), the following compounds are particularly preferred.

Rac-dimethylmethylenebis (indenyl) zirconium dichloride, rac-dimethylmethylenebis (2-methyl-1-indenyl) zirconium dichloride, rac-diphenylmethylenebis (2-methyl-
1-indenyl) zirconium dichloride, rac-ethylene (2-methyl-1-indenyl) ₂ -zirconium-dichloride, rac-dimethylsilylene (2-methyl-1-indenyl) ₂ -zirconium-dichloride, rac-dimethylsilylene (2 - methyl-1-indenyl) ₂ - zirconium - dimethyl, rac- ethylene - (2-methyl-1-indenyl) ₂ - zirconium - dimethyl, rac- phenyl (methyl) silylene - (2 Mechiru-1-indenyl) ₂ - Zirconium-dichloride, rac-diphenyl-silylene- (2-methyl-1-indenyl) ₂ -zirconium-dichloride, rac-methylethylene- (2-methyl-1-indenyl) ₂ -zirconium-dichloride, rac-dimethylsilylene- (2 -Ethyl-1-indenyl) ₂ -zirconium-dichloride. Such a metallocene can be produced by a conventionally known method (for example, see JP-A-4-268307).

In the present invention, a transition metal compound (metallocene compound) represented by the following formula [B] can be used as the bridge type metallocene compound.

[0109]

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[B] In the formula [B], M represents a transition metal atom of Group IVB of the periodic table, and specifically, titanium, zirconium, and hafnium.

R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group,
Oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group, specifically, halogen atom such as fluorine, chlorine, bromine, iodine; methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl , Dodecyl, eicosyl, norbornyl, alkyl groups such as adamantyl, vinyl, propenyl, alkenyl groups such as cyclohexenyl, benzyl, phenylethyl, arylalkyl groups such as phenylpropyl, phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, Propylphenyl, biphenyl, naphthyl,
A hydrocarbon group having 1 to 20 carbon atoms such as an aryl group such as methylnaphthyl, anthracenyl, and phenanthryl; a halogenated hydrocarbon group in which a halogen atom is substituted on the hydrocarbon group; a monohydrocarbon-substituted silyl such as methylsilyl and phenylsilyl; Dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl, trihydrocarbons such as trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl Substituted silyl, silyl ether of hydrocarbon-substituted silyl such as trimethylsilyl ether, silicon-substituted alkyl group such as trimethylsilylmethyl, silicon-substituted aryl group such as trimethylsilylphenyl, etc. Oxygen-containing groups such as hydroxy groups, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy; allyloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; and arylalkoxy groups such as phenylmethoxy and phenylethoxy. A sulfur-containing group such as a substituent in which the oxygen of the oxygen-containing group is substituted by sulfur; an amino group, an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino, a phenylamino group; A nitrogen-containing group such as an arylamino group or an alkylarylamino group such as diphenylamino, ditolylamino, dinaphthylamino, and methylphenylamino; dimethylphosphino;
It is a phosphorus-containing group such as a phosphino group such as diphenylphosphino.

Of these, R ¹ is preferably a hydrocarbon group, particularly methyl, ethyl and propyl having 1 carbon atom.
It is preferably from 3 to 3 hydrocarbon groups. R ² is preferably hydrogen or a hydrocarbon group, particularly preferably hydrogen or a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl and propyl.

R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms; Among them, hydrogen, a hydrocarbon group or a halogenated hydrocarbon group is preferable. R ³ and R ⁴ , R ⁴ and R ⁵ ,
At least one pair of R ⁵ and R ⁶ may form a monocyclic aromatic ring together with the carbon atom to which they are bonded.

In the case where there are two or more hydrocarbon groups or halogenated hydrocarbon groups, the groups other than the group forming an aromatic ring may be bonded to each other to form a ring. When R ⁶ is a substituent other than an aromatic group, it is preferably a hydrogen atom.

Specific examples of the halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a halogenated hydrocarbon group having 1 to 20 carbon atoms include the same groups as those described above for R ¹ and R ² . Examples of the ligand coordinated to M, including a monocyclic aromatic ring formed by combining at least one of R ³ and R ⁴ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ , are as follows. Some examples are shown below.

[0116]

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Among these, those represented by the above formula (1) are preferred. The aromatic ring is a halogen atom, having 1 to 1 carbon atoms.
It may be substituted with 20 hydrocarbon groups or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

Examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms and the halogenated hydrocarbon group having 1 to 20 carbon atoms to be substituted on the aromatic ring include the same groups as those described above for R ¹ and R ^2. .

X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group. And specifically, R ¹ and R
² the same halogen atom, hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, oxygen-containing groups can be exemplified.

Examples of the sulfur-containing group include the same groups as those described above for R ¹ and R ² and methylsulfonate, trifluoromethanesulfonate, phenylsulfonate, benzylsulfonate, p-toluenesulfonate and trimethylbenzenesulfonate. Sulfonate groups such as phonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, pentafluorobenzenesulfonate, methylsulfinate, phenylsulfinate, benzylsulfinate, p-toluenesulfinate , Trimethylbenzenesulfinate, pentafluorobenzenesulfinate and the like.

Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, 2
Divalent silicon-containing group, divalent germanium-containing group, divalent tin-containing group, -O-, -CO-, -S-, -SO-,-
^{_{SO 2 -, - NR 7 -}} , - P (R 7) -, - P (O)
^{(R 7) -, - BR} 7 - or -AlR ⁷ - [However,
R ⁷ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms], specifically, methylene, dimethylmethylene, 1,2-ethylene, Dimethyl-1,2-ethylene, 1,3-trimethylene,
Divalent having 1 to 20 carbon atoms such as alkylene groups such as 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene, and arylalkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene. A halogenated hydrocarbon group obtained by halogenating a divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene; methylsilylene, dimethylsilylene, diethylsilylene, di (n-
Alkyl silylenes such as propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene, alkylarylsilylene, aryl Silylene group,
Tetramethyl-1,2-disilylene, tetraphenyl-1,2-
A divalent silicon-containing group such as an alkyldisilylene such as disilylene, an alkylaryldisilylene, or an aryldisilylene group; a divalent germanium-containing group obtained by substituting silicon of the divalent silicon-containing group with germanium; A divalent tin-containing group substituent in which silicon of the silicon-containing group is substituted with tin, and the like. R ⁷ is the same halogen atom as R ¹ or R ² , a hydrocarbon group having 1 to 20 carbon atoms, a carbon number 1
To 20 halogenated hydrocarbon groups.

Of these, a divalent silicon-containing group, a divalent germanium-containing group, and a divalent tin-containing group are preferable, and a divalent silicon-containing group is more preferable.
Of these, alkylsilylene, alkylarylsilylene, and arylsilylene are particularly preferred.

Specific examples of the transition metal compound represented by the above formula [B] are shown below.

[0124]

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[0125]

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[0126]

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In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above compounds may be used. The transition metal compound is usually used as a catalyst component for olefin polymerization as a racemate, but may be an R-type or S-type.

Such an indene derivative ligand of a transition metal compound can be synthesized, for example, by the following reaction route using a conventional organic synthesis technique.

[0129]

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The transition metal compound used in the present invention can be synthesized from these indene derivatives by a known method, for example, a method described in JP-A-4-268307.

In the present invention, a transition metal compound (metallocene compound) represented by the following formula [C] can also be used as the bridge type metallocene compound.

[0132]

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[C] In the formula [C], M, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same as those in the above formula [B]. No.

Of R ³ , R ⁴ , R ⁵ and R ⁶ , R ³
Is preferably an alkyl group,
Preferably, R ³ and R ⁵ , or R ³ and R ⁶ are alkyl groups. This alkyl group is preferably a secondary or tertiary alkyl group. Also, this alkyl group is
A halogen atom, which may be substituted with a silicon-containing group,
Examples of the halogen atom and the silicon-containing group include the substituents exemplified for R ¹ and R ² .

Among the groups represented by R ³ , R ⁴ , R ⁵ and R ⁶ , the groups other than the alkyl groups are preferably hydrogen atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, A chain alkyl group and a cyclic alkyl group such as nonyl, dodecyl, eicosyl, norbornyl and adamantyl; an arylalkyl group such as benzyl, phenylethyl, phenylpropyl and tolylmethyl; and the like, including a double bond and a triple bond May be.

Further, two groups selected from R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a monocyclic or polycyclic ring other than an aromatic ring. As a halogen atom,
Specifically, the same groups as those for R ¹ and R ² can be exemplified.

X ¹ , X ² , Y and R ⁷ are the same as those in the above formula [B]. The metallocene compound (transition metal compound) represented by the formula [C] below
Here is a specific example.

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 (2,5,6-trimethyl
-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,5,6-tetramethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2,4,5,6,7-pentamethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-n-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) Zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-i-propyl-6-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-methyl-6
-i-propyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-i-propyl-5-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl -4,6-di (i-
Propyl) -1-indenyl) diruconium dichloride, ra
c-dimethylsilylene-bis (2-methyl-4,6-di (i-propyl) -7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-i-butyl
-7-methyl-1-indenyl) zirconium dichloride,
rac-Dimethylsilylene-bis (2-methyl-4-sec-butyl-7
-Methyl-1-indenyl) zirconium dichloride, rac
-Dimethylsilylene-bis (2-methyl-4,6-di (sec-butyl) -1-indenyl) diconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-tert-butyl-7-methyl
-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-cyclohexyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-benzyl-7 -Methyl-1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-phenylethyl-7-methyl
-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-phenyldichloromethyl
-7-methyl-1-indenyl) zirconium dichloride, r
ac-dimethylsilylene-bis (2-methyl-4-chloromethyl-
7-methyl-1-indenyl) zirconium dichloride, ra
c-dimethylsilylene-bis (2-methyl-4-trimethylsilylmethyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-trimethylsiloxymethyl-7-methyl-1- (Indenyl) zirconium dichloride, rac-diethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-di (i-propyl) silylene-bis (2-methyl-4 -i-propyl-7-methyl-1-indenyl)
Zirconium dichloride, rac-di (n-butyl) silylene
-Bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-di (cyclohexyl)
Silylene-bis (2-methyl-4-i-propyl-7-methyl-1-
(Indenyl) zirconium dichloride, rac-methylphenylsilylene-bis (2-methyl-4-i-propyl-7-methyl
-1-indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2-methyl-4-i-propyl-7-methyl
-1-indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2-methyl-4,6-di (i-propyl) -1-
(Indenyl) diruconium dichloride, rac-di (p-tolyl) silylene-bis (2-methyl-4-i-propyl-7-methyl
-1-indenyl) zirconium dichloride, rac-di (p-
(Chlorophenyl) silylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1- (Indenyl) zirconium dibromide, rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dimethyl, r
ac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-
Methyl-1-indenyl) zirconium methyl chloride,
rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7
-Methyl-1-indenyl) zirconium-bis (methanesulfonato), rac-dimethylsilylene-bis (2-methyl-4-i
-Propyl-7-methyl-1-indenyl) zirconium-bis (p-phenylsulfinato), rac-dimethylsilylene
-Bis (2-methyl-3-methyl-4-i-propyl-6-methyl-1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-ethyl-4-i-propyl-6-methyl-1-
(Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-phenyl-4-i-propyl-6-methyl-1-
Indenyl) zirconium dichloride.

In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above compounds can also be used. The transition metal compound is usually used as a racemic compound, but may be used in R-form or S-form.

Such an indene derivative ligand of a transition metal compound can be synthesized, for example, by the same reaction route as described above using a conventional organic synthesis technique. The transition metal compound (metallocene compound) represented by the above formula [C] can be synthesized from these indene derivatives by a known method, for example, a method described in JP-A-4-268307.

In the present invention, a transition metal compound (metallocene compound) represented by the following formula [D] can also be used as the bridge type metallocene compound.

[0142]

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[D] In the formula [D], M, R ¹ , X ¹ , X ² and Y are the same as those in the above formula [B] or the above formula [C]. Can be

Among them, R ¹ is preferably a hydrocarbon group, particularly preferably a hydrocarbon group having 1 to 4 carbon atoms such as methyl, ethyl, propyl and butyl. X ¹ and X ² are preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

R ² represents an aryl group having 6 to 16 carbon atoms. Specific examples include phenyl, α-naphthyl, β-naphthyl, anthracenyl, phenanthryl, pyrenyl, acenaphthyl, phenalenyl (perinaphthenyl), aceanthrenyl and the like. It is. Of these, phenyl and naphthyl are preferred. These aryl groups may be substituted with the same halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms as in R ¹ .

Specific examples of the transition metal compound (metallocene compound) represented by the above formula [D] are shown below. 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-anthracenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (2-anthracenyl) -1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (9-anthracenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (9-phenanthryl) 1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (p-fluorophenyl) -1-indenyl)
Zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (pentafluorophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (p-chlorophenyl) -1 -Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2
-Methyl-4- (m-chlorophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (o-chlorophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-
(o, p-dichlorophenyl) phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-
Methyl-4- (p-bromophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (p-tolyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (m-tolyl) -1-indenyl) zirconium dichloride, rac-
Dimethylsilylene-bis (2-methyl-4- (o-tolyl) -1-
Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (o, o'-dimethylphenyl) -1-
Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (p-ethylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (pi-propylphenyl) ) -1-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (p-benzylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-methyl-4- (p-biphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-
Methyl-4- (m-biphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-
(p-trimethylsilylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (m-trimethylsilylphenyl) -1-indenyl)
Zirconium dichloride, rac-dimethylsilylene-bis
(2-ethyl-4-phenyl-1-indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2-ethyl-4
-Phenyl-1-indenyl) zirconium muscidochloride, ra
c-dimethylsilylene-bis (2-phenyl-4-phenyl-1-
(Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-n-propyl-4-phenyl-1-indenyl) zirconium dichloride, rac-diethylsilylene-
Bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-di- (i-propyl) silylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-di- ( n-butyl) silylene-bis (2-methyl-4-phenyl-1-indenyl) diruconium dichloride, rac-dicyclohexylsilylene-bis (2-methyl-
4-phenyl-1-indenyl) zirconium dichloride,
rac-methylphenylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-di (p -Tolyl) silylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-methylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-ethylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylgermylene-bis ( 2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethyltin-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethyl Rylene - bis (2-methyl -
4-phenyl-1-indenyl) zirconium dibromide,
rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-
Indenyl) zirconium dimethyl, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium methyl chloride, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium chloride SO bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride OSO ₂ Me - ₂ Me, rac- dimethylsilylene.

In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above compounds can also be used. The transition metal compound represented by the formula [D] is described in Journa
l of Organometallic Chem. 288 (1985), pp. 63-67, EP-A-0,320,762 and examples, for example, as follows.

[0148]

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The transition metal compound [D] is usually used as a racemic compound, but may be used in the R or S form. In the present invention, a transition metal compound represented by the following general formula (VII) can also be used as the metallocene compound.

L ² M ² X ₂ (VII) M ² is a metal belonging to Group 4 of the periodic table or a lanthanide series, L ² is a derivative of a delocalized π-bonded group, and the metal M ² The active site is given a constrained geometry, and X is
May be the same or different from each other, and are a hydrogen atom or a halogen atom, or 20 or less carbon atoms,
It is a hydrocarbon group containing a silicon atom or a germanium atom, a silyl group or a germanyl group.

Among the compounds represented by the general formula (VII), a transition metal compound represented by the following general formula (VII ') is preferable.

[0152]

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In the formula, M ² is titanium, zirconium or hafnium, and X is the same as described above. Cp is M
A substituted cyclopentadienyl group having a π bond to ² and a substituent Z.

Z is oxygen, sulfur, boron or an element of group 14 of the periodic table (for example, silicon, germanium or tin), Y is a ligand containing nitrogen, phosphorus, oxygen or sulfur, and Z and Y And may form a fused ring.

Specific examples of the compound represented by the general formula (VII ′) include (dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane) titanium dichloride and (( t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl) titanium dichloride.

The above metallocene compounds 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.

Examples of such a particulate carrier include Si
O ₂ , Al ₂ O ₃ , B ₂ O ₃ , MgO, ZrO ₂ , Ca
Inorganic carrier such as O, TiO ₂ , ZnO, SnO ₂ , BaO, ThO, polyethylene, polypropylene, poly-1-
Organic carriers such as butene, poly-4-methyl-1-pentene, and styrene-divinylbenzene copolymer can be used. These particulate carriers can be used alone or in combination of two or more.

Next, a metallocene catalyst is formed (b-
2) The organic aluminum oxy compound and the ionized ionic compound will be described. (B-2) The organoaluminum oxy compound may be a conventionally known aluminoxane.
A benzene-insoluble organic aluminum oxy compound as exemplified in JP-A-87-87 may be used.

The conventionally known aluminoxane is specifically represented by the following general formula.

[0160]

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In the formula, R represents 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 is represented by 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 organic aluminum oxy compound may contain a small amount of an organic compound component of a metal other than aluminum. Examples of the ionized ionic 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). And 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
One type may be used alone, or two or more types may be used in combination. 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 may be used together with the organic aluminum oxy compound or ionized ionic 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 )) _n H _p X _q (wherein R ¹ and R ² may be the same or different from each other and usually have 1 to 15 carbon atoms; Preferably 1 to
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. In the present invention, (i) ethylene, (ii) an aromatic vinyl compound and (iii) a non-conjugated polyene and, if necessary, (iv) an α-olefin in a normal Copolymerize in phase. 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.
~ 0.1 mmol, preferably 0.0001-0.05
Used in millimolar amounts. The organic aluminum oxy compound has a molar ratio of aluminum atom (Al) to transition metal atom (M) in the metallocene compound (Al / M).
And it is used in an amount such that it becomes 1 to 10,000, preferably 10 to 5,000.

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 to 2
It is used in an amount such that it becomes 0, preferably 1 to 10.

When an organic aluminum 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.

The copolymerization reaction is usually carried out at a temperature of -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 .

(I) ethylene, (ii) an aromatic vinyl compound and (iii) a non-conjugated polyene, if necessary (iv)
The α-olefin is supplied to the polymerization system in such an amount that the (A) unsaturated olefin copolymer having the specific composition as described above is obtained. Further, upon copolymerization, a molecular weight regulator such as hydrogen may be used.

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

(B) Vulcanizing Agent The vulcanizing agent (B) includes sulfur and sulfur compounds. 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.
Sulfur compounds that release active sulfur at the vulcanization temperature and vulcanize, such as morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide, and the like can also be used.

Of these, powdered sulfur is preferably used. Further, as the vulcanizing agent (B), an organic peroxide can also be used. Specifically, as the organic peroxide,
Dicumyl peroxide, di-tert-butyl peroxide,
Di-tert-butylperoxy-3,3,5-trimethylcyclohexane, tert-butyldicumyl peroxide, di-tert-
Amyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di-
(Benzoylperoxy) hexane, 2,5-dimethyl-2,5
Alkyl peroxides such as -di- (tert-butylperoxy) hexane, α, α-bis (tert-butylperoxy-m-isopropyl) benzene and tert-butylhydroperoxide; tert-butylperoxyacetate, tert-
Butylperoxyisobutyrate, tert-butylperoxypivalate, tert-butylperoxymaleic acid, t
Peroxyesters such as ert-butylperoxy neodecanoate, tert-butylperoxybenzoate, and ditert-butylperoxyphthalate; ketone peroxides such as dicyclohexanone peroxide; These can be used alone or in combination of two or more.

Of these, the one-minute half-life temperature was 13
An organic peroxide having a temperature of 0 to 200 ° C. is preferred, and specifically, dicumyl peroxide, di-tert-butyl peroxide, di-tert-butylperoxy-3,3,5-trimethylcyclohexane, tert-butyl dicumyl peroxide , Di-te
Preferred are rt-amyl peroxide, tert-butyl hydroperoxide and the like.

In the present invention, among various vulcanizing agents (B) as described above, it is preferable to use sulfur or a sulfur-based compound, particularly sulfur, since a rubber composition having excellent properties can be obtained.

(C) Reinforcing Material Specifically, SRF, GPF, FEF, M
Examples thereof include carbon blacks such as AF, HAF, ISAF, SAF, FT, and MT, those obtained by subjecting these carbon blacks to surface treatment with a silane coupling agent, silica, activated calcium carbonate, fine talc, fine silica, and the like.

When such a reinforcing material is used, the tensile strength,
A vulcanizate having excellent mechanical properties such as tear strength and abrasion resistance can be obtained. (D) Liquid softener As the liquid softener, softeners conventionally compounded in rubber are widely used, and specifically, process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt,
Petroleum softeners such as petrolatum; coal tar softeners such as coal tar and coal tar pitch; fatty oil softeners such as castor oil, linseed oil, rapeseed oil and coconut oil; tall oil; sub; beeswax and carnauba wax And fatty acids such as ricinoleic acid, palmitic acid, barium stearate, calcium stearate, and zinc laurate; and synthetic high molecular substances such as petroleum resins, atactic polypropylene, and coumarone indene resins. Can be. Among them, a petroleum softener is preferably used, and particularly, a process oil is preferably used.

Vulcanizate The vulcanizate constituting the vulcanizate molded article having the surface decorative layer according to the present invention is obtained by vulcanizing the above-mentioned unsaturated olefin copolymer (A), Or an unsaturated olefin-based copolymer comprising (A) an unsaturated olefin-based copolymer and at least one compounding agent selected from (B) a vulcanizing agent, (C) a reinforcing material, and (D) a liquid softener. It is obtained by vulcanizing the copolymer composition.

In the above unsaturated olefin copolymer composition, when the vulcanizing agent (B) is sulfur or a sulfur compound, it is added to (A) 100 parts by weight of the unsaturated olefin copolymer. On the other hand, it can be used in an amount of usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight.

When the vulcanizing agent (B) is an organic peroxide, 0.05 to 15 parts by weight, preferably 0.1 to 15 parts by weight, per 100 parts by weight of the unsaturated olefin copolymer (A) is used. 1
It can be used in an amount of 5 to 5 parts by weight.

(C) The reinforcing agent is usually 300 parts by weight or less, preferably 10 to 300 parts by weight, more preferably 10 to 200 parts by weight, based on 100 parts by weight of the unsaturated olefin copolymer (A). Used in the ratio of

The (D) liquid softener is used in an amount of 200 parts by weight or less, preferably 5 to 200 parts by weight, more preferably 10 parts by weight, based on 100 parts by weight of the unsaturated olefin copolymer (A).
To 150 parts by weight, more preferably 10 to 100 parts by weight.

The unsaturated olefin copolymer composition comprises:
(A) an unsaturated olefin copolymer, and (B) at least one compounding agent selected from a vulcanizing agent, (C) a reinforcing agent, and (D) a liquid softening agent, and a Banbury mixer, a kneader, It can be manufactured by kneading by a conventionally known method such as a mixing method using an internal mixer such as an intermix.

To produce a vulcanizate from (A) an unsaturated olefin copolymer or (B) an unsaturated olefin copolymer composition containing no vulcanizing agent, a general rubber is usually used. As in the case of vulcanization, an unvulcanized compounded rubber may be prepared once, and then the compounded rubber may be formed into an intended shape and then vulcanized. A method of irradiating an electron beam is employed as a vulcanization method.

(B) In order to produce a vulcanizate from an unsaturated olefin copolymer composition containing a vulcanizing agent, a vulcanized compounded rubber may be prepared in the same manner as in the case of vulcanizing a general rubber. May be prepared once and then vulcanized after the compounded rubber is formed into an intended shape.

In the present invention, the aforementioned unvulcanized compounded rubber contains the above unsaturated olefin copolymer (A), vulcanizing agent (B), reinforcing agent (C) and liquid softening agent (D). In addition, vulcanization accelerators, vulcanization aids, fillers, tackifiers, anti-aging agents, foaming agents, processing aids, heat stabilizers, weather stabilizers,
A rubber compounding agent such as an antistatic agent, a colorant, a lubricant, a flame retardant, an anti-blooming agent, and an agent for improving the adhesion to the surface decorative layer can be compounded within a range that does not impair the object of the present invention.

Specific examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazole sulfenamide (OBS), and N, N-diisopropyl-2-benzo. Thiazolesulfenamide, 2-mercaptobenzothiazole, 2-
Thiazole compounds such as (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole, dibenzothiazyldisulfide; diphenylguanidine, triphenylguanidine, diorsonitrile guanidine , Guanidine compounds such as orthonitrile biguanide, diphenylguanidine phthalate; acetaldehyde-aniline reactant;
Aldehyde amines such as butyraldehyde-aniline condensate, hexamethylenetetramine, acetaldehyde ammonia or aldehyde-ammonia compounds; imidazoline compounds such as 2-mercaptoimidazoline; thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, diortho Thiourea compounds such as tolylthiourea; tetramethylthiuram monosulfide; thiuram compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate; Zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, Le zinc dithiocarbamate, sodium dimethyl dithiocarbamate, dimethyl dithiocarbamate selenium, dithio acid salt-based compounds such as dimethyl dithiocarbamate tellurium; dibutyl xanthate acid xanthate compounds such as zinc; and the like compounds such as zinc white. These vulcanization accelerators are used in an amount of 1 to 100 parts by weight of the unsaturated olefin-based copolymer (A).
It is used in an amount of 20 parts by weight, preferably 2 to 10 parts by weight.

Specific examples of the filler include light calcium carbonate, heavy calcium carbonate, talc, clay and the like. The filler is usually 300 parts by weight or less based on 100 parts by weight of the unsaturated olefin-based copolymer (A),
Preferably 10 to 300 parts by weight, more preferably 10
Used in an amount of ~ 200 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 blowing agent is an unsaturated olefin copolymer (A) 1
0.5 to 30 parts by weight, preferably 1 to 100 parts by weight
Used in amounts of up to 20 parts by weight. From the unsaturated olefin-based copolymer composition 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 olefin copolymer (A).

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

The adhesion improving agent improves the adhesion between the vulcanized product and a decorative layer such as a coating film. Examples thereof include an organotin compound, a tertiary amine compound, a hydroxyl group-containing (co) polymer, Metal hydroxide and the like.

Examples of the organotin compounds include dialkyltin dicarboxylates such as dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin dilaurate, 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;
Dialkyltin marker blades such as dibutyltin marker blade; alkyltrilaurates such as butyltin trilaurate and octyltin trilaurate; alkyltin trimaleates such as butyltin trimethyl maleate and butyl tin trioctyl maleate; butyl hydroxy Examples thereof include alkylhydroxytin dichlorides such as tin dichloride; trialkyltin tin maleates such as tribenzyltin 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 5 parts by weight, based on 100 parts by weight of the unsaturated olefin-based copolymer (A).

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. In addition, as a tertiary amino compound,
And high molecular compounds such as olefin (co) polymers having a higher amino group. 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 Having a structure in which a side chain having a tertiary amine structure is grafted,
0.1 to 50% by weight of the unsaturated compound having a primary amino group
It is. Such a tertiary amino group-containing olefin (co) polymer can be produced by a known method of copolymerizing using a tertiary amino group-containing unsaturated compound or graft-polymerizing a polyolefin. Among the tertiary amino compounds as described above, 1,4-diazabicyclo- [2.
2.2] -Octane is preferably used. The tertiary amino 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 olefin copolymer (A).
It is used in a proportion of from 0.5 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. Condensed diene polymer having a hydroxyl group; hydrogenated polybutadiene having a hydroxyl group at the molecular end; hydrogenated polyisoprene having a hydroxyl group at the molecular end; hydrogenated conjugated diene polymer 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 vulcanized product and the urethane resin-based coating film can be improved. The hydroxyl group-containing (co) polymer is used in an amount of 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the unsaturated olefin copolymer (A).

As the metal hydroxide, specifically, 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
20 to 200 parts by weight, preferably 20 to 15 parts by weight, per 100 parts by weight of the unsaturated olefin copolymer (A).
0 parts by weight, more preferably 50 to 150 parts by weight.

The method for producing the vulcanizate is not particularly limited, but specifically, for example, the following method is employed. That is, using a mixer such as a Banbury mixer, (A) an unsaturated olefin-based copolymer and, if necessary, (C) a filler, (D) a liquid softener, and other rubber compounding agents 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 vulcanizing agent and, if necessary, a vulcanization accelerator are additionally mixed, and a roll temperature of 40 to 80 ° C for 5 to 30 minutes. After kneading, the mixture is dispensed, and an unvulcanized compound rubber in the form of a ribbon or sheet is prepared. When the kneading temperature in the internal mixers is low, the vulcanizing agent (B), the vulcanization accelerator, the foaming agent and the like can be kneaded at the same time.

The unvulcanized compounded rubber thus prepared is molded into an intended shape by an extruder, a calender roll, or a press.
Heat at a temperature of 0 ° C. for 1 to 30 minutes, or introduce the molded product into a vulcanization tank,
A vulcanizate is obtained by heating for minutes. Vulcanization may be performed in a mold or without a mold. When a mold is not used, the steps of molding and vulcanization are usually performed continuously. As a heating method in the vulcanization 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 an electron beam is employed as a vulcanization method, a unsaturated olefin copolymer (A), a reinforcing agent (C) if necessary, D) After kneading a liquid softener, other rubber compounding agent, etc. at a temperature of 80 to 170 ° C. for 3 to 10 minutes,
Using rolls such as open rolls, roll temperature 40
After kneading at ８０80 ° C. for 5 to 30 minutes, the mixture is dispensed to prepare a ribbon-shaped or sheet-shaped unvulcanized compounded rubber. The unvulcanized compounded rubber thus prepared is molded into an intended shape by an extruder, a calender roll, or a press, and a vulcanized product is obtained by irradiating an electron beam.
The electron beam is irradiated with electrons having an energy of 0.1 to 10 MeV (mega electron volts), preferably 0.3 to 2 MeV, and an absorbed dose of 0.5 to 35 Mrad (mega rad), preferably 0.5 to 10 Mrad. It is desirable to perform so that

The vulcanizate molded article having a surface decorative layer according to the present invention can be prepared by coating the surface of the vulcanizate as described above, or by using an adhesive to bond other members such as metal and resin. It is obtained by bonding to form a decorative layer. Further, after forming a decorative layer on unvulcanized compounded rubber, the compounded rubber is vulcanized to obtain a vulcanized product having a surface decorative layer.

For coating of the vulcanized product or unvulcanized compounded rubber, generally used paints such as acrylic resin paint, epoxy resin paint, polyester resin paint, urethane resin paint and alkyd resin paint are used. Paints, melamine resin paints, silicone resin paints, and the like can be used.

Acrylic resin-based paints are mainly composed of acrylic acid, methacrylic acid and esters thereof, and are prepared by diluting a resin produced alone or with each other or by copolymerization with another resin with a solvent, or by solution polymerization or emulsion polymerization. A plasticizer, a second resin, and the like are added or not added to a varnish obtained as a vehicle, and as a clear,
Alternatively, it is a paint obtained as an enamel by adding 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-based paint is a paint obtained by thermosetting in combination with 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.

[0213] Silicone resin-based paints include silicone resin or alkyd, epoxy, phenol, acrylic,
A paint obtained by curing a silicone resin modified with melamine, urethane, or the like.

When acrylic resin-based paints, melamine resin-based paints, polyester resin-based paints, urethane resin-based paints, and silicone resin-based paints are used, the adhesion of the coating film is excellent, and particularly, urethane resin-based paints, silicone resin-based paints Is preferred because of 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 vulcanizate molded article having a surface decorative layer according to the present invention may be used for automobile industrial parts such as weather strips, door glass run channels, window frames, etc., and building materials such as glazing gaskets, joint gaskets, airtight gaskets and the like. Can be used for applications. When the vulcanized product is a foam, it can be used for heat insulating materials, cushioning materials, sealing materials, and the like.

[0219]

The vulcanizate molded article having the surface decorative layer according to the present invention has high adhesiveness to the surface decorative layer and excellent mechanical strength.

[0218]

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

[0219]

[Synthesis Example 1] A 1.5-liter autoclave was sufficiently replaced with nitrogen, and 430 ml of toluene and 75 m of styrene were used.
1,4-ethylidene-8-methyl-1,7-nonadiene (EMN
D) 5 ml was charged. 3.2 kg of propylene
/ Cm ² . Next, the temperature inside the system was raised to 50 ° C. while stirring, and ethylene was introduced so as to be 10 kg / cm ² . Next, methylaluminoxane (3% by weight toluene solution, manufactured by Tosoh Akzo) was placed in another reactor.
9.2 mmol, 0.018 m of (dimethyl (tert-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane) dichloride titanium synthesized by a known method
The mixture was stirred for 15 minutes, and then introduced into an autoclave to start polymerization. During this polymerization, ethylene was continuously supplied so that the pressure in the system was maintained at 10 kg / cm ² , and polymerization was performed for 30 minutes. Thereafter, 5 ml of methanol was added to terminate the polymerization. After completion of the polymerization, the polymer was precipitated from the polymerization solution with 1 liter of methanol. The precipitated polymer was further washed twice with 1 liter of methanol, and dried under reduced pressure at 130 ° C. for 12 hours. The obtained ethylene-propylene-styrene-EMND copolymer (copolymer (a)) is 24 g, and has a molar ratio of a structural unit derived from ethylene to a structural unit derived from propylene (ethylene / propylene). Is 73/27, and the molar ratio of the total amount of the constituent units derived from ethylene and the constituent units derived from propylene to the constituent unit derived from styrene (ethylene + propylene / styrene) is 90/27.
It was 10. The iodine value of this copolymer is 15,
The intrinsic viscosity [η] measured in decalin at 135 ° C. is 2.
It was 8 dl / g.

[0220]

[Synthesis Example 2] A 1.5-liter autoclave was sufficiently substituted with nitrogen, and 430 ml of toluene and 40 m of styrene were used.
l, 4.5 ml of EMND was charged. Further, 1-butene was introduced so as to be 2.0 kg / cm ² . Then, the temperature inside the system was raised to 50 ° C. while stirring, and ethylene was added at 10 kg / c.
m ² .

Thereafter, the pressure in the system during the polymerization was increased to 10 kg / c.
A polymerization reaction was carried out in the same manner as in Synthesis Example 1 except that ethylene was continuously supplied so as to maintain m ² . The obtained ethylene / 1-butene / styrene / EMND copolymer (copolymer (b)) is 23 g, and has a molar ratio of a structural unit derived from ethylene to a structural unit derived from 1-butene ( (Ethylene / 1-butene) is 80/20, and the molar ratio of the total amount of the structural units derived from ethylene and the structural units derived from 1-butene to the structural unit derived from styrene (ethylene + 1-butene / (Styrene) was 94/6. The iodine value of this copolymer is 13, 135 ° C,
The intrinsic viscosity [η] measured in decalin is 2.7 dl / g
Met.

[0222]

Synthesis Example 3 A 1.5-liter autoclave was sufficiently substituted with nitrogen, and 430 ml of toluene and 50 m of styrene were used.
1, 1-octene 40 ml and EMND 4.5 ml were charged. Then, the temperature inside the system was raised to 60 ° C. while stirring, and ethylene was introduced so as to be 10 kg / cm ² .

Thereafter, the pressure in the system during the polymerization was increased to 10 kg / c.
A polymerization reaction was carried out in the same manner as in Synthesis Example 1 except that ethylene was continuously supplied so as to maintain m ² . The obtained ethylene / 1-octene / styrene / EMND copolymer (copolymer (c)) is 20 g, and has a molar ratio of a structural unit derived from ethylene to a structural unit derived from 1-octene ( (Ethylene / 1-butene) is 83/17, and the molar ratio of the total amount of the constituent units derived from ethylene and the constituent units derived from 1-octene to the constituent unit derived from styrene (ethylene + 1-octene / (Styrene) was 93/7. The iodine value of this copolymer is 12 and 135
The intrinsic viscosity [η] measured in decalin at 2.6 ° C. is 2.6 dl.
/ G.

[0224]

Synthesis Example 4 A 1.5-liter autoclave was sufficiently replaced with nitrogen, and 430 ml of toluene and 40 m of styrene were used.
l, 8 ml of EMND was charged. Further, propylene was introduced so as to be 3.0 kg / cm ² . Then, the temperature inside the system was raised to 50 ° C. while stirring, and ethylene was added at 10 kg / c.
m ² .

Thereafter, the pressure in the system during the polymerization was increased to 10 kg / c.
A polymerization reaction was carried out in the same manner as in Synthesis Example 1 except that ethylene was continuously supplied so as to maintain m ² . The obtained ethylene-propylene-styrene-EMND copolymer (copolymer (d)) is 21 g, and has a molar ratio of a constitutional unit derived from ethylene to a constitutional unit derived from propylene (ethylene / propylene). Is 75/25, and the molar ratio of the total amount of the structural units derived from ethylene and the structural units derived from propylene to the structural unit derived from styrene (ethylene + propylene / styrene) is 93/7.
Met. The iodine value of this copolymer is 24 and 13
The intrinsic viscosity [η] measured in decalin at 5 ° C. is 2.7 d.
1 / g.

[0226]

[Synthesis Example 5] A 1.5-liter autoclave was sufficiently substituted with nitrogen, and 430 ml of toluene and 60 m of styrene were used.
1, 7.5 ml of EMND was charged. Further, 1-butene was introduced so as to be 2.0 kg / cm ² . Then, the temperature inside the system was raised to 50 ° C. while stirring, and ethylene was added at 10 kg / c.
m ² .

Thereafter, the pressure in the system during the polymerization was increased to 10 kg / c.
A polymerization reaction was carried out in the same manner as in Synthesis Example 1 except that ethylene was continuously supplied so as to maintain m ² . The amount of the obtained ethylene / 1-butene / styrene / EMND copolymer (copolymer (e)) was 18 g, and the molar ratio of the structural unit derived from ethylene to the structural unit derived from 1-butene ( (Ethylene / 1-butene) is 78/22, and the molar ratio of the total amount of the structural units derived from ethylene and the structural units derived from 1-butene to the structural unit derived from styrene (ethylene + 1-butene / (Styrene) was 92/8. The iodine value of this copolymer is 22, 135 ° C,
The intrinsic viscosity [η] measured in decalin is 2.4 dl / g
Met.

[0228]

Synthesis Example 6 In Synthesis Example 1, (dimethyl (tert-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane) dichloride titanium was converted to isopropylidene-bis (indenyl) zirconium dichloride synthesized by a known method. Except having changed, it carried out similarly to the synthesis example 1, and obtained ethylene-propylene-styrene-EMND copolymer (copolymer (h)). The obtained ethylene-propylene-styrene-EMND copolymer (copolymer (h))
The molar ratio of the structural unit derived from ethylene to the structural unit derived from propylene (ethylene / propylene) is 7
It was 5/25, and the molar ratio (ethylene + propylene / styrene) of the total amount of the structural units derived from ethylene and the structural units derived from propylene to the structural unit derived from styrene was 89/11. The iodine value of this copolymer was 16, and the intrinsic viscosity [η] measured in decalin at 135 ° C. was 2.1 dl / g.

[0229]

Example 1 The copolymer (a) produced in Synthesis Example 1 above, FEF carbon black (Asahi 60HG ^™ , manufactured by Asahi Carbon Co., Ltd.), paraffin oil (PS-430)
^TM (manufactured by Idemitsu Kosan Co., Ltd.)), stearic acid, zinc white, heavy calcium carbonate (Whiteton SB ^TM , Shiraishi Industry Co., Ltd.)
Manufactured), calcium oxide (Vesta BS ^™ , Inoue Lime Co., Ltd.)
Was mixed using a 4.3 liter Banbury mixer (manufactured by Kobe Steel Ltd.) for 6 minutes. This kneaded material is placed on a 14-inch open roll (front roll / rear roll:
(50/50 ° C.), sulfur, 2-mercaptobenzothiazole, dipentamethylenethiuram disulfide and tetrabutylthiuram disulfide were added, kneaded, and fractionated to obtain a compounded rubber.

Copolymer (a): 100 parts by weight FEF-carbon black: 160 parts by weight Paraffin oil: 90 parts by weight Stearic acid: 1 part by weight Zinc white flower: 5 parts by weight Heavy calcium carbonate: 35 parts by weight Calcium oxide: 5 parts by weight Sulfur: 0.8 parts by weight 2-mercaptobenzothiazole: 1.0 parts by weight Dipentamethylenethiuram disulfide: 0.4 parts by weight Tetrabutylthiuram disulfide: 0.4 parts by weight Obtained as described above. The compounded rubber was heated by a press heated to 160 ° C. for 10 minutes to produce a vulcanized sheet having a thickness of 2 mm. The vulcanized sheet was subjected to a tensile test,
A hardness test was performed.

Further, the compounded rubber was placed in a flat die (width: 50
(mm, wall thickness: 2 mm) were extruded using a 50 mm extruder at a die temperature of 80 ° C and a cylinder temperature of 60 ° C to form a flat plate. Then, a urethane resin paint (Mitsui Toatsu Chemical Co., Ltd .: Olester Q173 / Olester NP1100 (100/88)) is formed on the upper surface of the flat plate.
Was applied using a roll, and the molded body was vulcanized in a hot air vulcanization bath at 210 ° C. for 6 minutes to obtain a urethane-coated rubber plate. The adhesive strength of the coating film was measured for this urethane-coated rubber plate. Table 1 shows the results.

[Tensile test] A vulcanized sheet was punched out and J
3 described in IS K6301 (1989)
No. dumbbell test piece was prepared, and the same J
According to the method described in ISK6301 Paragraph 3, a tensile test was conducted at a measuring temperature of 500 ° C. and a tensile speed of 500 mm / min to measure a tensile strength (TB) and a tensile elongation at break (EB).

[Hardness Test] A spring hardness (HS: JIS A hardness) was measured in accordance with JIS K6301.

[Adhesion Test of Coating Film] Two plate-shaped vulcanizate test pieces each having a thickness of about 100 μm were prepared, and the rubber surface of one test piece and the coated surface of the other test piece were instantaneously measured. After laminating with an adhesive, a 10 mm wide strip was cut out and peeled at a rate of 200 mm / min in a direction of 90 ° using a tensile tester, and the peel strength was measured.

[Compression permanent set test]
In accordance with IS K6301, the compression set (CS) of a test piece aged at 100 ° C. for 22 hours was determined.

[0236]

Example 2 Example 1 was repeated except that 0.6 part by weight of dioctyltin maleate polymer and 4 parts by weight of hydroxyl group-containing polybutadiene (Polytail H ^™ , manufactured by Mitsubishi Chemical Corporation) were used. The same was done. Table 1 shows the results.

[0237]

Example 3 Example 2 was repeated except that 40 parts by weight of magnesium hydroxide was used instead of heavy calcium carbonate. Table 1 shows the results.

[0238]

Example 4 Example 1 was repeated except that the copolymer (b) produced in Synthesis Example 2 was used instead of the copolymer (a). Table 1 shows the results.

[0239]

Example 5 The procedure of Example 1 was repeated, except that the copolymer (c) produced in Synthesis Example 3 was used instead of the copolymer (a). Table 1 shows the results.

[0240]

Comparative Example 1 In Example 1, an ethylene / propylene / EMND copolymer (ethylene / propylene (molar ratio) = 72/28, iodine value: 1) was used in place of the copolymer (a).
2, intrinsic viscosity [η] measured in decalin at 135 ° C:
2.7 dl / g) (copolymer (f))
Performed in the same manner as in Example 1. Table 1 shows the results.

[0241]

Example 6 The copolymer (d) produced in Synthesis Example 4 above, SRF-H carbon black (Asahi # 60 ^™ , manufactured by Asahi Carbon Co., Ltd.), paraffin-based process oil (PW-3)
80 ^TM (made by Idemitsu Kosan), polyethylene glycol,
Stearic acid and zinc white were kneaded for 6 minutes using a 1.7 liter Banbury mixer (manufactured by Kobe Steel Ltd.). To this kneaded product, sulfur, 2-mercaptobenzothiazole, 2- (4'-morpholinodithio) benzothiazole,
Add zinc di-n-butyldithiocarbamate, 2-mercaptoimidazoline, p, p'-oxybisbenzenesulfonylhydrazide and calcium oxide, knead them with an 8-inch open roll (pre-roll / post-roll: 50/50 ° C.) and mix Obtained.

Copolymer (d): 100 parts by weight SRF-H-carbon black: 90 parts by weight Paraffin-based process oil: 70 parts by weight Polyethylene glycol: 1 part by weight Stearic acid: 2 parts by weight Zinc white: 5 parts by weight sulfur : 1.5 parts by weight Calcium oxide: 5 parts by weight 2-mercaptobenzothiazole: 0.8 parts by weight 2- (4'-morpholinodithio) benzothiazole: 1.2 parts by weight Zinc di-n-butyldithiocarbamate: 0 parts by weight 2-mercaptoimidazoline: 1.0 part by weight p, p'-oxybisbenzenesulfonylhydrazide: 3.5 parts by weight The compounded rubber obtained as described above was prepared by adding an inner diameter of 10 mm,
Using a 50 mm φ extruder equipped with a tube die with an inner thickness of 1 mm, the die temperature is 80 ° C and the cylinder temperature is 60 ° C
And extruded into a tube. This molded body is
Vulcanization was performed in a hot air vulcanization tank at 20 ° C. for 6 minutes to obtain a sponge-like rubber. This sponge-like rubber was measured for specific gravity, tensile test, and compression set.

Further, a flat die (width: 25 mm, height: 2 mm) was mounted in place of the tube die to obtain a flat vulcanized molded product. Next, the molded body was heated to 220 ° C.
For 6 minutes to obtain a sponge-like rubber plate. Continued
A urethane resin paint was applied to this rubber plate in the same manner as in Example 1, and heated at 200 ° C. for 6 minutes to obtain a urethane-coated sponge-like rubber plate. With respect to the urethane-coated sponge-like rubber plate, the adhesive strength and the like of the coating film were measured. Table 1 shows the results.

[0244]

Example 7 Example 7 was carried out in the same manner as in Example 1 except that the copolymer (d) produced in Synthesis Example 5 was used instead of the copolymer (d). Table 1 shows the results.

[0245]

Comparative Example 2 In Example 6, an ethylene / propylene / EMND copolymer (ethylene / propylene (molar ratio) = 70/30, iodine value: 2) was used in place of the copolymer (d).
2, intrinsic viscosity [η] measured in decalin at 135 ° C:
2.6 dl / g) (copolymer (g))
Performed in the same manner as in Example 1. Table 1 shows the results.

[0246]

Example 8 The procedure of Example 1 was repeated, except that the copolymer (h) produced in Synthesis Example 6 was used instead of the copolymer (a). Table 1 shows the results.

As shown in Table 1, the vulcanizate molded article having the surface decorative layer (coating film) of the present invention was not subjected to the surface treatment at the time of painting, but the surface decorative layer was not treated. Excellent bonding strength (coating adhesion strength).

[0248]

[Table 1]

Continued on the front page (72) Inventor Kenichi Mori Sono Mitsui Chemicals, Inc.

Claims (8)

[Claims] (1) ethylene, (ii) an aromatic vinyl compound represented by the following formula (I), (iii) a non-conjugated polyene, and, if necessary, (iv) a compound having 3 to 3 carbon atoms. 20 α-
A vulcanizate molded article having a surface decorative layer, characterized in that a decorative layer is provided on the surface of a vulcanizate of the unsaturated olefin copolymer (A) obtained from the olefin; 1) (In the formula, R ¹ , R ² and R ³ may be the same or different from each other, and represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and n is an integer of 0 to 5.) 2. A vulcanized product of an unsaturated olefin copolymer composition comprising (A) the unsaturated olefin copolymer according to claim 1 and (B) a vulcanizing agent. A vulcanizate molded article having a surface decorative layer, characterized by being provided with a decorative layer. 3. An unsaturated olefin copolymer composition comprising (A) the unsaturated olefin copolymer according to claim 1, (B) a vulcanizing agent, and (C) a reinforcing material. A vulcanizate molded article having a surface decorative layer, characterized in that a decorative layer is provided on the surface of the vulcanizate. 4. An unsaturated olefin copolymer composition comprising (A) the unsaturated olefin copolymer according to claim 1, (B) a vulcanizing agent, and (D) a liquid softener. A vulcanized product having a surface decorative layer, characterized in that a decorative layer is provided on the surface of a vulcanized product. 5. An unsaturated olefin copolymer according to claim 1, (B) a vulcanizing agent, and (C) a reinforcing material.
(D) a vulcanizate molded article having a surface decorative layer, wherein a decorative layer is provided on the surface of a vulcanizate of an unsaturated olefin copolymer composition comprising a liquid softener. . 6. The unsaturated olefin copolymer has a constitutional unit derived from ethylene (i) and a carbon number of 3 to 3.
The molar ratio (ethylene / α-olefin) to the structural unit derived from α-olefin (iv) is 100/0 to 4
Α / olefin (iv) having a constitutional unit derived from ethylene (i) and having 3 to 20 carbon atoms, which is in the range of 0/60.
And the molar ratio of the structural unit derived from the aromatic vinyl compound (ii) to the total amount of the structural unit derived from
α-olefin / aromatic vinyl compound) is 99.5 /
A vulcanizate molded article having a surface decorative layer according to any one of claims 1 to 5, which is in the range of 0.5 to 60/40. 7. The unsaturated olefin-based copolymer according to claim 1, wherein
The intrinsic viscosity [η] measured in decalin at 35 ° C. is 0.8 to
A vulcanizate molded article having a surface decorative layer according to any one of claims 1 to 6, which is in a range of 5.0 dl / g. 8. A coating film wherein the decorative layer is obtained from one kind of paint selected from the group consisting of acrylic resin paint, epoxy resin paint, polyester resin paint, urethane resin paint and alkyd resin paint. Claims 1 to 7
A vulcanizate molded article having the surface decorative layer according to any one of the above.