JP2002322224A - Cross-copolymerized olefin-aromatic vinyl compound- diene copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer satisfying heat resistance, various dynamics properties, compatibility and transparency, and having excellent molding processability, a composition of the same and a method for manufacturing the cross-copolymer in an industrially excellent manner; and further to provide various resin compositions containing an improved cross-copolymer and a molded product. SOLUTION: The cross-copolymer is obtained by cross-copolymerizing an olefin-aromatic vinyl compound copolymer to an olefin-styrene-diene copolymer consisting of styrene in an amount of >=0.03 mol% and <=96 mol%, a diene in an amount of >=0.0001 mol% and <=3 mol%, and an olefin in the balance. The cross-copolymer has excellent processability, dynamic specific characteristics, high temperature characteristics, compatibility and transparency, and it has high homogeneity. A composition of the same. A method for manufacturing the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (hereinafter sometimes abbreviated as cross-copolymer) having excellent moldability and its processability. Composition.

[0002]

2. Description of the Related Art Ethylene-aromatic vinyl compound (styrene) copolymer obtained by using a so-called homogeneous Ziegler-Natta catalyst system comprising a transition metal catalyst component and an organoaluminum compound. Some copolymers and a method for producing the same are known. JP-A-3-1630088 and JP-A-7-53618 disclose that a normal (ie, head-to-tail) styrene chain having a styrene content of 50 mol% or less obtained by using a complex having a so-called constrained geometric structure exists. No ethylene-styrene copolymers, so-called pseudo-random copolymers, are described. JP-A-6-49132, and Polymer Preprints, Japan,
42 , 2292 (1993) include a bridged metallocene system Z
Method for producing an ethylene-styrene copolymer having no aromatic vinyl compound chain and having an aromatic vinyl compound content of 50 mol% or less, that is, a so-called pseudo-random copolymer, using a catalyst comprising an r complex and a cocatalyst Is described. These copolymers do not have stereoregularity derived from aromatic vinyl compound units.

More recently, a specific bridged bisindenyl Zr complex, ie, racemic [ethylenebis (indenyl) zirconium dichloride] has been used at an extremely low temperature (−2
Under the condition of 5 ° C.), an ethylene-aromatic vinyl compound copolymer having a stereoregularity close to an alternating copolymer has been reported. (Macromol. Chem., RapidC.
ommun. , 17 , 745 (1996). )However,
The copolymer obtained with the present complex has a molecular weight that is not practically sufficient and has a large composition distribution. Also, JP-A-9-309
No. 925, Japanese Patent Application Laid-Open No. 11-130808,
It has a styrene content of 1 to 55 mol% and 1 to 99 mol%, respectively, has an ethylene-styrene alternating structure and a styrene chain structure, has isotactic stereoregularity, and has a head-tail styrene chain structure. , A high molecular weight novel ethylene-styrene copolymer having an alternating degree of copolymer (λ value in this specification) of 70 or less is described. Also,
This copolymer has high transparency.

[0004] Although the various ethylene-styrene random copolymers described above have various excellent characteristics, improvement of their heat resistance and physical properties at high temperatures is desired for practical use. . Further, conventional ethylene-styrene copolymers have remarkable changes in softness (Shore-A hardness, D hardness) depending on the styrene content. For example, Shore-A of a copolymer having a styrene content of about 5 mol%
The hardness is about 95, and decreases to about 85 at 10 mol%, and softens with an increase in the styrene content until the styrene content reaches about 25 mol%. However, when the styrene content of the copolymer increases, its heat resistance rapidly decreases. On the other hand, the cold resistance (brittleness temperature) of a copolymer having a low styrene content is excellent at -60 ° C. or lower, but the cold resistance deteriorates with an increase in the styrene content.
At about 0 ° C. and around 50 mol%, the temperature reaches room temperature. The copolymer having a styrene content of around 15 to 50 mol% is
It has a feel, flexibility and stress relaxation properties similar to PVC, and is useful as a substitute for PVC. In addition, it has excellent vibration damping and soundproofing properties. However, its heat resistance and cold resistance are poor and it is difficult to use it as it is.

[0005] When used as a stretch film, a copolymer having a styrene content of about 30 to 50 mol% exhibits a slow elongation recovery property at room temperature like a PVC stretch film, but becomes too hard under refrigerated or frozen conditions. . Further, if this film is to be manufactured by extrusion processing using a T-die or inflation molding, the films adhere to each other during winding because the film itself has high self-adhesiveness. Although a certain degree of self-adhesiveness is effective especially for replacing a PVC film as a stretch film for food packaging, it is difficult to achieve compatibility with film formability. Styrene content 40 mol%
The ethylene-styrene copolymer described above is excellent in printability and colorability, and also has improved compatibility with styrene-based resins. In particular, a copolymer having a styrene content of 20 mol% or less has poor printability and coloring properties, but has excellent compatibility with a polyolefin resin.

[0006] As described above, the physical properties and compatibility of these random ethylene-styrene copolymers are remarkably changed depending on the composition. And flexibility) cannot be satisfied at the same time. Conventionally,
In order to solve such problems, ethylene-styrene copolymers having different compositions may be mixed together to form a composition (Japanese Patent Application Laid-Open No. 2000-129043, WO98 / 10).
No. 018), a method of forming a composition with a polyolefin (WO98 / 10015), and crosslinking (US Pat. No. 5,869,591). However, ethylene-styrene copolymers having greatly different compositions have poor compatibility with each other, and their compositions and compositions with polyolefins are opaque, and their mechanical properties may be impaired, thus limiting their applications. In addition, when crosslinked, there is a problem that the secondary moldability and the recyclability are lost and the production cost is increased.

Ethylene-α-olefin copolymer Ethylene-α-olefin copolymer obtained by copolymerizing ethylene with 1-hexene, 1-octene, etc., so-called LLDPE
Is flexible and transparent and has high strength,
It is widely used as general-purpose films, packaging materials, containers and the like. However, the fate of the polyolefin resin is poor in printability and paintability, and a special treatment such as corona treatment is required for printing and painting. Furthermore, since it has low affinity with aromatic vinyl compound polymers such as polystyrene and polar polymers, it is necessary to use other expensive compatibilizers in order to obtain a composition having good mechanical properties with these resins. There was sex.

General Grafted Copolymer Conventionally, as a method for obtaining a graft copolymer, an olefin-based polymer or an olefin-based polymer can be prepared by polymerization using a generally known radical grafting method or by molding. A method for obtaining a graft copolymer of a styrene-based copolymer is known. However, in this method, it is difficult to obtain a high graft efficiency, which is disadvantageous in terms of cost, and the obtained graft copolymer is non-uniform and partially gels and becomes insoluble, or impairs moldability. And the like. The grafted copolymer thus obtained generally has a graft chain branched one by one from the polymer main chain. The strength is not enough.

[0009]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and satisfies the heat resistance, various mechanical properties, compatibility, transparency, and the moldability. Is a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer and a composition thereof. Secondly, the present invention solves the problems of the above-mentioned conventional various resin compositions and molded articles as applications of the cross copolymer of the present invention, and various resin compositions and molded articles containing the improved cross copolymers It provides things.

[0010]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and satisfies the heat resistance, various mechanical properties, compatibility, transparency, and the moldability. Cross-Copolymerized Olefin-Aromatic Vinyl Compound-
A diene copolymer and a composition thereof. Secondly, the present invention solves the problems of the above-mentioned conventional various resin compositions and molded articles as applications of the cross copolymer of the present invention, and various resin compositions and molded articles containing the improved cross copolymers Things.

[0011]

DISCLOSURE OF THE INVENTION <Cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (cross-copolymer)> In this specification, the content of the aromatic vinyl compound in the copolymer is included in the copolymer. The content of units derived from the aromatic vinyl compound monomer. The same applies to the olefin content and the diene content. The cross-copolymer of the present invention is an olefin-aromatic vinyl having an aromatic vinyl compound content of 0.03 mol% to 96 mol%, a diene content of 0.0001 mol% to 3 mol%, and a balance of olefin. The compound-diene copolymer is obtained by cross-copolymerizing an olefin-aromatic vinyl compound copolymer (which may contain a diene) whose aromatic vinyl compound content differs by 5 mol% or more. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer, comprising:
MFR measured at 0 ° C. under a load of 5 kg is 1.0 g / 10 min or more and 50 g / 10 min or less, preferably 1.0 g / 10 min or more and 20 g / 10 min or less. It is a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer. Preferably, the cross-copolymer of the present invention has an olefin-aromatic composition having an aromatic vinyl compound content of 0.03 mol% to 96 mol%, a diene content of 0.0001 mol% to 3 mol%, and a balance of olefin. Synthesis of an aromatic vinyl compound-diene copolymer,
Subsequently, the content of the aromatic vinyl compound is higher than 2.2 mol% and 96 mol% or less, and the content of the aromatic vinyl compound differs by 5 mol% or more from the olefin-aromatic vinyl compound copolymer (even if diene is contained). Good), and having an MFR measured at 230 ° C. under a load of 5 kg of 1.0 g / 10 min or more and 50 g / 10 min or less, preferably 1.0 g / 10 min or more and 20 g / min. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer excellent in moldability, characterized in that the time is 10 minutes or less. In the cross copolymer of the present invention, olefin-
Cross-copolymerization of an aromatic vinyl compound-diene copolymer with an olefin-aromatic vinyl compound copolymer having an aromatic vinyl compound content differing by 5 mol% or more results in copolymers having different aromatic vinyl compound contents. Can have both features, for example, heat resistance and softness.

The cross-copolymer of the present invention has an aromatic vinyl compound content of 0.03 mol% to 96 mol%, a diene content of 0.0001 mol% to 3 mol%, and a balance of olefin. A cross-copolymerized olefin-aromatic obtained by cross-copolymerizing an olefin-aromatic vinyl compound copolymer (which may contain a diene) with an olefin-aromatic vinyl compound-diene copolymer. An aromatic vinyl compound-diene copolymer, wherein the content of the aromatic vinyl compound differs from the olefin-aromatic vinyl compound-diene copolymer before cross-copolymerization by 2 mol% or more. It is a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer and has an MFR measured at 230 ° C. under a load of 5 kg of at least 1.0 g / 10 min. g / 10 minutes or less, preferably 1.0 g / 10 minutes or more and 20 g / 10 minutes or less, which is a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer excellent in moldability. . Preferably, the cross-copolymer of the present invention has an olefin-aromatic composition having an aromatic vinyl compound content of 0.03 mol% to 96 mol%, a diene content of 0.0001 mol% to 3 mol%, and a balance of olefin. An olefin-aromatic vinyl compound copolymer (which may contain a diene) having an aromatic vinyl compound content of more than 2.2 mol% and 96 mol% or less is cross-copolymerized with the aromatic vinyl compound-diene copolymer. What is claimed is: 1. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer characterized by being polymerized, wherein the content of the aromatic vinyl compound is higher than that of the olefin-aromatic vinyl compound-diene Compared to polymers,
A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer characterized by a difference of 2 mol% or more and an MFR of 1.degree.
0 g / 10 min or more and 50 g / 10 min or less, preferably 1.
A cross-copolymerized olefin excellent in moldability, characterized in that the olefin is from 0 g / 10 min to 20 g / 10 min.
It is an aromatic vinyl compound-diene copolymer. In the cross copolymer of the present invention, a finally obtained cross-copolymerized olefin-aromatic vinyl compound-diene copolymer,
The olefin-aromatic vinyl compound-diene copolymer before cross-copolymerization used has a different aromatic vinyl compound content of 2 mol% or more, so that various features of the copolymers having different aromatic vinyl compound contents, For example, it can have both heat resistance and softness. The cross copolymer of the present invention may finally have a composition in which the content of the aromatic vinyl compound is 5 mol% or more and 96 mol% or less, the diene content is 0.0001 mol% or more and 3 mol% or less, and the balance is olefin. it can. The cross-copolymer excellent in softness is preferably such that the final content of the aromatic vinyl compound is 5 mol% or more and 50 mol% or less, the diene content is 0.0001 mol% or more and 3 mol% or less, and the balance is olefin. It can have a composition.

The weight average molecular weight of the cross copolymer of the present invention is preferably 10,000 or more, more preferably 30,000 or more, particularly preferably 60,000 or more, and 1,000,000 or less, preferably 500,000 or less. The molecular weight distribution (Mw / Mn) is 1
0 or less, preferably 7 or less, most preferably 5 or less, and preferably 1.5 or more. In the specification of the present invention, the cross copolymer is a polymer that can be directly obtained by the production method described in the present specification.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION
It is preferably a cross-copolymer consisting of the structure shown in FIG. 1 or preferably containing mainly the structure shown in FIG. That is, as shown in FIG. 1, a structure in which a main chain olefin-aromatic vinyl compound-diene copolymer is bonded to a cross chain (cross bond or cross bond) at one or more points via a diene unit is mainly used. It is a copolymer having. Such a cross structure can be rephrased as a star structure. In addition, the classification by the American Chemical Society POLY subcommittee indicates that the segmented star cop
polymer (Polymer prints,
1998, March). Hereinafter, in the description of the present invention, an olefin-aromatic vinyl compound copolymer or an olefin (co) polymer cross-linked to a main chain olefin-aromatic vinyl compound-diene copolymer is referred to as a cross chain. On the other hand, as shown in FIG. 2, a graft copolymer known to those skilled in the art is a copolymer mainly having a polymer chain branched from one or more points of a main chain.
A structure in which the polymer main chain and other polymer chains cross-link (cross-link) (also referred to as a star structure) generally has a higher polymer microstructure than a grafted structure when used as a composition or compatibilizer. It is believed that excellent strength of the structural interface is obtained, giving high mechanical properties. Preferably, the cross copolymer of the present invention has a temperature of 230 ° C. and a load of 5 kg.
MFR measured at 1.0 g / 10 min or more and 50 g / 10
Min., Preferably 1.0 g / 10 min. To 20 g / 10 min.
Min, and at least one melting point of 6
5 ° C to 140 ° C, preferably 80 ° C to 140 ° C
℃ or less and its crystal heat of fusion is 10J
/ G to 150 J / g, preferably 20 J / g to 120 J / g. Further, preferably, the cross copolymer of the present invention has a crystal structure based on an ethylene chain structure. This crystal structure can be confirmed by a known method, for example, an X-ray diffraction method.

More preferably, the cross-copolymer of the present invention has at least one of the following relations among the aromatic vinyl compound content and the melting point having a heat of fusion of 10 J / g to 150 J / g measured by DSC. A cloth having an aromatic vinyl compound content of 5 mol% or more and 50 mol% or less, a diene content of 0.0001 mol% or more and 3 mol% or less, with the balance being ethylene or two or more olefins containing ethylene It is a copolymerized olefin-aromatic vinyl compound-diene copolymer. (5 ≦ St ≦ 20) −3 · St + 125 ≦ Tm ≦ 140 (20 <St ≦ 50) 65 ≦ Tm ≦ 140 Tm; Melting point (° C.) by DSC measurement St; Aromatic vinyl compound content (mol%)

More preferably, in the cross copolymer of the present invention, at least one of the aromatic vinyl compound content and the melting point having a heat of crystal fusion of 10 J / g or more and 150 J / g or less measured by DSC is as follows. A cloth having an aromatic vinyl compound content of 5 mol% or more and 50 mol% or less, a diene content of 0.0001 mol% or more and 3 mol% or less, and the balance being ethylene or two or more olefins containing ethylene. It is a copolymerized olefin-aromatic vinyl compound-diene copolymer. (5 ≦ St ≦ 15) −3 · St + 125 ≦ Tm ≦ 140 (15 <St ≦ 50) 80 ≦ Tm ≦ 140 Tm; Melting point (° C.) by DSC measurement St; Aromatic vinyl compound content (mol%)

More preferably, in the cross copolymer of the present invention, at least one of the aromatic vinyl compound content and the melting point having a crystal melting heat of 10 J / g or more and 150 J / g or less measured by DSC is as follows. A cloth having an aromatic vinyl compound content of 5 mol% or more and 15 mol% or less, a diene content of 0.0001 mol% or more and 3 mol% or less, and the balance being ethylene or two or more olefins containing ethylene. It is a copolymerized olefin-aromatic vinyl compound-diene copolymer. (5 ≦ St ≦ 10) −3 · St + 125 ≦ Tm ≦ 140 (10 <St ≦ 15) 95 ≦ Tm ≦ 140 Tm; Melting point (° C.) by DSC measurement St; Aromatic vinyl compound content (mol%) More preferably , A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer having one melting point observed by DSC and having the melting point satisfying the above relationship.

Among the cross copolymers of the present invention, the cross-copolymerized ethylene-styrene-divinylbenzene copolymer preferably has at least one glass transition point in the range of -15 ° C or lower and -30 ° C or higher. Can be. The glass transition point is determined by the tangent method (onse
glass transition point determined by t method). Cross-copolymerized olefin-aromatic vinyl compound-diene copolymer of the present invention, preferably having an aromatic vinyl compound content of 15 mol%
The following cross-copolymerized olefin-aromatic vinyl compound-diene copolymer is a 1 mm sheet molded product,
It can have a haze of 30% or less, preferably 20% or less. The cross-copolymerized olefin-aromatic vinyl compound-diene copolymer of the present invention, preferably a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer having an aromatic vinyl compound content of 15 mol% or less, is 1 m
m may have a total light transmittance of 70% or more, preferably 80% or more. Therefore, when the content of the aromatic vinyl compound is 5 mol% or more,
When the content is less than mol%, transparency and excellent heat resistance represented by the above formula can be combined.

Further, the present invention is characterized in that at 230 ° C., a load of 5 kg
MFR measured at 1.0 g / 10 min or more and 50 g / 10
Min., Preferably 1.0 g / 10 min. To 20 g / 10 min.
Min. Or less, and a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer excellent in moldability.
Furthermore, the present invention provides that the boiling xylene insolubles (gel content) determined by ASTM D-2765-84
Cross-copolymerized olefin-aromatic vinyl compound-diene having less than 0% by weight, preferably less than 1% by weight, and most preferably less than 0.1% by weight, low in gel content or substantially free of gel content It is a copolymer. The present invention
Preferably, the olefin is a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer in which the olefin is ethylene or two or more olefins containing ethylene. Also,
The cross copolymer of the present invention is a copolymer that can be obtained by the following production method.

The cross-copolymer of the present invention is not only a concept showing the cross-copolymer itself, but also the cross-copolymer, the first polymerization step, the second and subsequent polymerization steps (hereinafter referred to as the second polymerization step). (Which may be described below), the composition containing the non-crosslinked olefin-aromatic vinyl compound copolymer obtained in any ratio. The composition containing such a cross copolymer can be obtained by the production method described in the present specification. The cross copolymer of the present invention,
Since the content of the aromatic vinyl compound in the main chain and the cross chain is different, even if the olefin-aromatic vinyl compound copolymer having a different composition (aromatic vinyl compound content) obtained in each polymerization step is contained, these are compatible. It is thought to function as an agent. Therefore, the cross copolymer obtained by the production method described in the present specification has excellent mechanical properties, high heat resistance, transparency, and workability as compared with a normal olefin-aromatic vinyl compound copolymer. It is thought that. Further, the present invention provides a method for producing a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer excellent in economical efficiency, and a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer obtained by the method. A polymer is provided. These cross copolymers are extremely useful in a wide range of applications.

<Method for producing cross-copolymerized olefin-aromatic vinyl compound-diene copolymer> The present invention provides a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer obtainable by the following production method. It is a polymer (cross copolymer). Further, the present cross copolymer production method can produce a cross copolymer having uniformity, good processability, and excellent transparency and mechanical properties with efficiency and economy suitable for industrialization. That is,
The cross-copolymerized olefin-aromatic vinyl compound-diene copolymer of the present invention comprises a first polymerization step (main chain polymerization step).
A copolymerization of an aromatic vinyl compound monomer, an olefin monomer and a diene monomer using a coordination polymerization catalyst to synthesize an olefin-aromatic vinyl compound-diene copolymer, and then a second polymerization step (cross-linking) In step (2), the copolymer is produced by cross-copolymerizing an olefin-aromatic vinyl compound copolymer using the copolymer, an olefin and an aromatic vinyl compound monomer, and a coordination polymerization catalyst. This production method is a production method using two or more polymerization steps including the first polymerization step (main chain polymerization step) and the second polymerization step (cross-forming step).

The aromatic vinyl compound content of the olefin-aromatic vinyl compound-diene copolymer to be polymerized in the first polymerization step (main chain polymerization step) of the present invention and the second and subsequent polymerization steps (hereinafter referred to as the second polymerization step) The olefin-aromatic vinyl compound copolymer polymerized in the step (may be referred to as step) (when the polymerization solution obtained in the first polymerization step is used as it is in the second polymerization step, a small amount of The residual aromatic diene is copolymerized) should differ by at least 5 mol%, preferably 10 mol%, most preferably 15 mol% or more. The aromatic vinyl compound content of the olefin-aromatic vinyl compound copolymer polymerized in the second and subsequent polymerization steps (cross-forming step) is preferably higher than 2.2 mol%. Alternatively, the aromatic vinyl compound content of the olefin-aromatic vinyl compound-diene copolymer obtained in the first polymerization step and the aromaticity of the finally obtained cross-copolymerized olefin-aromatic vinyl compound-diene copolymer The vinyl compound content must differ by at least 2 mol%, preferably by at least 5 mol%.

<First Polymerization Step (Main Chain Polymerization Step)> The olefin-aromatic vinyl compound-diene copolymer used in the present invention comprises a single-site coordination of an aromatic vinyl compound monomer, an olefin monomer, and a diene monomer. It is obtained by copolymerization in the presence of a polymerization catalyst. As the olefins used in the present invention, ethylene, an α-olefin having 3 to 20 carbon atoms, ie, propylene,
Examples thereof include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and cyclic olefins, that is, cyclopentene and norbornene. Preferably, a mixture of ethylene and an α-olefin such as propylene, 1-butene, 1-hexene, or 1-octene, an α-olefin such as propylene, or ethylene is used. More preferably, ethylene, ethylene and α-olefin are used. Mixtures of olefins are used, particularly preferably ethylene.

Styrene is preferably used as the aromatic vinyl compound used in the present invention, but other aromatic vinyl compounds such as p-chlorostyrene, p-tert-butylstyrene, α-methylstyrene, vinylnaphthalene, p- Methylstyrene, vinylnaphthalene, vinylanthracene and the like can be used, and a mixture thereof may be used. Further, as the diene used in the present invention, a diene capable of coordination polymerization is used. Preferably 1,4-hexadiene, 1,5-hexadiene, ethylidene norbornene, dicyclopentadiene,
Norbornadiene, 4-vinyl-1-cyclohexene, 3
-Vinyl-1 cyclohexene, 2-vinyl-1 cyclohexene, 1-vinyl-1 cyclohexene, orthodivinylbenzene, paradivinylbenzene, metadivinylbenzene or a mixture thereof. Further, a diene in which a plurality of double bonds (vinyl groups) are bonded via a hydrocarbon group having 6 to 30 carbon atoms containing one or more aromatic vinyl ring structures can be used. Also, JP-A-6-136060 and JP-A-11-124420
Dienes described in Japanese Patent Application Laid-Open No. H10-208 can also be used in the present invention. Preferably, dienes in which one of the double bonds (vinyl group) is used for coordination polymerization and the remaining double bond is polymerizable by coordination polymerization, most preferably orthodivinylbenzene, palladium One or a mixture of two or more of vinylbenzene and metadivinylbenzene is suitably used.

In the present invention, the amount of diene used in the main chain polymerization step is 1/100 to 1 / 50,000 or more, preferably 1/4, of the amount of styrene used in a molar ratio.
00 or less and 1/20000 or more. When the main chain polymerization step is carried out at a diene concentration higher than this, a large amount of the crosslinked structure of the polymer is formed during the polymerization and gelation occurs, or the processability of the cross copolymer finally obtained through the crossing step is improved. It is not preferable because physical properties deteriorate. Further, when the main chain polymerization step is performed at a diene concentration higher than this, the residual diene concentration in the polymerization solution increases, so that when this polymerization solution is used as it is in the cross-forming step, a large number of cross-linked structures are generated, The processability and physical properties of the obtained cross copolymer similarly deteriorate. In particular, in order to obtain a cross copolymer having excellent flexibility, the olefin-aromatic vinyl compound-diene copolymer polymerized in the first polymerization step (main chain polymerization step) has an aromatic vinyl compound content of about 15%. It is preferable that the composition has a composition in which the content of diene is at least 0.001 mol% and less than 0.5 mol%, and the balance is olefin. In particular, in order to obtain a cross-copolymer having characteristics similar to soft PVC (tactile sensation such as softness, tan δ component near room temperature in viscoelastic spectrum), the aromatic vinyl compound is particularly preferably styrene. A styrene content of about 20 mol% to 50 mol% and a diene content of 0.001 mol% to less than 0.5 mol%;
An olefin-aromatic vinyl compound-diene copolymer whose balance is an olefin is used. Further, in order to obtain a cross-copolymer having both softness and cold resistance, the olefin-aromatic vinyl compound-diene copolymer polymerized in the first polymerization step (main chain polymerization step) must be an aromatic vinyl copolymer. It is preferable to have a composition in which the compound content is from 10 mol% to 30 mol%, the diene content is from 0.001 mol% to less than 0.5 mol%, and the balance is olefin. The diene content of the olefin-aromatic vinyl compound-diene copolymer obtained in the first polymerization step (main chain polymerization step) is as follows:
0.0001 mol% or more and 3 mol% or less, preferably 0.1 mol% or less.
It is at least 001 mol% and less than 0.5 mol%, most preferably at least 0.01 mol% and less than 0.3 mol%. If the diene content in the copolymer is lower, the efficiency of the cross-copolymerization decreases, and if the diene content is higher, the processability of the cross-copolymer finally obtained through the second polymerization step (cross-forming step) deteriorates, which is preferable. Absent.

As the single-site coordination polymerization catalyst used in the first polymerization step (main chain polymerization step), a polymerization catalyst comprising a transition metal compound and a cocatalyst, that is, a soluble Z
ieglar-Natta catalysts, transition metal compound catalysts activated with methylaluminoxane, boron compounds, etc. (so-called metallocene catalysts, half metallocene catalysts, CGC
T catalyst and the like). Specifically, polymerization catalysts described in the following documents and patents can be used. For example, in the case of metallocene catalysts, US Pat. No. 5,324,800, JP-B-7-37488, JP-A-6-49132, Polymer Preprints, Japan
n, 42 , 2292 (1993), Macromol.
Chem. , Rapid Commun. , 17 ,
745 (1996), JP-A-9-309925,
EP0872492A2, JP-A-6-18417
No. 9 gazette. For half metallocene catalysts, Makromomo
l. Chem. 191 , 2387 (1990). CGC
For the T catalyst, Japanese Patent Application Laid-Open Nos.
-53618, EP-A-416815.
In the case of a soluble Zieglar-Natta catalyst, Japanese Unexamined Patent Publication No.
-250007, Stud. Surf. Sci.
Catal. , 517 (1990).

An olefin-aromatic vinyl compound-diene copolymer having a uniform composition in which the diene is uniformly contained in the polymer is preferably used to obtain the cross copolymer of the present invention. It is difficult to obtain a copolymer having such a uniform composition with a Zieglar-Natta catalyst, and a single-site coordination polymerization catalyst is used.
A single-site coordination polymerization catalyst is a polymerization catalyst composed of a transition metal compound and a co-catalyst, and is a transition metal compound catalyst (a so-called metallocene catalyst, half metallocene catalyst, CGC
T catalyst etc.). In the present invention, a single-site coordination polymerization catalyst composed of one type of transition metal compound and a co-catalyst is preferably used. In the present invention, the most preferably used single-site coordination polymerization catalyst is a polymerization catalyst comprising a transition metal compound represented by the following general formula (1) and a cocatalyst. When a polymerization catalyst composed of a transition metal compound represented by the following general formula (1) and a cocatalyst is used, it is possible to copolymerize a diene, particularly divinylbenzene, with a polymer with high efficiency. It is possible to greatly reduce the amount of diene used in the first polymerization step (main chain polymerization step) and the amount of unreacted diene remaining in the polymerization solution.

If the amount of diene used in the main chain polymerization step is high, that is, if the concentration is high, a large amount of cross-linking of the polymer occurs during the main chain polymerization with the diene unit structure as a cross-linking point, resulting in gelation and insolubilization, and further cross-linking. It deteriorates the processability of the copolymer or cross copolymer. Also, if a large amount of unpolymerized dienes remains in the polymerization solution obtained in the main chain polymerization step, the degree of cross-linking of the cross chains will be significantly increased during the subsequent cross-polymerization step, and the resulting cross-linked The copolymer or the cross-copolymer is insolubilized, gelled, or deteriorates in processability. Further, the following general formula (1)
When a polymerization catalyst composed of a transition metal compound represented by and a cocatalyst is used, it is possible to produce an olefin-aromatic vinyl compound-diene copolymer having a very high activity and a uniform composition suitable for industrialization. It is. In addition, a highly transparent copolymer can be provided. Further, it is possible to provide an olefin-aromatic vinyl compound-diene copolymer having excellent mechanical properties and having isotactic stereoregularity and a head-tail styrene chain structure.

[0029]

Embedded image

In the formula, A and B are each independently selected from an unsubstituted or substituted benzoindenyl group, an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group, and an unsubstituted or substituted fluorenyl group. Group. Y has a bond with A and B, and further contains a group containing hydrogen or a hydrocarbon having 1 to 20 carbon atoms (this group is 1 to
5 nitrogen, boron, silicon, phosphorus, selenium, oxygen, fluorine,
A methylene group, a silylene group, an ethylene group, a germylene group, or a boron residue having a substituent (which may contain a chlorine or sulfur atom). The substituents may be different or the same. Y may have a cyclic structure such as a cyclohexylidene group and a cyclopentylidene group. X
Are each independently hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms,
An alkylaryl group having 12 carbon atoms, a silyl group having a hydrocarbon substituent having 1 to 4 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or hydrogen, or an amide group having a hydrocarbon substituent having 1 to 22 carbon atoms. . n is an integer of 0, 1 or 2. M is zirconium, hafnium, or titanium.

Particularly preferably, at least one of A and B
One is an unsubstituted or substituted benzoindenyl group,
Is a group selected from unsubstituted or substituted indenyl groups
From the transition metal compound of the above general formula (1) and a co-catalyst.
The polymerization catalyst to be formed. Unsubstituted or substituted benzoin
The benzyl group can be represented by the following formulas (2) to (4). following
In the chemical formula, R1b to R3b are each independently water
Element, 1-3 nitrogen, boron, silicon, phosphorus, selenium, oxygen
C1-20 hydrocarbons which may contain sulfur atoms
Group, preferably an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms
10 to 10 aryl groups, 7 to 20 carbon atoms alkyl aryl
Group, or halogen atom, OSiR _ThreeGroup, SiR_ThreeGroup,
NR_TwoGroup or PR_TwoGroup (R is a group having 1 to 10 carbon atoms
Represents a hydrocarbon group). In addition, these adjacent groups
Is a single or multiple 5- to 10-membered ring
An aromatic ring or an aliphatic ring may be formed. Also, R1a to R3
a is each independently hydrogen, 1 to 3 nitrogen, boron, silicon
May contain elemental, phosphorus, selenium, oxygen or sulfur atoms
C1-C20 hydrocarbon group, preferably C1-C2
0 alkyl group, 6-10 carbon aryl group, carbon number
7-20 alkylaryl groups or halogen atoms,
OSiR_ThreeGroup, SiR_ThreeGroup, NR_TwoGroup or PR_TwoGroup (R is
Each represents a hydrocarbon group having 1 to 10 carbon atoms).
Is preferably hydrogen.

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[0033]

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[0034]

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As unsubstituted benzoindenyl groups, 4,5
-Benzo-1-indenyl, (also known as benzo (e) indenyl), 5,6-benzo-1-indenyl, and 6,7-benzo-1-indenyl were substituted with α-acenaphth-1- as a substituted benzoindenyl group. Examples include indenyl, 3-cyclopenta [c] phenanthryl, and 1-cyclopenta [l] phenanthryl. Particularly preferably, as an unsubstituted benzoindenyl group, 4,5-benzo-1-indenyl (also called benzo (e) indenyl) is used, and as a substituted benzoindenyl group, α-acenaphth-1-indenyl, 3-cyclopenta [ c] phenanthryl, 1-cyclopenta [l] phenanthryl group and the like. The unsubstituted or substituted indenyl group, unsubstituted or substituted fluorenyl group or unsubstituted or substituted cyclopentadienyl group can be represented by the following formulas (5) to (7).

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[0037]

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[0038]

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R4b and R6 are each independently hydrogen, 1 to
Three nitrogen, boron, silicon, phosphorus, selenium, oxygen or sulfur
A C 1-20 hydrocarbon group which may contain a yellow atom,
Preferably, the alkyl group has 1 to 20 carbon atoms, and 6 to 10 carbon atoms.
An aryl group, an alkylaryl group having 7 to 20 carbon atoms,
Or halogen atom, OSiR_ThreeGroup, SiR_ThreeGroup, NR _Two
Group or PR_TwoGroup (R is a carbonized carbon atom having 1 to 10 carbon atoms)
Represents a hydrogen group). Also, these adjacent groups are
A single or multiple 5- to 10-membered rings (6-membered rings)
Even if it forms an aromatic or alicyclic ring
good. However, it is preferably hydrogen. R5 is each
Independently hydrogen, 1 to 3 nitrogen, boron, silicon, phosphorus, selenium
Carbon atoms which may contain oxygen, oxygen or sulfur atoms
0 hydrocarbon group, preferably alkyl having 1 to 20 carbon atoms
Group, an aryl group having 6 to 10 carbon atoms, an aryl group having 7 to 20 carbon atoms
Alkylaryl group or halogen atom, OSiR
_ThreeGroup, SiR_ThreeGroup, NR_TwoGroup or PR_TwoGroup (R is any
Represents a hydrocarbon group having 1 to 10 carbon atoms). Also next to
These groups that are in contact with one another
It may form a 5- to 10-membered aromatic or aliphatic ring.
However, it is preferably hydrogen. Also, R4a
Independently hydrogen, 1 to 3 nitrogen, boron, silicon, phosphorus, selenium
Carbon atoms which may contain oxygen, oxygen or sulfur atoms
0 hydrocarbon group, preferably alkyl having 1 to 20 carbon atoms
Group, an aryl group having 6 to 10 carbon atoms, an aryl group having 7 to 20 carbon atoms
Alkylaryl group or halogen atom, OSiR
_ThreeGroup, SiR_ThreeGroup, NR _TwoGroup or PR_TwoGroup (R is any
Represents a hydrocarbon group having 1 to 10 carbon atoms),
Preferably, there is. Both A and B are unsubstituted or substituted
Zoindenyl group or unsubstituted or substituted indenyl
And when they are the same, they may be the same or different.
No. In producing the copolymer used in the present invention
Is that at least one of A and B is unsubstituted or substituted
Particularly preferred is a benzoindenyl group. Further
And both are unsubstituted or substituted benzoindenyl groups
Most preferably.

In the above general formula (1), Y is A, B
And a hydrogen atom or a carbon atom having 1 as a substituent.
Groups containing up to 20 hydrocarbons, which groups have 1 to 5 nitrogens,
A methylene group, a silylene group, an ethylene group, a germylene group, or a boron residue having a boron, silicon, phosphorus, selenium, oxygen, fluorine, chlorine or sulfur atom). The substituents may be different or the same. Y may have a cyclic structure such as a cyclohexylidene group and a cyclopentylidene group. Preferably, Y has a bond to A and B, and is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a substituted methylene group or a substituted boron group substituted with an amino group or a trimethylsilyl group. Most preferably, Y has a bond with A and B, and is hydrogen or carbon atom 1
To 20 substituted methylene groups. Examples of the hydrocarbon substituent include an alkyl group, an aryl group, a cycloalkyl group, and a cycloaryl group. The substituents may be different or the same. Preferred examples, Y _{is, -CH 2 -, - CMe 2} -, - C
_{Et 2 -, - CPh 2 -} , cyclohexylidene, a cyclopentylidene group. Here, Me is a methyl group, Et
Represents an ethyl group, and Ph represents a phenyl group.

X is each independently hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 8 to 12 carbon atoms,
A silyl group having 4 hydrocarbon substituents, having 1 to 10 carbon atoms
Or an amide group or an amino group having a hydrogen or a hydrocarbon substituent having 1 to 22 carbon atoms. n is an integer of 0, 1 or 2. Halogen is chlorine, bromine, fluorine, etc., alkyl is methyl, ethyl, etc., aryl is phenyl, etc., alkylaryl is benzyl, silyl is trimethylsilyl, etc. And alkoxy groups include methoxy, ethoxy and isopropoxy groups, and amide groups such as dialkylamide groups such as dimethylamide groups and arylamide groups such as N-methylanilide, N-phenylanilide and anilide groups. Is mentioned. Further, as X, U.S. Pat. No. 5,859,276,
The groups described in US Pat. No. 5,892,075 can also be used. M is zirconium, hafnium, or titanium. Particularly preferred is zirconium.

Examples of such transition metal compounds include EP
-0872492A2, JP-A-11-130808
JP, JP-A-9-309925, WO00 / 2
0426, EP0985689A2, JP-A-6
And transition metal compounds described in JP-A-184179. Particularly preferably, EP-0872492
A2, JP-A-11-130808, JP-A-9
It is a transition metal compound having a substituted methylene bridge structure specifically exemplified in JP-A-309925.

As the cocatalyst used in the production method of the present invention, known cocatalysts and alkylaluminum compounds conventionally used in combination with a transition metal compound can be used. Aluminoxanes (or methylalumoxane or MAO) or boron compounds are preferably used. Examples of the cocatalyst and the alkylaluminum compound to be used are disclosed in EP-0872492A2 and JP-A-11-1.
No. 30808, JP-A-9-309925, W
Co-catalysts and alkylaluminum compounds described in O00 / 20426, EP0985689A2, and JP-A-6-184179. Further, the co-catalyst used at that time is represented by the following general formula (2):
The aluminoxane (or alumoxane) represented by (3) is preferred.

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In the formula, R represents an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or hydrogen, and m represents 2 to 10 carbon atoms.
It is an integer of 0. Each R may be the same or different.

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In the formula, R ′ is an alkyl group having 1 to 5 carbon atoms,
An aryl group having 6 to 10 carbon atoms or hydrogen, and n is 2 to 1
It is an integer of 00. Each R 'may be the same or different.

In producing the olefin-aromatic vinyl compound-diene copolymer used in the present invention,
Each monomer, metal complex (transition metal compound) and cocatalyst exemplified above are brought into contact with each other, and the order of contact and the contacting method may be any known methods. As a method of the above copolymerization or polymerization, a method of polymerizing in a liquid monomer without using a solvent, or pentane, hexane, heptane, cyclohexane, benzene, toluene,
There is a method using a saturated aliphatic or aromatic hydrocarbon or a halogenated hydrocarbon alone or a mixed solvent such as ethylbenzene, xylene, chloro-substituted benzene, chloro-substituted toluene, methylene chloride and chloroform. Preferably, a mixed alkane solvent, cyclohexane, toluene, or ethylbenzene is used. The polymerization form may be either solution polymerization or slurry polymerization. In addition, polymerization is a batch type, a batch type,
Any type of continuous type may be used. As the polymerization apparatus, a known apparatus such as a tank type, a single linear or loop type or a plurality of connected pipes, or a tower type can be used. In this case, the pipe-shaped polymerization apparatus includes various known mixers such as a dynamic or static mixer and a static mixer that also serves as heat removal, and a cooler equipped with a heat removal thin tube. It may have various known coolers. Moreover, you may have a batch type pre-polymerization can. Further, a method such as gas phase polymerization can be used.

The polymerization temperature is suitably from -78 ° C to 200 ° C. A polymerization temperature lower than -78 ° C is industrially disadvantageous, and a temperature higher than 200 ° C is not suitable because decomposition of the metal complex occurs. Industrially preferably, it is 0 ° C to 160 ° C.
° C, particularly preferably 30 ° C to 160 ° C. The pressure at the time of polymerization is generally from 0.1 to 1000 atm, preferably from 1 to 100 atm, particularly preferably from 1 to 30 atm. When an organoaluminum compound is used as a cocatalyst,
0.1 to 1000 in terms of aluminum atom / complex metal atom ratio
00, preferably 10 to 10,000.
If it is less than 0.1, the metal complex cannot be activated effectively,
If it exceeds 00000, it is economically disadvantageous. When a boron compound is used as a co-catalyst, it is used in a ratio of boron atom / complex metal atom ratio of 0.01 to 100, preferably 0.1 to 10, particularly preferably 1.
If it is less than 0.01, the metal complex cannot be activated effectively,
If it exceeds 100, it is economically disadvantageous. The metal complex and the cocatalyst may be mixed and prepared outside the polymerization tank, or may be mixed in the tank during polymerization.

In the first polymerization step of the present invention, the olefin partial pressure can be changed continuously or stepwise within a range of less than 150% or more than 50% of the olefin partial pressure at the start of the polymerization. The olefin partial pressure in the first polymerization step is preferably kept constant during the polymerization. In the first polymerization step of the present invention, the concentration of the aromatic vinyl compound in the polymerization liquid is higher than 30% and higher than the concentration at the start of polymerization by 200%.
It can be changed continuously or stepwise in a lower range. Preferably, the aromatic vinyl compound monomer is not added and the conversion of the aromatic vinyl compound monomer is less than 70% (the concentration of the aromatic vinyl compound is higher than 30% as compared with that at the start of polymerization). Is good.

<Olefin-Aromatic Vinyl Compound-Diene Copolymer Used in the Present Invention> The olefin-aromatic vinyl compound-diene copolymer used in the present invention has a single-site coordination in the first polymerization step. It is synthesized from monomers of an aromatic vinyl compound, an olefin and a diene using a polymerization catalyst. The olefin-aromatic vinyl compound-diene copolymer obtained in the first polymerization step (main chain polymerization step) of the present invention is preferably an ethylene-styrene-diene copolymer or ethylene-styrene-α.
-An olefin-diene copolymer or an ethylene-styrene-cyclic olefin-diene copolymer, particularly preferably an ethylene-styrene-diene copolymer is used.
Further, the olefin-aromatic vinyl compound-diene copolymer obtained in the first polymerization step (main chain polymerization step) of the present invention may have a cross structure or a cross-linked structure in the diene monomer unit contained therein. , Gel content is 10
It must be less than 0.1% by weight, preferably less than 0.1% by weight.

Hereinafter, typical and suitable ethylene-styrene-diene copolymers used in the present invention will be described. The ethylene-styrene-diene copolymer obtained in the first polymerization step (main chain polymerization step) is 1 based on TMS.
It preferably has a chain structure of styrene units of the head-tail attributed to a peak observed at 40 to 45 ppm by 3C-NMR measurement, and further,
42.3-43.1 ppm, 43.7-44.5 pp
m, 40.4-41.0 ppm, 43.0-43.6p
It preferably has a chain structure of styrene units assigned by the peak observed in pm. Further, the copolymer suitably used in the present invention is an ethylene-styrene-diene copolymer obtained by using a metallocene catalyst capable of producing isotactic polystyrene by homopolymerization of styrene, and An ethylene-styrene-diene copolymer obtained using a metallocene catalyst capable of producing polyethylene by homopolymerization of ethylene. Therefore, the obtained ethylene-styrene-diene copolymer can have both an ethylene chain structure, a head-tail styrene chain structure, and a structure in which an ethylene unit and a styrene unit are bonded in its main chain.

The ethylene-styrene-diene copolymer obtained in the first polymerization step (main chain polymerization step) preferably used in the present invention is a styrene represented by the following general formula (4) contained in its structure. The stereoregularity of the phenyl group in the alternating structure of ethylene and ethylene is greater than 0.5, preferably greater than 0.75, particularly preferably greater than 0.95 in isotactic dyad fraction (or meso dyad fraction) m. It is a copolymer. The isotactic dyad fraction m of the alternating copolymer structure of ethylene and styrene is represented by r of the methylene carbon peak appearing at about 25 ppm.
The peak area Ar derived from the structure and the area Am of the peak derived from the m-structure can be determined by the following formula (ii). m = Am / (Ar + Am) Formula (ii) The appearance position of the peak may be slightly shifted depending on the measurement conditions and the solvent. For example, using deuterated chloroform as a solvent,
Based on TMS, the peak derived from the r-structure is
A peak derived from the m-structure appears at around 25.4 to 25.5 ppm, and a peak at around 25.2 to 25.3 ppm. Also,
When heavy tetrachloroethane is used as a solvent and the center peak of the triplet of heavy tetrachloroethane is set as 73.89 ppm, the peak derived from the r structure is 25.3 to 25.3.
Around 5.4 ppm, the peak derived from the m-structure was 25.
Appears around 1-25.2 ppm. Note that the m structure indicates a meso diad structure, and the r structure indicates a racemic diad structure.

The ethylene-styrene-diene copolymer obtained in the first polymerization step (main chain polymerization step) has a ratio of an alternating structure of styrene and ethylene represented by the general formula (4) contained in the copolymer structure. The copolymer preferably has an alternating structure index λ (represented by the following formula (i)) of less than 70, more than 0.01, preferably less than 30, and more than 0.1. λ = A3 / A2 × 100 Formula (i) Here, A3 represents three types of peaks a and b derived from an ethylene-styrene alternating structure represented by the following general formula (4 ′) and obtained by 13 C-NMR measurement. , C is the sum of the areas. A2 is 13C-NM based on TMS.
It is the sum of the areas of peaks derived from main chain methylene and main chain methine carbon observed in the range of 0 to 50 ppm by R.

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(Where Ph is a phenyl group, x is the number of repeating units and is an integer of 2 or more.) An ethylene-styrene-diene copolymer having a diene content of 3 mol% or less, preferably less than 1 mol%. Has a head-tail styrene chain and / or has an isotactic stereoregularity in an ethylene-styrene alternating structure and / or has an alternating structure index λ value of 70.
Smaller is effective because it is an elastomer copolymer having high transparency and high mechanical strength such as breaking strength, and a copolymer having such characteristics can be suitably used in the present invention. . In particular, the ethylene-styrene alternating structure has a high degree of isotactic stereoregularity, and
A copolymer having an alternating structure index λ value of less than 70 is preferable as the copolymer of the present invention. Further, the copolymer has a head-tail styrene chain and has an ethylene-styrene alternating structure having isotactic stereoregularity. A copolymer having an alternating structure index λ value of less than 70 is particularly preferred as the copolymer of the present invention.

That is, the preferred ethylene-styrene-diene copolymer of the present invention has an ethylene-styrene alternating structure having high stereoregularity, an ethylene chain of various lengths, a heterogeneous bond of styrene, and various lengths. It has the feature of having various structures such as styrene chains. Further, the ethylene-styrene-diene copolymer of the present invention, the polymerization catalyst and polymerization conditions to be used, the ratio of the alternating structure depending on the styrene content in the copolymer, the λ value obtained from the above formula is from 0.01 to λ value. Various changes can be made in a large range of less than 70. An alternating index λ value of less than 70 means that the crystalline polymer has significant mechanical strength,
It is important to provide solvent resistance, toughness, and transparency, and to be a partially crystalline polymer or an amorphous polymer.

The olefin-aromatic vinyl compound-diene copolymer preferably used in the present invention, particularly the ethylene-styrene-divinylbenzene copolymer described above, is
It can be obtained by a polymerization catalyst composed of the transition metal compound represented by the general formula (1) and a co-catalyst. As described above, the ethylene-styrene-diene copolymer as a representative and preferred example of the olefin-aromatic vinyl compound-diene copolymer used in the present invention has been described. The vinyl compound-diene copolymer is not limited to this.

The weight average molecular weight of the olefin-aromatic vinyl compound-diene copolymer used in the present invention is preferably 10,000 or more, more preferably 30,000 or more, particularly preferably 60,000 or more, and 1,000,000 or less. , Preferably 500,000 or less. The molecular weight distribution (Mw / Mn) is at most 6, preferably at most 4, and most preferably at most 3. Here, the weight average molecular weight refers to a molecular weight in terms of polystyrene determined by GPC using standard polystyrene. The same applies to the following description. The weight average molecular weight of the olefin-aromatic vinyl compound-diene copolymer used in the present invention is within the above range as required by a known method using a chain transfer agent such as hydrogen, or by changing the polymerization temperature. It is possible to adjust. The olefin-aromatic vinyl compound-diene copolymer obtained in the first polymerization step (main chain polymerization step) of the present invention may have a partial cross structure or a branched structure via a diene unit contained therein. good.

B) Second Polymerization Step (Cross-forming Step) As the second polymerization step of the present invention, coordination polymerization using the above-described single-site coordination polymerization catalyst is employed. Preferably, a single-site coordination polymerization catalyst comprising a transition metal compound represented by the same general formula (1) and a cocatalyst as in the first polymerization step is employed. The single-site coordination polymerization catalyst composed of the transition metal compound represented by the general formula (1) and a cocatalyst is a diene unit copolymerized in a polymer main chain,
In particular, the present invention is preferable in the present invention because the residual coordination polymerizable double bond of divinylbenzene can be copolymerized with high efficiency. In the second polymerization step of the present invention, it is most preferable to use the same single-site coordination polymerization catalyst (same transition metal compound, same cocatalyst) as in the first polymerization step. The copolymer obtained in the second polymerization step of the present invention preferably has the same structure as the copolymer in the first polymerization step. In the second polymerization step of the present invention, the same method as the polymerization method used in the first polymerization step is used. In this case, each monomer of olefins and aromatic vinyl compounds used in the first polymerization step can be used. The second polymerization step of the present invention is preferably carried out using the polymerization solution obtained in the above-mentioned first polymerization step and subsequently to the first polymerization step. However, the copolymer obtained in the above-mentioned first polymerization step is recovered from the polymerization solution, dissolved in a new solvent, and the monomer used is added, and the second polymerization step is performed in the presence of a single-site coordination polymerization catalyst. May be implemented.

The olefin-aromatic vinyl compound-diene copolymer polymerized in the first polymerization step (main chain polymerization step) of the present invention and the olefin-aromatic polymerized in the second and subsequent polymerization steps (cross-forming step) Group vinyl compound copolymer or olefin-aromatic vinyl compound-diene copolymer (when the polymerization solution obtained in the first polymerization step is used as it is in the second and subsequent polymerization steps, a small amount of residual The aromatic vinyl compound content of the diene) must differ by at least 5 mol%, preferably 10 mol%, most preferably 15 mol% or more. The aromatic vinyl compound content of the olefin-aromatic vinyl compound copolymer polymerized in the second and subsequent polymerization steps (cross-forming step) may be 0 mol% in extreme cases, but may be higher than 2.2 mol%. preferable. Alternatively, the aromatic vinyl compound content of the olefin-aromatic vinyl compound-diene copolymer obtained in the first polymerization step and the aromaticity of the finally obtained cross-copolymerized olefin-aromatic vinyl compound-diene copolymer The vinyl compound content must differ by at least 2 mol%, preferably by at least 5 mol%.
When the polymerization liquid obtained in the first polymerization step is used in the second polymerization step, unreacted diene remaining in the polymerization liquid is copolymerized in the second polymerization step, and the diene content is determined by the second polymerization step. In the olefin-aromatic vinyl compound copolymer (including cross chains) obtained in the step, it is usually in the range of 0.0001 to 3 mol%, preferably 0.001 to 3 mol%.
1 mol% or more and less than 0.5 mol%. If the diene content is higher than this, the finally obtained cross-copolymer is insolubilized, gelled, or deteriorates in processability, which is not preferable. However, the polymer obtained in the second polymerization step (cross-chain polymerization step) of the present invention may partially have a cross structure or a branched structure via a small amount of a diene unit contained.

A specific method for producing the cross copolymer of the present invention satisfying the above conditions will be described below. That is, as a first polymerization step (main chain polymerization step), an aromatic vinyl compound monomer, an olefin monomer and a diene monomer are copolymerized using a coordination polymerization catalyst to form an olefin-aromatic vinyl compound-diene copolymer. The olefin-aromatic vinyl compound-diene copolymer is co-polymerized with at least an olefin and an aromatic vinyl compound monomer. A method for producing a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer produced by using at least a two-stage polymerization method in which a polymerization is carried out using a catalyst, and more preferably, at least one of the following conditions: This is a manufacturing method satisfying the above.

1) The olefin partial pressure of the polymerization system in the second and subsequent polymerization steps is 150% or more or 50% or less with respect to the olefin partial pressure at the start of the first polymerization step. However, the olefin partial pressure in the second and subsequent polymerization steps is industrially preferably at most 1,000 atm, and preferably at most 100 atm. On the other hand, in the present invention, the olefin partial pressure in the first polymerization step is adjusted to a range higher than 50% and lower than 150% of the olefin pressure at the start of the polymerization, but it is more preferable that the olefin partial pressure is constant. 2) The concentration of the aromatic vinyl compound in the polymerization liquid at the start of the second and subsequent polymerization steps is 30% or less, or 200% or more, relative to the aromatic vinyl compound concentration at the start of the first polymerization step. However, the aromatic vinyl compound concentration in the first step in the present invention is maintained in a range higher than 30% of the concentration at the start of polymerization. 3) Different single-site coordination polymerization catalysts are used in the first polymerization step and the second and subsequent polymerization steps. 4) The type of olefin used for the polymerization is different between the first polymerization step and the second and subsequent polymerization steps.

The first polymerization step and the second polymerization step are distinguished when the operation for changing these conditions is started or when these changes are satisfied. The change satisfying the above conditions is performed as rapidly as possible and completed, preferably within 50% of the polymerization time of the second polymerization step,
More preferably, it is completed within 30%, most preferably within 10%. It is preferable that the polymerization temperatures of the first polymerization step and the second polymerization step are the same. If different, a temperature difference within a maximum of 100 ° C., preferably 70 ° C. is appropriate. As a method of changing the monomer composition ratio in the polymerization liquid, the olefin partial pressure of the polymerization system in the second and subsequent polymerization steps is set to 150% or more, preferably 200%, and most preferably 300% or more with respect to the first polymerization step. There is a way to change. For example, when ethylene is used as the olefin, when the first polymerization step is performed at an ethylene pressure of 0.2 MPa, 0.3 M is used in the second polymerization step.
It is carried out at a pressure of at least Pa, preferably at least 0.4 MPa, most preferably at least 0.6 MPa.

In the first and second polymerization steps, the olefin partial pressure of the polymerization system in the second and subsequent polymerization steps may be changed to 50% or less, preferably 20% or less. For example, when the first polymerization step is performed at an ethylene pressure of 1.0 MPa,
In the second polymerization step, 0.5 MPa or less, preferably 0.2 MPa
It is carried out at a pressure of MPa or less. The olefin partial pressure in the second polymerization step may be constant during the polymerization, or may be changed stepwise or continuously as long as the above conditions are satisfied. Further, as a method of changing the monomer composition ratio in the polymerization liquid, the concentration of the aromatic vinyl compound in the polymerization liquid at the start of the polymerization in the second and subsequent polymerization steps is 30% with respect to the first polymerization step.
Hereinafter, a method of changing the content to preferably 20% or less, or 200% or more, preferably 500% or more is also applicable. For example, when styrene is used as the aromatic vinyl compound, when the first polymerization step is started at a styrene concentration of 1 mol / L in the polymerization liquid, 0.5 mol / L is used in the second polymerization step.
Hereinafter, the reaction is preferably performed at 0.2 mol / L or less, or 2 mol / L or more, preferably 5 mol / L or more. Furthermore, you may apply combining the said olefin partial pressure and the change of an aromatic vinyl compound density | concentration.

The copolymer obtained in the first polymerization step is recovered from the polymerization solution, dissolved in a new solvent, an olefin and an aromatic vinyl compound monomer are added, and the copolymer is added in the presence of a single-site coordination polymerization catalyst. When performing the two polymerization step,
A single site polymerization catalyst different from the first polymerization step can be used.

In the first polymerization step and the second and subsequent polymerization steps, by changing the type of olefin used for the polymerization, the aromatic vinyl compound of the copolymer polymerized in the first polymerization step and the second polymerization step is obtained. The content and the aromatic vinyl compound content of the finally obtained cross-copolymer can be changed as described above. The second polymerization step is carried out subsequent to the first polymerization step using the polymerization liquid obtained in the above first polymerization step, and remains in the first polymerization step polymerization liquid without addition of a new aromatic vinyl compound monomer. When the monomer is used in the second polymerization step, the conversion of the aromatic vinyl compound monomer species through all the polymerization steps is preferably at least 50% by mass, particularly preferably at least 60% by mass. As the conversion of the aromatic vinyl compound monomer increases, the probability that the polymerizable double bond of the diene unit of the copolymer main chain is cross-copolymerized increases.

In the production of the cross copolymer of the present invention, a production method that satisfies the above conditions 1) and 2) is preferably employed. That is, in the second polymerization step, it is preferable to use the same single-site coordination polymerization catalyst (the same transition metal compound and the same cocatalyst) as in the first polymerization step. In the first polymerization step and the second and subsequent polymerization steps, it is preferable that the type of olefin used for the polymerization is the same. Further, in the production of the cross-copolymer of the present invention, a production method that satisfies 1) among the above conditions is most preferably employed. In the production of the cross-copolymer of the present invention, a method is preferably employed in which the partial pressure of the olefin in the polymerization system in the second and subsequent polymerization steps is changed to 300% or more with respect to the first polymerization step. Also,
When the olefin partial pressure in the first polymerization step is not constant, that is, when the olefin partial pressure fluctuates within the above range, the olefin partial pressure in the second and subsequent polymerization steps is most preferably relative to the olefin partial pressure at the start of the first polymerization step. A method of changing the pressure to 300% or more is adopted.

The proportion of the copolymer obtained in the first polymerization step must account for at least 10% by mass or more, preferably 30% by mass or more of the finally obtained cross copolymer. Further, the amount of the polymer (including the mass of the cross chain) obtained in the second polymerization step needs to account for at least 10% by mass or more, preferably 30% by mass or more of the finally obtained cross copolymer. If the proportion of the copolymer obtained in the first polymerization step or the second polymerization step is less than 10% by weight of the finally obtained cross copolymer, the characteristics of the copolymer having a small amount of components will not be sufficiently exhibited. The first polymerization step and the second polymerization step can be performed in different reactors. These steps can also be performed using a single reactor. In this case, the first polymerization step and the second polymerization step are performed when the operation for changing these conditions is started, or when the above-mentioned 1) to
A distinction is made when the condition change of 4) is satisfied. The cross-copolymer of the present invention, in a single reactor, while continuously changing the olefin or aromatic vinyl compound concentration, the copolymerization of olefin, aromatic vinyl compound, diene using a coordination polymerization catalyst It can also be manufactured. It is necessary that at least one of the above conditions 1) to 4) is substantially satisfied between the initial stage and the end of the polymerization.

Further, the cross copolymer of the present invention comprises 230
It is a cross copolymer excellent in moldability, characterized in that the MFR (melt flow rate) measured at a temperature of 5 ° C. and a load of 5 kg is 1.0 g / 10 min or more and 50 g / 10 min or less. The method for producing the cross copolymer of the present invention is not particularly limited, but a production method that satisfies one or more of the following production conditions is preferable. a) In the first and / or second polymerization step, substantially always at least 80 ° C., preferably at least 85 ° C., 160 ° C. during the polymerization.
The polymerization temperature is as follows. b) The aromatic vinyl compound content of the polymer obtained in the first polymerization step is 30 mol% or more, and the weight average molecular weight is 250,000 or less. c) The diene used is metadivinylbenzene having an isomer purity of 80% by mass or more, preferably 90% by mass or more. The cross copolymer of the present invention can be produced by a production method including the first polymerization step (main chain polymerization step) and the second polymerization step (cross-forming step). The process can use any known method. For example, a method in which the first polymerization step is performed by batch polymerization or continuous polymerization (batch polymerization) of complete mixing, and the second polymerization step is performed by the same batch polymerization or continuous polymerization (batch polymerization), or a method in which the first polymerization step is performed. Is a completely mixed batch polymerization or continuous polymerization (batch polymerization)
And a method in which the second polymerization step is performed by plug flow polymerization. Here, the complete mixing type polymerization is a known method using, for example, a tank-shaped, tower-shaped or loop-shaped reactor, and the polymerization liquid is relatively well stirred and mixed in the reactor, substantially This is a polymerization method capable of having a uniform composition. In addition, the plug flow polymerization is a polymerization method in which mass transfer is restricted in a reactor, and a polymerization solution has a continuous or discontinuous composition distribution in a polymerization liquid from an inlet to an outlet of the reactor. In the second polymerization step of the present invention, from the viewpoint of efficiently removing heat because the viscosity of the polymerization solution increases, various types of coolers and mixers are provided, and a loop type or plug flow having a pipe shape is provided. The polymerization method of the formula is preferred.

The physical properties of the cross-copolymerized ethylene-styrene-divinylbenzene copolymer as a typical example of the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer of the present invention and its use will be described below. The cross copolymer of the present invention is characterized in that the composition (styrene content) of the main chain and the cross chain is largely different. Either the main chain or the cross chain can have a composition having a low styrene content (that is, a crystal structure derived from an ethylene chain). In addition, the cross-copolymer of the present invention may be an ethylene-styrene copolymer (which may contain a small amount of divinylbenzene) having a different styrene content corresponding to the styrene content of the main chain and the cross-chain, respectively. Can be included in proportions. However, since the cross copolymer functions as a compatibilizing agent, it is possible to combine various characteristics with high transparency.

Since the cross copolymer of the present invention has a crystal structure derived from an ethylene chain, it has good heat resistance. Furthermore, the low glass transition temperature and low embrittlement temperature of an ethylene-styrene copolymer having a low styrene content (−
(At 50 ° C. or lower) and high mechanical properties (rupture strength, tensile modulus). Also,
Since it can have a composition having a relatively high styrene content in either the main chain or the cross chain, it can have the following characteristics of an ethylene-styrene copolymer having a relatively high styrene content. That is, a relatively low tensile modulus, surface hardness, flexibility, a tan δ component near room temperature in the viscoelastic spectrum (0.05 to 0.80 at 0 ° C. or 25 ° C.), scratch resistance,
It can have a PVC-like feel, coloring property, and printability.
The cross copolymer of the present invention comprises a main chain copolymer (a copolymer component obtained in the first polymerization step) and a cross chain copolymer (a copolymer component obtained in the second polymerization step). By changing the weight ratio of the resin, even in the category of soft resin, from relatively hard resin (Shore-A hardness of 88 or more) to soft resin (Shore-A hardness of 87 or less, about 60 or more) The hardness can be arbitrarily changed. In particular, in order for the Shore-A hardness of the cross copolymer of the present invention to be 87 or less, either the first polymerization step or the copolymer obtained in the second polymerization step is substantially non-crystalline. Preferably, the substantially non-crystalline copolymer accounts for at least 60% by mass or more of the finally obtained cross copolymer. Further, the copolymer obtained in the first polymerization step is substantially non-crystalline, and this substantially non-crystalline copolymer occupies at least 60% by mass or more of the finally obtained cross copolymer. Is particularly preferred. The term "substantially non-crystalline" as used herein means that the melting point of the crystal peak observed in DSC is 50 ° C. or less, more preferably the heat of fusion is 15 J / g or less, or the crystal calculated by the X-ray diffraction method. It means that the degree of crystallization (crystallinity) is 10% or less. Further, the glass transition point of the copolymer obtained in the first polymerization step is 5 ° C. or less, preferably 0 ° C. or less.
It is important to: The cross-copolymerized ethylene-styrene-diene copolymer of the present invention can be used alone and suitably used as a substitute for known transparent soft resins such as soft PVC.

The cross-copolymer of the present invention contains a stabilizer, an antioxidant, a light resistance improver, an ultraviolet absorber, a plasticizer, a softener, a lubricant, a processing aid, a colorant, Antistatic agents, antifogging agents, antiblocking agents, crystal nucleating agents and the like can be added. These can be used alone or in combination of two or more. The cross-copolymer of the present invention, because of its excellent characteristics, as a composition mainly containing itself or itself, as a substitute for a known transparent soft resin such as soft PVC, a stretch film, a shrink film or a package material, a sheet Can be suitably used as a tube or hose

When the cloth copolymer of the present invention is used as a film or a film for stretch packaging, the thickness thereof is not particularly limited, but is generally 3 μm to 1 mm, preferably 10 μm to 0.1 μm.
5 mm. In order to use it suitably as a stretch packaging film for foods, it is preferably 5 to 100.
μm, more preferably 10 to 50 μm. In order to produce a transparent film or a film for stretch packaging comprising the cross copolymer of the present invention, a usual extrusion film forming method such as an inflation method or a T-die method can be employed. The film of the present invention or the film for stretch wrapping, for the purpose of improving the physical properties, other suitable films, for example, isotactic or syndiotactic polypropylene, high-density polyethylene,
Low density polyethylene (LDPE or LLDPE),
It can be multilayered with a film of polystyrene, polyethylene terephthalate, ethylene-vinyl acetate copolymer (EVA) or the like.

Furthermore, the film or stretch packaging film of the present invention can have self-adhesiveness and adhesiveness by appropriately selecting the composition of the main chain or the cross chain. However, when stronger self-adhesiveness is required, a multilayer film with another film having self-adhesiveness can be used. Furthermore, when it is desired to form a stretch packaging film having a non-adhesive surface and an adhesive surface on the front and back, a linear low-density polyethylene having a density of 0.916 g / cm ³ or more is about 5 to 30% of the total thickness, The ethylene-styrene copolymer used in the present invention is added to the adhesive layer, and the ethylene-styrene copolymer used in the present invention is added with 2 to 10% by mass of liquid polyisobutylene, liquid polybutadiene, or the like, or the adhesive layer has a density of 0. 916 g / cm ³
The following linear low-density polyethylene is obtained by adding liquid polyisobutylene, liquid polybutadiene, etc. in an amount of 2 to 10% by mass, or a multilayer film in which an ethylene-vinyl acetate copolymer is laminated in an amount of about 5 to 30% based on the total thickness. You can do it. Further, an appropriate tackifier may be added and used in an appropriate amount.

Although the specific application of the film of the present invention is not particularly limited, it is useful as a general packaging material or container.
It can be used for packaging films, bags, pouches and the like. In particular, it can be suitably used for a stretch packaging film for food packaging, a pallet stretch film, and the like. The molded article of the present invention, particularly a film or a film for stretch packaging, can be subjected to surface treatment such as corona, ozone, plasma, etc., antifogging agent application, lubricant application, printing and the like, as necessary.

The film or stretch packaging film of the molded article of the present invention can be produced as a stretched film which is uniaxially or biaxially stretched as required. The film of the present invention, or the film for stretch packaging, if necessary, heat, ultrasonic waves, fusion by a method such as high frequency, the film between by a method such as adhesion with a solvent or the like, and other materials such as thermoplastic resin and the like Can be joined. When used as a stretch packaging film for food, it can be suitably packaged by an automatic packaging machine or a manual packaging machine. Further, when the film of the present invention has a thickness of, for example, 100 μm or more, a packaging tray for foods, electric products, and the like can be formed by a method such as vacuum forming, compression molding, or thermoforming such as pressure forming. Furthermore, since the cross copolymer of the present invention basically does not contain an elutable plasticizer or a halogen, it has a basic feature of high environmental adaptability and safety.

The cross copolymer of the present invention may be used as a composition with another polymer. Conventionally, polymers and additives known as a composition with an ethylene-styrene copolymer can be used as a composition with the cross copolymer of the present invention. Examples of such polymers and additives include the following. The following polymers can be added in the range of 1 to 99% by mass, preferably 30 to 95% by mass, based on the composition using the cross copolymer of the present invention. That is, the cross copolymer of the present invention is 1 to 99% by mass, preferably 5 to 70% by mass based on the present composition.
Can be included. In addition, the cross copolymer of the present invention can be used as a compatibilizer between an “aromatic vinyl compound polymer” and an “olefin polymer”. The cross-copolymer of the present invention can significantly change the olefin / aromatic vinyl compound content ratio of the main chain and the cross-chain, so that it is possible to enhance the compatibility with each polymer, Therefore, it can be suitably used as a compatibilizer. In this case, the cross copolymer of the present invention can be used in an amount of 1 to 50% by mass, preferably 1 to 20% by mass, based on the composition. Furthermore, "Filler-"
And in the case of a "plasticizer", it can be used in an amount of 1 to 80% by mass, preferably 5 to 50% by mass based on the composition.

"Aromatic vinyl compound polymer" The content of the aromatic vinyl compound is at least 10% by mass, preferably a polymer of the aromatic vinyl compound alone and at least one monomer component copolymerizable with the aromatic vinyl compound. Is a copolymer of 30% by mass or more. Examples of the aromatic vinyl compound monomer used in the aromatic vinyl compound-based polymer include styrene and various substituted styrenes such as p-methylstyrene, m-styrene.
-Methylstyrene, o-methylstyrene, ot-butylstyrene, mt-butylstyrene, pt-butylstyrene, α-methylstyrene and the like. And the like. Further, a copolymer between these plural aromatic vinyl compounds is also used. The stereoregularity between the aromatic groups of the aromatic vinyl compound may be any of atactic, isotactic and syndiotactic.

The monomers copolymerizable with the aromatic vinyl compound include butadiene, isoprene, other conjugated dienes, acrylic acid, methacrylic acid and amide derivatives and ester derivatives, and maleic anhydride and its derivatives. The copolymerization method may be any of block copolymerization, tapered block copolymerization, random copolymerization, and alternating copolymerization. Further, a polymer obtained by graft-polymerizing the aromatic vinyl compound to a polymer composed of the above-mentioned monomer and containing the aromatic vinyl compound in an amount of 10% by mass or more, preferably 30% by mass or more may be used. The above aromatic vinyl compound-based polymer needs to have a weight average molecular weight in terms of styrene of 30,000 or more, preferably 50,000 or more, in order to exhibit the performance as a practical resin.

As the aromatic vinyl compound resin used, for example, isotactic polystyrene (IP
S), syndiotactic polystyrene (s-PS),
Atactic polystyrene (a-PS), rubber-reinforced polystyrene (HIPS), acrylonitrile-butadiene-styrene copolymer (ABS) resin, styrene-acrylonitrile copolymer (AS resin), styrene-methyl methacrylate copolymer, etc. Styrene-methacrylate copolymer, styrene-diene block / tapered copolymer (SBS, SIS, etc.), hydrogenated styrene-diene block / tapered copolymer (SEBS, SEPS, etc.), styrene-diene copolymer ( SBR), hydrogenated styrene-diene copolymer (hydrogenated SBR, etc.), styrene-maleic acid copolymer, and styrene-imidized maleic acid copolymer. The concept also includes petroleum resin.

"Olefin Polymer" Linear low density polyethylene (LLDPE), isotactic polypropylene (i-PP), syndiotactic polypropylene (s-PP), atactic polypropylene (a-P)
P), propylene-ethylene block copolymer, propylene-ethylene random copolymer, ethylene-propylene-diene copolymer (EPDM), ethylene-vinyl acetate copolymer, polyisobutene, polybutene, cyclic olefin such as polynorbornene And a cyclic olefin copolymer such as an ethylene-norbornene copolymer. If necessary, an olefin resin obtained by copolymerizing a diene such as butadiene or α-ω diene may be used. The above-mentioned olefin polymer needs to have a weight average molecular weight in terms of styrene of 10,000 or more, preferably 30,000 or more, in order to exhibit the performance as a practical resin.

[Other Resins, Elastomers, and Rubbers] For example, polyamides such as nylon, polyesters such as polyimide and polyethylene terephthalate, polyvinyl alcohol, SBS (styrene-butadiene block copolymer), SEBS (hydrogenated styrene-butadiene block) Styrene (styrene-isoprene block copolymer), SEPS (hydrogenated styrene-isoprene block copolymer), SBR (styrene-butadiene block copolymer), styrene-based block copolymer such as hydrogenated SBR And natural rubber, silicone resin, and silicone rubber which do not fall into the category of the above-mentioned aromatic vinyl compound resin.

[0085] Fillers known in the art can be used. Preferred examples are calcium carbonate, talc,
Examples include clay, calcium silicate, magnesium carbonate, magnesium hydroxide, mica, barium sulfate, titanium oxide, aluminum hydroxide, silica, carbon black, wood flour, wood pulp, and the like. Further, a conductive filler such as glass fiber, known graphite, and carbon fiber can be used.

[Plasticizers] Known plasticizers such as paraffinic, naphthenic, aroma-based process oils, mineral oil-based softeners such as liquid paraffin, castor oil, linseed oil, olefin-based waxes, mineral-based waxes and various esters. used.

For producing the polymer composition of the present invention, a known suitable blending method can be used. For example,
Melt mixing can be performed using a single-screw or twin-screw extruder, a Banbury mixer, a plast mill, a co-kneader, a heating roll, or the like. Before performing melt mixing, use a Henschel mixer, ribbon blender, super mixer,
Each raw material may be uniformly mixed with a tumbler or the like. The melting and mixing temperature is not particularly limited, but may be 100 to 30.
0 ° C., preferably 150-250 ° C. is common. As the molding method of the various compositions of the present invention, known molding methods such as vacuum molding, injection molding, blow molding, extrusion molding, and extrusion molding can be used. Compositions containing the cross-copolymer of the present invention, various films and packaging materials, sheets, tubes and hoses, gaskets, and even flooring,
It can be suitably used as a building material such as a wall material or an interior material of an automobile.

[0088]

The present invention will be described below with reference to examples.
The present invention is not limited to the following examples. Analysis of the copolymers obtained in each of the examples and comparative examples was performed by the following means. The 13C-NMR spectrum was determined using α-500 manufactured by JEOL Ltd. and using a heavy chloroform solvent or a heavy 1,1,2,2-tetrachloroethane solvent.
The measurement was based on MS. Here, the measurement based on TMS is as follows. First, the shift value of the center peak of the triplet 13C-NMR peak of heavy 1,1,2,2-tetrachloroethane was determined based on TMS. Next, the copolymer was dissolved in heavy 1,1,2,2-tetrachloroethane and 13C-NMR was measured.
The calculation was based on the center line of the overlap line. Weight 1,1,2,
The shift value of the triplet center peak of 2-tetrachloroethane was 73.89 ppm. The measurement was performed by dissolving the polymer in 3% by mass / volume in these solvents.

The 13C-NMR spectrum measurement for quantifying the peak area was performed by a proton gate decoupling method with NOE eliminated, using a pulse width of 45 ° and a repetition time of 5 seconds as a standard. By the way,
The measurement was carried out under the same conditions except that the repetition time was changed to 1.5 seconds. The quantitative value of the peak area of the copolymer coincided with the case of the repetition time of 5 seconds within the measurement error range. The determination of the styrene content in the copolymer was performed by 1H-NMR, and the equipment was α-500 manufactured by JEOL Ltd. and A manufactured by BRUCKER
C-250 was used. It was dissolved in heavy 1,1,2,2-tetrachloroethane, and the measurement was performed at 80 to 100 ° C. T
The intensity was compared between the peak derived from the phenyl group proton (6.5 to 7.5 ppm) and the proton peak derived from the alkyl group (0.8 to 3 ppm) based on MS.

The molecular weight in the examples was determined by GPC (gel permeation chromatography) using a weight average molecular weight in terms of standard polystyrene. The copolymer soluble in THF at room temperature is obtained by using Tosoh HLC
It measured using -8020. For a copolymer insoluble in THF at room temperature, measurement was performed using ortho-dichlorobenzene as a solvent.
It measured at 145 degreeC using HLS-8121 apparatus made by Tosoh. The detector used was a RI (differential refractometer).
The cross-copolymer of this example has a main chain component and a cross-chain component, in which the refractive index to the solvent orthodichlorobenzene is inverted, so that the molecular weight of the cross copolymer obtained by the RI detector is not accurate, It is a reference value.

The DSC measurement was performed using a DSC2 manufactured by Seiko Denshi Co., Ltd.
The temperature was increased at a rate of 10 ° C./min under a stream of N ₂ .
Using 10 mg of sample, 240 at a heating rate of 20 ° C./min
(1st run) and -100 with liquid nitrogen.
Quenched to below ℃ (pretreatment), then from -100 ℃ to 10
The temperature was raised at a rate of 2 ° C./min and the DSC measurement was performed up to 240 ° C. (2nd
run), melting point, heat of crystal fusion, and glass transition point. The glass transition point was determined by a tangent method.

The sample for evaluating physical properties was prepared by a hot press method (temperature: 180 ° C., time: 3 minutes, pressure: 50 kg / cm ² ).
A sheet having a thickness of 1.0 mm formed by the method described above was used. <Tensile test> According to JIS K-6251, the sheet was cut into a No. 1 test piece shape, and the Shimadzu AGS was used.
Using a -100D type tensile tester, a tensile speed of 500 mm /
Measured in minutes. <Permanent elongation> The strain recovery value in the tensile test was measured by the following method. Using a JIS No. 2 small (1/2) test piece, pull up to 100% strain with a tensile tester,
It was held for 10 minutes, after which the stress was released quickly (without bouncing) and the percent strain recovery after 10 minutes was expressed in%.

<MFR> Measured according to JIS K7210. Measurement temperature is 230 ° C, load is 5kg or 1
It was measured at 0 kg. <Measurement of Dynamic Viscoelasticity> The loss tangent tan δ was measured using a dynamic viscoelasticity measuring device (RSA-II, Rheometrics), at a frequency of 1 Hz and a temperature range of −120 ° C. to + 150 ° C. (Slightly changed depending on the characteristics). 0.1m thickness created by hot press
A sample for measurement (3 mm × 40 mm) was obtained from the m sheet. <X-ray diffraction> X-ray diffraction is measured by MacP
A -18 type high-power X-ray diffractometer was used, and the radiation source was measured using a Cu-enclosed counter electrode (wavelength: 1.5405 angstroms).

<Hardness> Hardness was measured using a type A according to JIS K-7215 plastic durometer hardness test method.
And D were measured for durometer hardness. <Total light transmittance, haze> Transparency is determined according to JIS K-7105 Plastic Optical Property Test Method by molding a sheet to a thickness of 1 mm by a hot press method (temperature 200 ° C., time 4 minutes, pressure 50 kg / cm ² G). The total light transmittance and haze were measured using a turbidimeter NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd. <Divinylbenzene> The divinylbenzene (meta-form and para-form mixture) used in Examples 1 to 3 was manufactured by Aldrich (purity as divinylbenzene 80%, meta-form, para-form mixture, meta-form: para-form mass) Since the ratio is 70:30, the isomeric purity of metadivinylbenzene is 70% by mass.)
It is. In the following polymerization, 1 ml (5.5 mmol as divinylbenzene) per 400 ml of styrene
When used, the amount of divinylbenzene corresponds to a molar ratio of 1/640 of the amount of styrene. As metadivinylbenzene, metadivinylbenzene (isomeric purity: 97% or more) manufactured by Asahi Kasei Finechem Co., Ltd. was used. The isomer purity in this case is the ratio of metadivinylbenzene to various divinylbenzene isomers of ortho, meta and para.

Example 1 <Synthesis of cross-copolymerized ethylene-styrene-divinylbenzene copolymer> Using rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride as a catalyst, Carried out. Capacity 1
Polymerization was carried out using an autoclave equipped with a stirrer and a jacket for heating and cooling. 4400 ml of toluene, 400 ml of styrene and 2.0 ml of divinylbenzene manufactured by Aldrich were charged, and the mixture was heated and stirred at an internal temperature of 70 ° C. About 200 L of nitrogen was bubbled through to purge the system and the polymerization solution. 8.4 mmol of triisobutylaluminum, methylalumoxane (PMAO-3 manufactured by Tosoh Akzo Co., Ltd.)
A) was added in an amount of 21 mmol based on Al, ethylene was immediately introduced, and the pressure was 0.25 MPa (1.5 kg / cm
After stabilization at ² G), rac-dimethylmethylenebis (4,5
-Benzo-1-indenyl) zirconium dichloride in 8.4 μmol, triisobutylaluminum 0.8
About 50 ml of a toluene solution of 4 mmol was added to the autoclave. Internal temperature 70 ° C, pressure 0.25MP
Polymerization (first polymerization step) was carried out for 24 minutes while maintaining at a. The integrated flow rate of ethylene at this stage was about 100 L in a standard state. While the temperature of the polymerization liquid was started, a part of the polymerization liquid was sampled, and a polymer sample (P-1A) of the first polymerization step was obtained by meta-precipitation. Ethylene is rapidly introduced and the pressure in the system is increased to 1.1MP over 12 minutes.
a. In the second polymerization step, the polymerization temperature is 97 ° C.
To 105 ° C. Pressure 1.1MPa
And the second polymerization step was carried out for a total of 18 minutes.

After completion of the polymerization, the obtained polymer liquid was poured little by little into a large amount of vigorously stirred methanol liquid.
The polymer was recovered. The polymer was air-dried at room temperature for 24 hours, and then dried at 80 ° C. in vacuo until no change in mass was observed. 784 g of polymer (P-1C) was obtained.

Table 1 summarizes the polymerization conditions of each example. Table 2 shows the analysis results of the polymers obtained in the respective examples.

[0098]

[Table 1]

[0099]

[Table 2]

Table 2 shows that, in addition to the polymer (P-1A) obtained in the first polymerization step and the polymer (P-1C) finally obtained through the second polymerization step, The values obtained by mass and composition of the polymerized polymer (P-1B) are also shown.

Examples 2-3 Under the conditions shown in Table 1, polymerization and post-treatment were carried out in the same manner as in Example 1.

Examples 4 to 6 Under the conditions shown in Table 1, polymerization and post-treatment were carried out in the same manner as in Example 1. However, divinylbenzene to be used was metadivinylbenzene manufactured by Asahi Kasei Finechem Co., Ltd. (isomer purity: 97
%). The cross-copolymerization conditions in these examples satisfy the preferable conditions for obtaining a cross-copolymer having good moldability as described below.

Example 1 satisfies the condition that a) the polymerization temperature is always at least 80 ° C., preferably at least 85 ° C. and at most 160 ° C. during the first and / or second polymerization step. . Example 2 satisfies the condition that a) the polymerization temperature is substantially always at least 80 ° C., preferably at least 85 ° C. and at most 160 ° C. during the first and / or second polymerization step. Example 3 satisfies the condition that the aromatic vinyl compound content of the polymer obtained in b) the first polymerization step is 30 mol% or more and the weight average molecular weight is 250,000 or less.

In Examples 4 to 6, a) the polymerization temperature is always at least 80 ° C., preferably at least 85 ° C. and at most 160 ° C. during the first and / or second polymerization step substantially during the polymerization;
c) The condition that the diene used is metadivinylbenzene having an isomer purity of 80% by mass or more, preferably 90% by mass or more is satisfied.

The amount of divinylbenzene remaining in the polymerization solution was determined by gas chromatography analysis of the polymerization solution extracted at the end of the first polymerization step, and the amount of divinylbenzene consumed in the first polymerization step was determined. When the divinylbenzene content in the copolymer obtained in each of the first polymerization steps was determined from the values, polymer P-1A was about 0.06 mol%, polymer P-2A was about 0.03 mol%, About 0.04 mol% of polymer P-3A, about 0.03 mol% of polymer P-4A, about 0.04 mol% of P-5A, and about 0.04 mol% of P-6A
3 mol%.

The structure index λ value of the cross-copolymer obtained in each example and the isotactic dyad fraction m value of the styrene unit-ethylene unit alternating structure were determined according to the above formulas (i) and (ii), respectively. I asked. P-1A, P-2A, P-4A, P-5A obtained in the first polymerization step,
The λ value of P-6A was a value within the range of 12 to 20.
The λ value of P-3A was 39. Cross copolymers P-1C, P-2C, P-4C obtained through the second polymerization step,
The λ values of P-5C and P-6C were values in the range of 7 to 15. The λ value of P-3C was 24. The m value was 0.95 or more for all the polymers. Table 3 shows the measurement results such as the mechanical properties of the obtained polymer.

[0107]

[Table 3]

Comparative Examples 1 to 6 rac-dimethylmethylenebis (4,5-benzo-1-
Indenyl) zirconium dichloride as a catalyst,
EP-0 using methylalumoxane (MAO) as a co-catalyst
Table 4 shows ethylene-styrene copolymers having various styrene contents obtained by polymerization according to the methods (polymerization temperature of 50 to 70 ° C.) described in JP-A-872492A2 and JP-A-11-130808. (These copolymers are not cross-copolymerized.)

[0109]

[Table 4]

Comparative Example 7 Brabender Plasticorder (Bravebender PLE)
331 type), and each of R-2 and R-6 copolymers is 25
g after melting, kneading (external temperature 180 ° C, rotation speed 60R
PM, time 10 minutes) to obtain a composition. A sheet having a thickness of 1 mm was formed from the obtained ethylene-styrene copolymer composition by the press molding, and various physical properties were evaluated. Table 5 shows the physical property test results of the comparative polymer obtained.

[0111]

[Table 5]

The cross-copolymerized styrene-ethylene-divinylbenzene copolymer of this example has high mechanical strength,
It turns out that it has a high melting point and transparency. When compared with an ethylene-styrene copolymer having the same composition (styrene content) and its physical properties, it shows a higher melting point. In addition, it shows transparency equal to or higher than that of the ethylene-styrene copolymer. The melting point of the cross-copolymer of this example is a high value which is almost equal to or higher than that of the ethylene-styrene copolymer having the same styrene content as the cross-chain component polymerized in the second polymerization step (cross-forming step). Take. That is, the first embodiment
Has an average styrene content of 10.6 mol%, but its melting point is significantly higher than that of the ethylene-styrene copolymer having the same styrene content. On the other hand, Shore-A, D hardness and tensile modulus of the cross copolymer show almost the same values as the ethylene-styrene copolymer of the same composition, indicating that they have both heat resistance and softness. . This is considered to be due to the effect of the main chain component (component obtained in the first polymerization step) having a high styrene content and low crystallinity of the cross copolymer.

FIG. 3 shows the relationship between the styrene content and the DSC melting point of the cross-copolymer obtained in this example and the ethylene-styrene copolymer of the comparative example. As a comparative experiment, an ethylene-styrene copolymer (R-2 and R-2) having a styrene content close to that of the main chain and the cross chain of the cross copolymer (P-1C) was used.
-6) were kneaded at a mass ratio of 1: 1 to obtain a composition. The resulting composition was opaque as shown in the table. Thus, it can be seen that in the case of a composition of ethylene-styrene copolymers having greatly different compositions (for example, different styrene contents of 10 mol% or more), transparency is deteriorated due to poor compatibility.

The cross-copolymerized polystyrene obtained in this example
The ethylene-diene copolymer has good processability (MF
R, load 5kg, MFR measured at 230 ° C is 1.0g
/ 10 minutes or more and 50 g / 10 minutes or less). (Table 6) Generally, the final conversion of styrene (through all polymerization steps)
Conversion rate of aromatic vinyl compound monomer species)
, The processability (MFR) tends to decrease. This
Deterioration of the formability is caused by the polymer obtained in the first polymerization step.
When the aromatic vinyl compound content of the mer is less than 30 mol%
In particular. But especially as a diene,
Isomeric purity of 80% by mass or more, preferably 90%
When using more than 5% by mass of metadivinylbenzene
Examples 4, 5), Final conversion of styrene (aromatic vinyl compound)
The cross-copolymer is manufactured under the condition that the conversion is 70% or more.
Also, the obtained cross copolymer has good processability (MFR,
MFR measured under a load of 5 kg and 230 ° C. is 1.0 g / 1.
(0 min to 50 g / 10 min). Meta
Under such conditions, divinylbenzene is adopted.
Even while maintaining various physical properties such as heat resistance and transparency,
In giving moldability (MFR), the cross-copolymer
Preferred for manufacturing.

[0115]

[Table 6]

The gel content of the cross-copolymer was measured according to ASTM D-2765-84. That is, a precisely weighed 1.0 g polymer (molded product having a diameter of about 1 mm and a length of about 3 mm) was wrapped in a 100-mesh stainless steel mesh bag and weighed precisely. After extracting this in boiling xylene for about 5 hours, the net bag was recovered and dried in vacuum at 90 ° C. for 10 hours or more. After cooling sufficiently, the net bag was precisely weighed, and the amount of polymer gel was calculated by the following equation. Gel amount = A / B × 100 A = mass of polymer remaining in mesh bag B = initial polymer mass The gel amount is 0% by mass (lower limit of measurement: 0.1% by mass) for both cross copolymers of Examples. It can be seen that the cross copolymer has a very low gel content and a low degree of crosslinking.

This is because the coordination polymerization catalyst used in the present example can copolymerize diene with high efficiency, and cross-linking proceeds sufficiently at a very low level of diene. is there. It is considered that when the amount / concentration of the residual diene in the polymerization solution is sufficiently small, crosslinking of the copolymer in the diene unit during polymerization is suppressed to an extremely low level, and the generation of a gel component is suppressed. Also in the crossing step, the generation of the gel component is suppressed because the residual diene amount / concentration is low. Therefore, it is considered that good moldability is obtained.

By X-ray diffraction, a crystal structure derived from an ethylene chain was confirmed in the cross copolymer of this example.
The embrittlement temperature of the cross copolymer of this example was determined according to JIS K-6.
723, K-7216. As a result, the cross copolymers P-1C, P-2C, P-4C, P-5C,
Each of P-6C showed an embrittlement temperature of −60 ° C. or less.
Transparent soft PVC compound (DENKA, VINICON S210
0-50) showed an embrittlement temperature of approximately -25 ° C. FIG. 4 shows a transmission electron microscope (TEM) photograph of the cross copolymer obtained in Example 1, and FIG. 5 shows a TEM photograph of the ethylene-styrene copolymer composition of Comparative Example 7. Ethylene-
In the case of a styrene copolymer composition, the low styrene content copolymer (white portion) and the relatively high styrene content copolymer portion (black portion) are phase-separated by several microns. The crystalline lamellas (white needles) are only present inside the low styrene content copolymer region. This result indicates low compatibility between ethylene-styrene copolymers having different compositions. On the other hand, in the cross copolymer, the low styrene content portion (white portion) and the relatively high styrene content portion (black portion) are both finely dispersed in a size of about 0.1 μm or less. I have.
Further, crystalline lamellas (white needle-like) are often present at the interface, and many of them enter the high styrene region, and have a specific structure that bridges both phases.

Examples 7 to 12 and Comparative Example 8 A copolymer composition was obtained according to the compounding ratio shown in Table 7, and the C-set and heat resistance were measured by the following methods. <Measurement of C-Set> Using a Brabender plastic coder (Model PLE331, Brabender), the polymer was melted and kneaded at 200 ° C., 60 rpm for 10 minutes with the composition shown in Table 7 to prepare a sample. The sample was press-molded, the mechanical properties were measured, and the high-temperature compression set (C-set) after pressure heat treatment at 70 ° C. for 24 hours was measured according to JIS K6262 (Table 7). Heat resistance of dumbbells obtained by press molding was measured (dumbbells were suspended in a gear oven at 120 ° C for 2 hours and deformation was observed).
Was evaluated. The cross copolymer of this example has a low C
-Has a set value (65%). This indicates that the present cross copolymer has good elastic recovery under high temperature conditions. Also,
Heat resistance is relatively good. Furthermore, it is possible to improve the C-set value and to lower the hardness by blending with a plasticizer. On the other hand, the C-set values of the ethylene-styrene copolymer of the comparative example and the composition of the comparative ethylene-styrene copolymer having different compositions were 93%, respectively.
It is inferior to 100% and has poor heat resistance. Further, the composition of polyolefin (polyethylene) and the plasticizer showed good C-set value (47 to 53) and high heat resistance (Examples 11 and 12). Furthermore, the composition with polypropylene did not deform by heat treatment at 120 ° C. for 2 hours and showed high heat resistance.

[0120]

[Table 7]

[0121]

According to the present invention, mechanical characteristics, high temperature characteristics,
Provided is a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer having excellent compatibility and transparency, and a composition thereof, and an industrially excellent method for producing the cross copolymer and the composition. Is done.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram showing a cross-linked copolymer of the present invention.

FIG. 2 is a conceptual diagram showing a conventional grafted copolymer.

FIG. 3 is a graph showing the relationship between the composition and the melting point of the cross-linked copolymer and the ethylene-styrene copolymer of the present invention.

FIG. 4 Transmission electron microscope (TEM) of the cross-copolymer
Photo.

FIG. 5 is a TEM photograph of the ethylene-styrene copolymer composition of Comparative Example 7.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4F071 AA15 AA15X AA22 AA22X AA76 AE04 AF30 BB05 BB06 BC01 4J002 AE053 BB03X BB12X BB15X BB18X BC04W EH006 FD010 FD023 FD026 4J0A04 A03A03 A03A03 AB16R AS11R AU21R DA43

Claims (17)

[Claims] 1. An olefin-aromatic vinyl compound-diene copolymer having an aromatic vinyl compound content of 0.03 mol% to 96 mol%, a diene content of 0.0001 mol% to 3 mol%, and a balance of olefin. Cross-copolymerized olefin-aromatic vinyl obtained by cross-copolymerizing an olefin-aromatic vinyl compound copolymer (which may contain a diene) having an aromatic vinyl compound content different by 5 mol% or more from the polymer A compound-diene copolymer, wherein 2
MFR measured at 30 ° C. under a load of 5 kg is 1.0 g / 10
A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer having a length of at least 50 g / 10 min. 2. An olefin-aromatic vinyl compound-diene copolymer having an aromatic vinyl compound content of 0.03 to 96 mol%, a diene content of 0.0001 to 3 mol%, and a balance of olefin. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer obtained by cross-copolymerizing an olefin-aromatic vinyl compound copolymer (which may contain a diene) into the polymer,
The aromatic vinyl compound content differs from the olefin-aromatic vinyl compound-diene copolymer before cross-copolymerization by 2 mol% or more, and the MFR measured at 230 ° C. under a load of 5 kg is 1.0 g / 10 min. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer having a weight of 50 g / 10 min or less. 3. The composition according to claim 1, wherein the content of the aromatic vinyl compound is 5 mol% or more and 50 mol% or less, the diene content is 0.0001 mol% or more and 3 mol% or less, and the balance is olefin. 2. The cross-copolymer according to 2. 4. MFR measured at 230 ° C. under a load of 5 kg
Is 1.0 g / 10 min or more and 50 g / 10 min or less, has a crystal structure derived from an ethylene chain structure, and has an aromatic vinyl compound content and a heat of crystal fusion of 10 as measured by DSC.
At least one of the melting points of not less than J / g and not more than 150 J / g satisfies the following relationship, the content of the aromatic vinyl compound is not less than 5 mol% and not more than 50 mol%, and the content of the diene is 0.00
Cross-copolymerized olefin-aromatic vinyl compound-characterized in that it is at least 01 mol% and at most 3 mol%, the balance being ethylene or two or more olefins containing ethylene.
Diene copolymer. (5 ≦ St ≦ 20) −3 · St + 125 ≦ Tm ≦ 140 (20 <St ≦ 50) 65 ≦ Tm ≦ 140 Tm; Melting point (° C.) by DSC measurement St; Aromatic vinyl compound content (mol%) 5. The cross-copolymerized olefin-aromatic vinyl compound-diene copolymer according to claim 1, wherein the olefin is ethylene or two or more olefins containing ethylene. United. 6. The cross-copolymerized olefin-aromatic vinyl compound-diene copolymer according to claim 1, wherein the aromatic vinyl compound is styrene. 7. The method according to claim 1, wherein the diene used is any one or a mixture of two or more of orthodivinylbenzene, paradivinylbenzene and metadivinylbenzene. Cross-copolymerized olefin-aromatic vinyl compound-diene copolymer. 8. The cross-copolymerized olefin-aromatic vinyl compound according to claim 1, wherein the diene used is metadivinylbenzene having an isomer purity of 80% by mass or more. Diene copolymer. 9. The cross-copolymerized olefin-aromatic vinyl compound-diene copolymer according to claim 1, wherein the gel content is less than 10% by mass. 10. The molded product having a thickness of 1 mm has a total light transmittance of 70% or more.
5. The cross-copolymerized olefin-aromatic vinyl compound-diene copolymer according to any one of 4. 11. The cross-copolymerized olefin-aromatic vinyl compound-diene copolymer according to claim 1, which has a haze of 30% or less in a molded article having a thickness of 1 mm. United. 12. A molded product obtained by molding the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer according to claim 1. Description: 13. A film comprising the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer according to any one of claims 1 to 4. 14. A composition comprising 1 to 99% by mass of the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer according to any one of claims 1 to 4. 15. A composition comprising the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer according to claim 1 and a plasticizer. 16. A composition comprising the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer according to any one of claims 1 to 4 and a polyolefin. 17. A molded article obtained by molding the composition according to any one of claims 14 to 16.