JP2002265700A - Olefinic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new resin composition having excellent mechanical properties, weatherability, heat resistance and chemical resistance and suitably usable in applications including extrusion molded products. SOLUTION: This new resin composition comprises an olefinic polymer and a new cross-copolymerized olefin-aromatic vinyl compound-diene copolymer having specific composition and structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an olefin resin comprising an olefin polymer (component (A)) and a novel cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)). Composition.

More specifically, the present invention relates to an olefin-aromatic vinyl having an aromatic vinyl compound content of 1 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 and / or an olefin-aromatic vinyl compound, wherein the content of the aromatic vinyl compound in the compound-diene copolymer is at least 5 mol% different from that of the copolymer.
The diene copolymer is characterized in that it has been cross-copolymerized, and comprises, for example, a novel cross-copolymerized olefin having properties such as a thermoplastic elastomer-aromatic vinyl compound-diene copolymer, The present invention relates to a novel resin composition which is excellent in mechanical properties, weather resistance, heat resistance and chemical resistance and is suitably used for applications such as injection molded articles and extruded molded articles.

[0003]

2. Description of the Related Art Polyolefins such as polypropylene and polyethylene are representative of general-purpose plastics, and are used in large quantities in household goods and the like. On the other hand, in recent years, high-performance polyolefins have been obtained by improvement in polyolefin polymerization technology, and attempts have been made to use them in fields where engineering plastics were conventionally used, such as automobile bumpers. However, for use in applications requiring high strength, it is necessary to further improve mechanical properties such as strength.

Propylene polymers have excellent mechanical strength, moldability, heat resistance, chemical resistance, etc.
As a general-purpose resin for containers, etc., it is used in various fields, but it has insufficient impact resistance, so it is used for housing parts of home appliances such as bumpers, instrument panels, refrigerators, washing machines, etc. A copolymer of ethylene and an α-olefin, particularly one obtained by blending an olefin elastomer such as ethylene-propylene rubber, polyisobutylene, or polybutadiene with a propylene polymer is used. As described above, the blend of the olefin-based elastomer with the propylene-based polymer has a disadvantage that the surface hardness is lowered and the olefin-based elastomer is easily damaged. Thus, there is a method of further increasing the surface hardness by further blending an inorganic filler such as calcium carbonate, but has the disadvantage that the specific gravity increases and the impact resistance decreases.

[0005] Polyethylene polymers have excellent physical properties and processing characteristics, and are used for a wide range of applications such as films and sheets. However, there is a demand for imparting various characteristics for the purpose of further expanding the applications. In order to respond to such demands, studies such as copolymerization and addition of other types of materials have been made so far. A method of imparting flexibility by adding a soft component such as ethylene propylene rubber to a polyethylene-based resin is known, but has a drawback that the surface hardness is reduced and it is easily damaged as in the case of the propylene-based polymer.

[0006] Compositions of an ethylene-styrene copolymer and an olefin polymer are also known. For example, JP-A-10-60194 discloses a polypropylene-based resin composition comprising a propylene-based polymer and an ethylene-styrene pseudo-random copolymer obtained using a so-called geometrically constrained structure type catalyst (CGCT type catalyst). A composition comprising an olefin-aromatic vinyl compound random copolymer and a polypropylene-based polymer is also disclosed in JP-A-10-087918.
However, the balance between the compatibility, impact strength and elastic modulus is not sufficient. Further, heat resistance and chemical resistance are not sufficient.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to improve the disadvantages of such conventional olefin resin compositions,
An object of the present invention is to provide a novel resin composition which is excellent in mechanical properties, weather resistance, heat resistance and chemical resistance and is suitably used for applications such as injection molded products and extruded products.

[0008]

The present invention provides a resin composition containing an olefin polymer and a novel cross-copolymerized olefin-aromatic vinyl compound-diene copolymer having a specific composition and structure. This has solved the above-mentioned problem. That is, the present invention is an olefin-based resin composition containing the following components (A) and (B). Component (A): 50 to 95% by weight of olefin polymer. Component (B): The aromatic vinyl compound content is 1 mol% or more and 9
6 mol% or less, diene content is 0.0001 mol% or more, 3
Olefin-aromatic vinyl compound-diene copolymer in which the content of aromatic vinyl compound differs from the olefin-aromatic vinyl compound-diene copolymer by 5 mol% or less as compared with the copolymer, And / or 5% by weight or more and less than 50% by weight of a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer, wherein the olefin-aromatic vinyl compound-diene copolymer is cross-copolymerized. Here, the total of the components (A) and (B) is 100% by weight.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an olefin polymer (component (A)) and a novel cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)). It is a resin composition. Hereinafter, each component will be described in detail.

[Olefin Polymer (Component (A))] The olefin polymer of the component (A) constituting the olefin resin composition of the present invention includes an ethylene polymer and a propylene polymer. Can be Specific examples of the ethylene polymer include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, ethylene-α-olefin copolymer, ethylene-α-olefin copolymer rubber, and ethylene-vinyl acetate copolymer. And the like.
Specific examples of the polypropylene-based polymer include homopolypropylene, block polypropylene, random polypropylene, and propylene-ethylene copolymer. The component (A) used in the present invention may be a mixture of an ethylene polymer and a propylene polymer.

The component (A) is preferably an ethylene-based polymer or a propylene-based polymer, and is preferably a low-density polyethylene, a high-density polyethylene, a copolymer of ethylene and an α-olefin having 2 to 8 carbon atoms, or ethylene and a carbon number. Particularly preferred are copolymer rubbers with 2 to 8 α-olefins, homopolypropylene, and propylene-ethylene copolymers. When a propylene-ethylene copolymer is used as the component (A), a resin composition having an effect of improving impact strength and having an excellent elastic modulus and impact strength when used together with an ethylene-α-olefin copolymer rubber. You can get things. The molecular weight of the olefin polymer (component (A)) is preferably 10,000 or more and 1,000,000 or less.

[Cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B))] The cross-copolymerized olefin-aromatic vinyl compound-diene copolymer constituting the olefin resin composition of the present invention. The polymer (component (B)) (hereinafter referred to as a cross-copolymer) has an aromatic vinyl compound content of 1 mol% to 96 mol%, a diene content of 0.0001 mol% to 3 mol%, and the balance Olefin-aromatic vinyl compound-diene copolymer and olefin-aromatic vinyl compound copolymer and / or olefin-aromatic vinyl compound-diene copolymer whose aromatic vinyl compound content differs by 5 mol% or more from olefin Is a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer.

As used herein, the term “cross-copolymer” means that a main-chain olefin-aromatic vinyl compound-diene copolymer and a vinyl compound polymer are linked via a diene unit at one or more points as shown in FIG. Bond with cross strand (cross-link)
It is a copolymer mainly having the structure shown below. Such a cross structure can be rephrased as a star structure. In addition, classification by the American Chemical Society POLY subcommittee
graded star copolymer
(Polymer prints, 1998,
March). Hereinafter, the olefin-aromatic vinyl compound copolymer and / or the olefin-aromatic vinyl compound-diene copolymer cross-linked to the 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.

The cross-copolymer constituting the olefin resin composition of the present invention has an aromatic vinyl compound content of 1 mol% or more and 96 mol% or less, and a diene content of 0.000 mol% or less.
An olefin-aromatic vinyl compound-diene copolymer having 1 mol% or more and 3 mol% or less, and the balance being olefin, is mixed with an olefin-aromatic vinyl compound copolymer and / or an olefin-aromatic vinyl compound-diene copolymer. A cross-copolymerized olefin characterized by being cross-copolymerized-an aromatic vinyl compound-a diene copolymer,
The cross-chain aromatic vinyl compound content is 5 mol% as compared with the aromatic vinyl compound content of the main chain olefin-aromatic vinyl compound-diene copolymer before cross-copolymerization.
A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer characterized by the above differences. More preferably, the cross copolymer constituting the olefin resin composition of the present invention has an aromatic vinyl compound content of 1 mol% or more and 96 mol% or less, a diene content of 0.0001 mol% or more and 3 mol% or less, It is characterized in that an olefin-aromatic vinyl compound-diene copolymer whose balance is an olefin is cross-copolymerized with an olefin-aromatic vinyl compound copolymer and / or an olefin-aromatic vinyl compound-diene copolymer. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer, wherein the aromatic vinyl compound content is at least as compared with the olefin-aromatic vinyl compound-diene copolymer before cross-copolymerization. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer characterized by a difference of 5 mol% or more.

The cross copolymer used in the present invention is:
Not only is it a concept showing the cross copolymer itself,
Cross copolymer, and the first polymerization step shown below, non-cross-linked olefin obtained in the second polymerization step-
The term includes a composition containing an aromatic vinyl compound copolymer and / or an olefin-aromatic vinyl compound-diene copolymer in an arbitrary ratio. The composition containing such a cross copolymer can be obtained by the following production method.

An example of the method for producing the cross-copolymer used in the present invention will be described, but is not limited to the following production method. The cross-copolymer production method is preferably uniform and can be produced with efficiency and economy suitable for industrialization.

That is, as a first polymerization step, an olefin monomer, an aromatic vinyl compound monomer and a diene monomer are copolymerized to synthesize an olefin-aromatic vinyl compound-diene copolymer, and then as a second polymerization step. ,
In this production method, a cross-copolymer is obtained by cross-copolymerizing the copolymer with an olefin and an aromatic vinyl compound monomer and, if necessary, a diene monomer. A coordination polymerization catalyst is preferably used in both the first polymerization step and the second polymerization step, and a single-site catalyst is particularly preferable.

The aromatic vinyl compound content of the olefin-aromatic vinyl compound-diene copolymer polymerized in the first polymerization step and the olefin-aromatic vinyl compound copolymer polymerized in the second polymerization step (first polymerization When the polymerization solution obtained in the step is used as it is in the second polymerization step, a small amount of residual diene is copolymerized in the polymer obtained here), and the content of the aromatic vinyl compound differs by at least 5 mol% or more. It is necessary to be. Preferably at least 10 mol%,
Most preferably, they differ by at least 15 mol%. Preferably, the olefin obtained in the first polymerization step
The aromatic vinyl compound content of the aromatic vinyl compound-diene copolymer and the aromatic vinyl compound content of the finally obtained cross-copolymerized olefin-aromatic vinyl compound-diene copolymer are at least 5 mol%, preferably at least 5 mol%. Is different by 10 mol% or more.

The olefins used in the first polymerization step include ethylene, α-olefins having 3 to 20 carbon atoms,
That is, propylene, 1-butene, 1-hexene, 4-
Examples include methyl-1-pentene, 1-octene and cyclic olefins, ie, cyclopentene and norbornene. Preferably, ethylene, ethylene and propylene, 1
Α- such as butene, 1-hexene or 1-octene
A mixture with an olefin, an α-olefin such as propylene is used, and more preferably, ethylene, ethylene and α
A mixture of olefins is used, particularly preferably ethylene.

Styrene is preferably used as the aromatic vinyl compound used in the first polymerization step, but other aromatic vinyl compounds such as p-chlorostyrene, p-tert-butylstyrene, α-methylstyrene, vinyl Naphthalene, p-methylstyrene, vinyl naphthalene,
Vinyl anthracene or the like can be used, and a mixture thereof may be used.

As the diene used in the first polymerization step, a diene capable of coordination polymerization is preferably used. For example, butadiene, isoprene, chloroprene and the like described in JP-A-6-136060, and paradivinylbenzene and metadivinylbenzene described in JP-A-11-124420 are exemplified. Preferably 1,4-hexadiene, 1,5-
Hexadiene, ethylidene norbornene, dicyclopentadiene, norbornadiene, 4-vinyl-1cyclohexene, 3-vinyl-1cyclohexene, 2-vinyl-
1-cyclohexene, 1-vinyl-1-cyclohexene, paradivinylbenzene, metadivinylbenzene or a mixture thereof is used. 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. Preferably, dienes in which one of the double bonds (vinyl group) is used for coordination polymerization and the remaining double bond in the polymerized state is coordinatively polymerizable, most preferably para, meta divinyl Benzene and mixtures thereof are preferably used.

The olefin-aromatic vinyl compound-diene copolymer obtained in the first polymerization step has an aromatic vinyl compound content of 1 mol% to 96 mol%, and a diene content of 0.0001 mol% to 3 mol%. The balance is an olefin, preferably an aromatic vinyl compound content of 1 mol% to 50 mol%, a diene content of 0.001 mol% to less than 0.5 mol%, and a balance of olefin. If the content of the aromatic vinyl compound is 1 mol% or less, the effect of modifying the olefin, such as scratch resistance, is small, and if it is 96 mol% or more, the compatibility with the olefin becomes poor.

When the first polymerization step is carried out at a diene concentration higher than the required amount, a large amount of the crosslinked structure of the polymer is formed during the polymerization to cause gelation or the like. It is not preferable because the processability and physical properties of the polymer deteriorate. For example, if the first polymerization step is performed at a diene concentration higher than the required amount, the residual diene concentration in the polymerization liquid will increase. Also, the obtained cross-copolymer similarly deteriorates processability and physical properties.
Conversely, if the first polymerization step is carried out at a diene concentration less than the required amount, the crossing density is small and the crossing effect is not sufficient. When the gel content of the cross-copolymer is 10% by weight or more, moldability such as fluidity is remarkably reduced, which is disadvantageous when the molded article is recycled. From these, the amount of the diene used in the first polymerization step is preferably 1/100 or less with respect to the amount of the aromatic vinyl compound used in a molar ratio.
/ 50,000 or more, more preferably 1/400 or less
It is 20,000 or more.

The single-site coordination polymerization catalyst preferably used in the first polymerization step includes a polymerization catalyst comprising a transition metal compound and a co-catalyst, soluble Zieglar-N
Atta catalysts, transition metal compound catalysts activated with methylaluminoxane, boron compounds, and the like (so-called metallocene catalysts, half-metallocene catalysts, CGCT catalysts, and the like) are exemplified. Specifically, polymerization catalysts described in the following documents and patents can be used. For example, in the case of metallocene catalysts, US Pat.
No. 88, JP-A-6-49132, Polym
er Preprints, Japan, 42, 229
2 (1993), Macromol. Chem. ,
Rapid Commun. , 17, 745 (199
6), JP-A-9-309925, EP08724
92A2, JP-A-6-184179. In half metallocene catalysts, Makromol. Chem.
191, 387 (1990). For CGCT catalysts, JP-A-3-1630088, JP-A-7-53618, and EP-A-416815. Soluble Zieg
For the lar-Natta catalyst, JP-A-3-250007
No., 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 a copolymer having such a uniform composition, Zieglar
It is difficult with a -Natta catalyst, and a single-site coordination polymerization catalyst is preferably used. A single-site coordination polymerization catalyst is a polymerization catalyst composed of a transition metal compound and a co-catalyst, and a transition metal compound catalyst activated by methylaluminoxane, boron compound, or the like (a so-called metallocene catalyst, half metallocene catalyst, CGCT catalyst, etc.). ).

The most preferably used single-site coordination polymerization catalyst is a polymerization catalyst comprising a transition metal compound represented by the following chemical formula (1) and a co-catalyst. When a polymerization catalyst composed of a transition metal compound represented by the following chemical 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 reduce the amount of diene used in the first polymerization step and the amount of unreacted diene remaining in the polymerization solution.

Further, when a polymerization catalyst comprising a transition metal compound represented by the following chemical formula (1) and a cocatalyst is used, an olefin-aromatic vinyl compound having a high activity and a uniform composition suitable for industrialization- It is possible to produce diene copolymers. An olefin-aromatic vinyl compound-diene copolymer having isotactic stereoregularity and a head-tail styrene chain structure in a composition having an aromatic vinyl compound content of 1 mol% or more and 96 mol% or less. Can be.

Embedded image In the formula, A and B are each independently a group selected from an unsubstituted or substituted benzoindenyl group, an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group, or an unsubstituted or substituted fluorenyl group. . Y has a bond to A and B, and further contains a hydrogen or a hydrocarbon group having 1 to 20 carbon atoms (this group has 1 to 3 nitrogen, boron, silicon, phosphorus, selenium, oxygen or sulfur atom. (Which may be included) as a substituent.
The substituents may be different or the same. Also, Y
May have a cyclic structure such as a cyclohexylidene group or a cyclopentylidene group. X is each independently hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms,
An aryl group having 10 to 10 carbon atoms, an alkylaryl group having 8 to 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 a hydrogen atom having 1 to 22 carbon atoms. An amide group having a hydrocarbon substituent. n is an integer of 0, 1 or 2. M is zirconium, hafnium, or titanium. Particularly preferably, at least one of A and B is a group selected from an unsubstituted or substituted benzoindenyl group or an unsubstituted or substituted indenyl group, and the transition metal compound of the above general formula (1) and a cocatalyst. And a polymerization catalyst.

As the cocatalyst used in the first polymerization step, known cocatalysts and alkylaluminum compounds conventionally used in combination with a transition metal compound can be used. (Or as methylalumoxane or MAO)
Alternatively, a boron compound is suitably used. Examples of cocatalysts and alkylaluminum compounds used include EP
-0872492A2, JP-A-11-13080
No. 8, JP-A-9-309925, WO00 /
Co-catalysts and alkylaluminum compounds described in JP-A-20426, EP0985689A2, and JP-A-6-184179.

In producing the olefin-aromatic vinyl compound-diene copolymer, each monomer, metal complex (transition metal compound) and co-catalyst exemplified above are brought into contact with each other. Can be used.

As the method of the first polymerization step, a method of polymerizing in a liquid monomer without using a solvent, or pentane, hexane, heptane, cyclohexane, benzene, toluene, ethylbenzene, xylene, chloro-substituted benzene, chloro-substituted toluene , Methylene chloride, chloroform and the like using a saturated or aromatic hydrocarbon or a halogenated hydrocarbon alone or in a mixed solvent. Preferably, a mixed alkane solvent, cyclohexane, toluene, or ethylbenzene is used. The polymerization form may be either solution polymerization or slurry polymerization. If necessary, known methods such as batch polymerization, continuous polymerization, and multistage polymerization can be used.

It is also possible to use a single linear or loop, or a plurality of connected pipes. In this case, the pipe-shaped polymerization can includes various known mixers such as a dynamic or static mixer and a static mixer that also serves as heat removal, a cooler equipped with a heat removal thin tube, and the like. 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 during the 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, an aluminum atom /
The complex metal atom ratio is 0.1 to 100,000, preferably 1
Used at a ratio of 0 to 10,000. If it is less than 0.1, the metal complex cannot be activated effectively, and if it exceeds 100,000, it is economically disadvantageous. When a boron compound is used as a co-catalyst, a boron atom / complex metal atom ratio of 0.01 to 1 is used.
It is used at a ratio of 00, preferably 0.1 to 10, particularly preferably 1. If it is less than 0.01, the metal complex cannot be activated effectively, and 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% and more than 50% of the olefin partial pressure at the start of the polymerization. However, the olefin partial pressure in the first polymerization step is preferably kept constant during the polymerization.

The olefin-aromatic vinyl compound-diene copolymer obtained in the first polymerization step is preferably an ethylene-styrene-diene copolymer, an ethylene-α-olefin-styrene-diene copolymer, or An ethylene-cyclic olefin-styrene-diene copolymer, particularly preferably an ethylene-styrene-divinylbenzene copolymer is used. In addition, the olefin-aromatic vinyl compound-diene copolymer obtained in the first polymerization step may have a cross structure or a cross-linked structure in the diene monomer unit included, but the gel content is 10% of the whole.
Less than 1% by weight, preferably less than 1% by weight.

The typical and preferred ethylene-styrene-divinylbenzene copolymer used in the present invention will be described below. The ethylene-styrene-divinylbenzene copolymer obtained in the first polymerization step has a head-tail styrene unit chain structure attributed to a peak observed at 40 to 45 ppm by 13C-NMR measurement based on TMS. And preferably 42.3-43.1 ppm, 43.7-44.5 p
pm, 40.4-41.0 ppm, 43.0-43.6
It preferably has a chain structure of styrene units assigned by the peak observed in ppm.

Further, an ethylene-styrene-divinylbenzene copolymer obtained by using a metallocene catalyst capable of producing isotactic polystyrene by homopolymerization of styrene and producing polyethylene by homopolymerization of ethylene. Coalescing is preferred. Therefore, the obtained ethylene-styrene-divinylbenzene 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 the main chain.

The ethylene-styrene-divinylbenzene copolymer obtained in the first polymerization step, which is preferably used, has a phenyl group having an alternating structure of styrene and ethylene represented by the following general formula (1) contained in the structure. Is a copolymer having a stereoregularity of isotactic dyad fraction (or meso dyad fraction) Pm of more than 0.5, preferably more than 0.75, particularly preferably more than 0.95. The isotactic dyad fraction Pm of the alternating copolymer structure of ethylene and styrene has a peak area Ar derived from an r-structure of a methylene carbon peak appearing at around 25 ppm by 13C-NMR measurement based on TMS, and an m-structure. From the area Am of the peak derived,
It can be obtained by the following equation (1). Pm = Am / (Ar + Am) General formula (1) The appearance position of the peak may be slightly shifted depending on the measurement conditions and the solvent. The m structure is a meso diad structure,
The r structure represents a racemic diad structure.

The ethylene-styrene-divinylbenzene copolymer obtained in the first polymerization step has an alternating structure having a ratio of an alternating structure of styrene and ethylene represented by the following general formula (2) contained in the copolymer structure. The index λ is smaller than 70, larger than 0.01, preferably smaller than 30,
Preferably, the copolymer is greater than 0.1. λ = A3 / A2 × 100 General formula (2) Here, A3 is obtained by 13 C-NMR measurement and has three types of peaks a, b, and 3 derived from an ethylene-styrene alternating structure represented by the following chemical formula (2) This is the sum of the areas of c. A2 is 13C-NMR based on TMS.
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.

Embedded image (In the formula, Ph represents a phenyl group, x represents the number of repeating units, and represents an integer of 2 or more.)

In particular, a copolymer having a high isotactic stereoregularity in the ethylene-styrene alternating structure and having an alternating structure index λ of less than 70 is preferred as the copolymer of the present invention. -A copolymer having a styrene chain of a tail, and having an isotactic stereoregularity in an ethylene-styrene alternating structure, and having an alternating structure index λ value of less than 70 is particularly preferred as the copolymer of the present invention. .

That is, the olefin-aromatic vinyl compound-diene copolymer obtained in the preferred first polymerization step used in the present invention has an alternating structure of ethylene and styrene having high stereoregularity and simultaneously various lengths. It is characterized by having various structures such as ethylene chains, styrene hetero bonds, and styrene chains of various lengths. Also,
The olefin-aromatic vinyl compound-diene copolymer of the present invention has an alternating structure ratio of 0 in the λ value obtained by the above formula depending on the polymerization catalyst used, the polymerization conditions, and the content of the aromatic vinyl compound in the copolymer. Various changes can be made within a range of greater than 0.01 and less than 70.

The olefin-aromatic vinyl compound-diene copolymer obtained in the first polymerization step suitably used in the present invention, particularly the ethylene-styrene-divinylbenzene copolymer described above, is preferably prepared by the above-mentioned chemical formula ( It can be obtained by a polymerization catalyst comprising the transition metal compound represented by 1) and a co-catalyst.

As described above, olefin-aromatic vinyl compound-
The representative and preferred example of the ethylene-styrene-divinylbenzene copolymer obtained in the first polymerization step in producing the diene copolymer has been described, but of course the olefin-aromatic vinyl compound used in the present invention -The diene copolymer is not limited to this.

The weight average molecular weight of the olefin-aromatic vinyl compound-diene copolymer obtained in the first polymerization step is as follows:
It is 10,000 or 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, most preferably at most 3. Here, the weight average molecular weight refers to a molecular weight in terms of polystyrene obtained by using GPC with 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 may be adjusted within a range described above by a known method using a chain transfer agent such as hydrogen, or by changing the polymerization temperature if necessary. Can be adjusted. The olefin obtained in the first polymerization step
The aromatic vinyl compound-diene copolymer may partially have a cross structure or a branched structure via the included diene unit.

Next, the second polymerization step will be described. The second polymerization step here may be composed of a plurality of polymerization steps having different conditions and the like. As the second polymerization step, coordination polymerization using a single-site coordination polymerization catalyst is preferably employed. More preferably, a single-site coordination polymerization catalyst comprising the same transition metal compound represented by the chemical 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 chemical formula (1) and the co-catalyst forms a residual coordination polymerizable double bond of a diene unit copolymerized in a polymer main chain, particularly, divinylbenzene. Because it can be copolymerized with high efficiency,
It is also preferred as a catalyst for the second polymerization step. The copolymer obtained in the second polymerization step preferably has the same structure as the copolymer in the first polymerization step, but the composition is such that the content of the aromatic vinyl compound is that of the copolymer in the first polymerization step. It is necessary that the difference be at least 5 mol%.

In the second polymerization step, for example, a method similar to the polymerization method used in the first polymerization step is used. In this case, olefins and aromatic vinyl compounds used in the first polymerization step, and diene monomers remaining as needed or remaining in the polymerization solution can be used. The second polymerization step is preferably performed following the first polymerization step using the polymerization liquid obtained in the first polymerization step. However, the copolymer obtained in the first polymerization step is recovered from the polymerization solution, dissolved in a new solvent, and a monomer such as an olefin is newly added. A two-polymerization step may be performed.

The olefin-aromatic vinyl compound copolymer or olefin-aromatic vinyl compound which is polymerized in the second polymerization step compared to the olefin-aromatic vinyl compound-diene copolymer polymerized in the first polymerization step The aromatic vinyl compound content of the diene copolymer (when the polymerization solution obtained in the first polymerization step is used as it is in the second polymerization step, a small amount of residual diene is copolymerized in the obtained polymer) is at least It is necessary that they differ by 5 mol%. Preferably it differs by at least 10 mol%, most preferably by at least 15 mol%. The aromatic vinyl compound content of the polymer obtained in the first polymerization step and the aromatic vinyl compound content of the finally obtained cross-copolymer are at least 5%.
Preferably, they differ by at least mol%.

If the aromatic vinyl compound content of the polymer obtained in the first polymerization step and the polymer obtained in the second polymerization step do not differ by at least 5 mol%, the polymer obtained in the first polymerization step as a cross-copolymer And only the average physical properties of the polymer obtained in the second polymerization step are obtained, whereas if the aromatic vinyl compound content is different by 5 mol% or more, the polymer obtained in the first polymerization step and the polymer obtained in the second polymerization step The characteristics of both the obtained polymers appear. The features include, for example, flexibility, heat resistance, permanent compression set, rheological properties, chemical resistance, moldability, and the like. These features are combined, and various properties can be simultaneously provided. Further, the aromatic vinyl compound content of the polymer obtained in the first polymerization step and the aromatic vinyl compound content of the finally obtained cross-copolymer are preferably different from each other by 5 mol% or more. When the aromatic vinyl compound content of the polymer obtained in the polymerization step and the aromatic vinyl compound content of the finally obtained cross-copolymer differ from each other by 5 mol% or more, the polymer obtained in the first polymerization step and the second polymerization step The characteristics of both of the polymers obtained in the above appear.

The polymer obtained in the second polymerization step may have a branched structure via the diene unit contained.

A specific manufacturing method satisfying the above is described below. That is, as a first polymerization step, an aromatic vinyl compound monomer, an olefin monomer and a diene monomer are copolymerized using a coordination polymerization catalyst to synthesize an olefin-aromatic vinyl compound-diene copolymer, and then As a second polymerization step having different polymerization conditions, at least two polymerization using a coordination polymerization catalyst in the presence of the olefin-aromatic vinyl compound-diene copolymer and at least an olefin, an aromatic vinyl compound, and if necessary a diene. This is a step polymerization method. Further, the production method preferably satisfies at least one or more of the following conditions. 1) The olefin partial pressure of the polymerization solution in the second polymerization step is 1 to the olefin partial pressure immediately before the start of the polymerization in the first polymerization step.
50% or more or 50% or less. 2) The concentration of the aromatic vinyl compound in the polymerization liquid immediately before the start of the polymerization in the second polymerization step is 30% or less, or 20% or less, of the concentration of the aromatic vinyl compound immediately before the start of the polymerization in the first polymerization step.
0% or more. 3) Use different single-site coordination polymerization catalysts in the first polymerization step and the second polymerization step. 4) In the first polymerization step and the second polymerization step, the type of olefin used for the polymerization is different. Here, the first polymerization step and the second polymerization step are distinguished when the operation for changing these conditions is started.

The change satisfying the above conditions is performed as rapidly as possible and completed, preferably within 50%, more preferably within 30%, even more preferably within 10% of the polymerization time of the second polymerization step. It is preferable to complete. Further, the polymerization temperature in the first polymerization step and the polymerization temperature in the second polymerization step are preferably the same. If different, a temperature difference within about 100 ° C. is appropriate.

As a method of changing the monomer composition ratio in the polymerization liquid, for example, the olefin partial pressure of the polymerization liquid in the second polymerization step is set to 150% or more, preferably 200% or more, most preferably to the first polymerization step. There is a method to change it to 300% or more. As an 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 MPa is used in the second polymerization step.
Above, preferably at least 0.4 MPa, most preferably at least 0.6 MPa. In addition, the olefin partial pressure of the polymerization solution in the second polymerization step is 5 relative to the first polymerization step.
It may be changed to 0% or less, preferably 20% or less. For example, when the first polymerization step is performed at an ethylene pressure of 1.0 MPa, the second polymerization step is performed at 0.5 MPa or less, preferably 0.2 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 an example of a method for changing the monomer composition ratio in the polymerization liquid, the concentration of the aromatic vinyl compound in the polymerization liquid immediately before the start of the polymerization in the second polymerization step is compared with that immediately before the start of the polymerization in the first polymerization step. 30% or less, preferably 20% or less, or 200% or more, preferably 500%
The above-mentioned changing method 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, 0.3 mol / L or less, preferably 0.1 mol / L or less in the second polymerization step. It is carried out at 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, and an olefin and an aromatic vinyl compound monomer are added. 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 polymerization step, the kind of the olefin used for the polymerization is changed to reduce the content of the aromatic vinyl compound in the copolymer polymerized in the first polymerization step and the second polymerization step. It is also possible to change as described above.

Further, the second polymerization step is carried out subsequent to the first polymerization step using the polymerization solution obtained in the first polymerization step, and without adding a new aromatic vinyl compound monomer. When the monomer remaining in the liquid is used in the second polymerization step, the conversion of the aromatic vinyl compound monomer species through all the polymerization steps is preferably 50% by weight or more, particularly preferably 60% by weight or more. is there. The higher the conversion of the aromatic vinyl compound monomer through the second polymerization step or all the polymerization steps, the higher the probability that the polymerizable double bond of the diene unit of the copolymer main chain is cross-copolymerized.

In the production of the cross copolymer, preferably, among the conditions described in paragraph [0049], 1)
Alternatively, a manufacturing method that satisfies 2) is adopted, and among the above conditions, a manufacturing method that satisfies 1) is more preferably adopted. In the production method that satisfies 1), a method is more preferably employed in which the olefin partial pressure of the polymerization solution in the second polymerization step is changed to 300% or more with respect to the first polymerization step. 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 polymerization in the second polymerization step is preferably performed with respect to the olefin partial pressure immediately before the start of the polymerization in the first polymerization step. A method is employed in which the olefin partial pressure of the polymerization liquid immediately before the start is maintained at 300% or more.

The proportion of the copolymer obtained in the first polymerization step is at least 10% by weight or more, preferably 30% by weight or more of the finally obtained cross copolymer. The amount of the polymer (including the cross chain weight) obtained in the second polymerization step is at least 10% of the finally obtained cross copolymer.
% By weight, preferably 30% by weight or more. If either of them is 10% by weight or less or 90% by weight or more, the characteristics of the polymer having a small amount of components are not sufficiently exhibited. For example, flexibility, heat resistance, permanent compression set, rheological properties, chemical resistance, moldability, and the like are mentioned.
If the content is more than 10% by weight, these features cannot be provided together, and as a result, various properties as exemplified above cannot be simultaneously provided. Here, the aromatic vinyl compound content of the finally obtained cross copolymer is preferably from 1 mol% to 96 mol%, and the diene content is 0.0001 mol%.
It is preferably at least 3 mol%.

The first polymerization step and the second polymerization step can be carried out in different reactors. These steps can also be performed using a single reactor. Cross-copolymerization of olefins, aromatic vinyl compounds, and dienes using a coordination polymerization catalyst in a single reactor while continuously changing the olefin or aromatic vinyl compound concentration You can also.

The physical properties of the cross-copolymerized ethylene-styrene-divinylbenzene copolymer as a typical example of the cross-copolymer of the present invention will be described below. The cross copolymer (component (B)) used in the present invention has, for example, thermoplastic elastomer-like properties. Further, it is characterized in that the composition of the main chain and the cross chain (styrene content in the case of the cross-copolymerized ethylene-styrene-divinylbenzene copolymer) 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). Further, the cross-copolymer of the present invention can be obtained by optionally preparing an ethylene-styrene copolymer having a different styrene content (which may contain a small amount of divinylbenzene) corresponding to the styrene content of the main chain and the cross-chain, respectively. Can be included in proportions. This is because the cross copolymer functions as these compatibilizers, and thus can have various characteristics.

When ethylene is used as the olefin, the cross copolymer can have a crystal structure derived from an ethylene chain, and thus has good heat resistance. Further, the ethylene-styrene copolymer having a low styrene content can have characteristics such as a low glass transition temperature, a low embrittlement temperature (−50 ° C. or lower), and high mechanical properties (rupture strength, tensile elastic modulus). . In addition, since it can have a composition having a relatively high styrene content in either the main chain or the cross chain, it can have characteristics of an ethylene-styrene copolymer having a relatively high styrene content shown below. . That is, a relatively low tensile modulus, surface hardness, flexibility, a tan δ component (0.05 to 0.80 at 0 ° C. or 25 ° C.) near room temperature in the viscoelastic spectrum, scratch resistance, and PVC-like feel , Coloring and printing properties. That is,
Characteristically, it is excellent in heat resistance, compatibilization, scratch resistance, abrasion resistance, chemical resistance and the like as compared with the conventional ethylene-styrene copolymer.

The cross copolymer used in the present invention is D
The melting point is preferably from 65 ° C to 140 ° C by SC,
More preferably, at least one is observed at 80 ° C. or more and 130 ° C. or less, and its melting point is 10 J / g or more,
J / g or less, preferably 20 J / g or more and 120 J / g or less. The cross copolymer used in the present invention preferably 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. further,
The cross-copolymerized olefin-aromatic vinyl compound-diene copolymer has an aromatic vinyl compound content of 5 mol% or more and 5 mol% or more.
0 mol% or less, the aromatic vinyl compound content,
Heat of crystal fusion measured by DSC is 10 J / g or more and 150 J
/ G or less preferably satisfies the following relationship. (5 ≦ St ≦ 20) −3 · St + 125 ≦ Tm ≦ 140 (20 <St ≦ 50) 65 ≦ Tm ≦ 140 Tm; The heat of crystal fusion measured by DSC is 10 J / g or more and 1
Melting point (° C.) not more than 50 J / g St; Aromatic vinyl compound content (mol%) Known so-called pseudo-random copolymers, JP-A-9-309925, JP-A-11-13
No. 0808 discloses that the cross-copolymer has a higher melting point than the olefin-aromatic vinyl compound random copolymer.

When the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer has an aromatic vinyl compound content of 5 to 20 mol%, the aromatic vinyl compound content and the Vicat softening point are as follows. It is preferable to satisfy the relationship. (5 ≦ St ≦ 20) −3 · St + 120 ≦ Tvicat ≦ 140 Tvicat; Vicat softening point (° C.) St; Aromatic vinyl compound content (mol%) So-called pseudo-random copolymers known from JP-A-163088 and JP-A-7-53618, JP-A-9-309925, JP-A-11-13
No. 0808 discloses that the cross-copolymer has a higher Vicat softening point than the olefin-aromatic vinyl compound random copolymer.

The compounding amount of the cross copolymer is 5% by weight or more and less than 50% by weight, preferably 10% by weight or more and 40% by weight or less in the polyolefin resin composition of the present invention. If the amount is less than 5% by weight, the coloring properties, printability, scratch resistance, and impact strength-improving effects of the cross copolymer are not sufficiently exhibited. Characteristics such as rigidity and moldability of the polymer are lost.

Further, in addition to the essential components (A) and (B), other additional components (optional components) can be added to the olefin resin composition of the present invention. Such additional components include hydrogenated styrene-butadiene-
Copolymer rubbers such as styrene block copolymer, styrene-butadiene-styrene block copolymer, hydrogenated styrene-butadiene copolymer, and hydrogenated styrene-isoprene-styrene block copolymer can be exemplified. In addition, known additives can be added.
That is, phenolic and phosphorus-based antioxidants, hindered amine-based, benzophenone-based, benzotriazole-based anti-photodegradation inhibitors, organoaluminum compounds, nucleating agents such as organic phosphorus compounds, dispersants represented by stearic acid metal salts, Coloring substances such as phthalocyanine, titanium oxide and carbon black, calcium carbonate, talc, clay, calcium silicate, magnesium carbonate, magnesium hydroxide, mica, inorganic additives such as barium sulfate, titanium oxide, aluminum hydroxide, silica, and carbon black , Wood flour, filler such as wood pulp, paraffin, naphthene, aroma-based process oil, mineral oil softener such as liquid paraffin, castor oil, linseed oil, olefin wax, mineral wax, various esters, etc. And the like.

The olefin resin composition of the present invention can be obtained by uniformly mixing and kneading the above essential components (A) and (B) and, if necessary, additional optional components and additives. Although there is no particular limitation on the method, dry blending is performed with a mixer such as a Henschel mixer or a tumbler which is generally used, and a set temperature of 180 ° C. is set using a kneader such as an extruder, a Banbury mixer, a roll, or a kneader.
It is manufactured by kneading at ~ 250 ° C. Among these, it is preferable to manufacture using an extruder, especially a twin-screw extruder.

The olefin resin composition of the present invention has rigidity,
It has excellent impact strength and can be processed into various molded products. Among them, automotive interior and exterior products such as bumpers, side moldings, airbag covers, housing materials and parts for home electric appliances, daily miscellaneous goods, industrial parts For example, it can be suitably used as a film or a sheet.

[0067]

The present invention will be described below with reference to examples.
The present invention is not limited to the following examples. The copolymer obtained in each of the following Reference Examples was analyzed by the following means. The 13C-nmr measurement was performed using a device manufactured by JEOL Ltd. α-50.
0, the solvent used was heavy 1,1,2,2-tetrachloroethane, and the measurement was performed based on tetramethylsilane (TMS). Here, the measurement based on TMS is as follows. First, weight 1,1, based on TMS
The shift value of the central peak of the triplet 13C-nmr peak of 2,2-tetrachloroethane was determined. Next, the copolymer was dissolved in heavy 1,1,2,2-tetrachloroethane to obtain 1
3C-nmr was measured, and each peak shift value was
Calculated based on the triplet center peak of 1,2,2-tetrachloroethane. The shift value of the triplet center peak of heavy 1,1,2,2-tetrachloroethane is 73.89 pp.
m. The measurement was carried out using 3 parts of the copolymer against these solvents.
The dissolution was performed by weight / volume%.

The determination of the styrene content in the copolymer is as follows.
The peak was derived from a phenyl group proton based on TMS using a 1,1,2,2-tetrachloroethane solvent (6. H-nmr). 5 to 7.5 ppm) and a proton peak derived from an alkyl group (0.8 to 3 ppm).
At the end of the first and second polymerization steps, the amount of divinylbenzene in the polymerization liquid was determined by gas chromatography measurement of the polymerization liquid extracted at the end of the second polymerization step, and the amount of divinylbenzene consumed in the first and second polymerization steps ,
From this value, the divinylbenzene content of the polymer obtained in the first polymerization step and the divinylbenzene content of the finally obtained cross copolymer were determined. The molecular weight was determined using GPC (gel permeation chromatography) in terms of standard polystyrene. The measurement was performed using tetrahydrofuran (THF) as a solvent and HLC-8020 manufactured by Tosoh Corporation as a measuring instrument. The DSC was measured using a DSC200 manufactured by Seiko Denshi Co., Ltd. at a temperature rising rate of 10 ° C./min under a nitrogen stream. For a copolymer insoluble in THF at room temperature, ortho-dichlorobenzene was used as a solvent, and Tosoh HLC-812 was used as a measuring instrument.
The measurement was performed at 145 ° C. using No. 1. The gel content was measured as follows according to ASTM D-2765-84. About 1.0 g of the precisely weighed 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 net bag and weighed accurately. After extracting this in boiling xylene for about 5 hours, the net bag is collected,
Dried in vacuum at 90 ° C for more than 10 hours. After cooling sufficiently, the net bag was precisely weighed, and the amount of polymer gel was calculated by the following equation. [Gel content (%)] = [weight of polymer remaining in mesh bag after test (g)] / [weight of polymer in mesh bag before test (g)] × 100

The physical properties of the resin compositions of the examples were evaluated by the following methods. The molded piece is PS manufactured by Nissei Plastic Industry
(1) Flexural modulus: 23 ° C. according to ASTM D790
The measurement was performed at a bending speed of 15 mm / min using an injection molded product having a thickness of 1/4 inch. (2) Impact resistance: 1 / thickness according to ASTM D256
A 4-inch injection molded product was cut with a notch and the Izod impact strength at 23 ° C. was measured. (3) Vicat softening point: A Vicat softening point was measured at a load of 1 kgf using an injection molded product having a thickness of 1/4 inch according to JIS K7206. However, the Vicat softening points of Reference Examples 1 to 7 were measured under a load of 200 gf. (4) Tensile test: 2 in accordance with JIS K-7113
Using a No. 1/2 type dumbbell, pulling speed 100 mm / m
Measured in.

[Raw materials] (1) Component of olefin polymer (A) Block polypropylene copolymer: Chisso Polypro K7719 manufactured by Chisso Corporation was used. In the table, it is described as bPP. Random polypropylene: F23 manufactured by Grand Polymer
7BB was used. In the table, it is described as rPP. High density polyethylene: HIZEX 700 manufactured by Mitsui Chemicals, Inc.
0F was used. In the table, it is described as HDPE. Ethylene-vinyl acetate copolymer: NU manufactured by Nippon Unicar
C3830 was used. In the table, it is described as EVA. (2) Cross-copolymerized olefin-aromatic vinyl compound-diene copolymer of component (B) It was synthesized by the method described in Reference Examples 1 to 3. (3) Ethylene-styrene copolymer in Comparative Example It was synthesized by the methods described in Reference Examples 4 to 7.

Reference Example 1 <Synthesis of cross-copolymerized ethylene-styrene-divinylbenzene copolymer (C-1)> rac-dimethylmethylenebis (4,5-benzo-1-indenyl) was used as a catalyst.
It carried out as follows using zirconium dichloride. Polymerization was carried out using an autoclave having a capacity of 10 L, a stirrer and a jacket for heating and cooling. Toluene 440
0 mL, 400 mL of styrene, and 0.5 mL of divinylbenzene (purity: 80%, manufactured by Aldrich) were charged, and heated and stirred at an internal temperature of 70 ° C. About 100 L of nitrogen was bubbled through to purge the system and the polymerization solution. Triisobutylaluminum 8.4 mmol, methylalumoxane (manufactured by Tosoh Akzo Co., Ltd., PMAO-s) is 21 based on Al.
mmol, ethylene was immediately introduced, and the pressure was 0.2
After stabilizing at 5 MPa (1.5 kg / cm 2 G), 8.4 μmol of rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride and 1 mmol of triisobutylaluminum were added from a catalyst tank installed on an autoclave. About 50 ml of the dissolved toluene solution was added to the autoclave. 70 internal temperature
The polymerization was carried out for 46 minutes while maintaining the pressure at 0.25 MPa at ° C (first polymerization step). The consumption of ethylene at this stage was about 100 L under standard conditions. A part of the polymerization solution was sampled, and a polymer sample (polymer 1-A) in the first polymerization step was obtained by meta-precipitation. Ethylene was rapidly introduced, and the pressure in the system was adjusted to 1.1 MPa over 25 minutes. By increasing the pressure of ethylene, polymerization was promoted, and the internal temperature was temporarily increased from 70 ° C to 80 ° C. Polymerization was performed for 25 minutes while maintaining the pressure at 1.1 MPa (second polymerization step). After completion of the polymerization, the obtained polymer solution was added little by little into a large amount of vigorously stirred methanol solution to recover the polymer. 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. 860 g of a polymer (Polymer 1-C) was obtained. Table 1 shows the polymerization conditions of Reference Example 1 and Table 2 shows the polymerization conditions.
Shows the results of analysis of the obtained cross-copolymerized ethylene-styrene-divinylbenzene copolymer. Further, the polymer produced in the second polymerization step (1-
The calculated value of B) is shown in the table.

Reference Examples 2 and 3 Polymerization and post-treatment were carried out in the same manner as in Reference Example 1 under the conditions shown in Table 1. Table 2 shows the analysis results of the obtained cross-copolymerized ethylene-styrene-divinylbenzene copolymers. The results of calculating the components generated in the second polymerization step from the polymerization conditions and the polymerization results shown in Tables 1 and 2 are also 2-B,
Also shown in Table 2 as 3-B.

[0073]

[Table 1]

[0074]

[Table 2]

Reference Example 4 Polymerization was carried out using a polymerization vessel having a capacity of 150 L, a stirrer and a jacket for heating and cooling. After the inside of the system was replaced with nitrogen, 76 L of dehydrated cyclohexane and 3 L of dehydrated styrene were charged into a polymerization vessel, and heated and stirred at an internal temperature of 65 ° C. 84 mmol of triisobutylaluminum and 84 mol of methylalumoxane (PMAO-s, manufactured by Tosoh Akzo Co., Ltd.) based on Al
mmol was added. Immediately introduced ethylene, pressure 1.
After stabilizing at 0 MPa, the catalyst, rac dimethyl methylene bis (4,5-
84 μmol of benzo-1-indenyl) zirconium dichloride, 2 mmol of triisobutylaluminum
About 100 ml of a toluene solution in which was dissolved was added to the polymerization vessel. The polymerization was carried out for 120 minutes while maintaining the internal temperature at 65 ° C. and the ethylene pressure at 1.0 MPa. After depressurizing ethylene,
The polymerization vessel gas phase was purged several times with nitrogen. Next, the polymerization solution was put into 150 L of 85 ° C. heated water containing a dispersant (Pluronic P-103; manufactured by Asahi Denka Co., Ltd.) with vigorous stirring over 1 hour. After stirring at 97 ° C for 30 minutes,
Hot water containing crumbs was put into the cooling water, and the crumbs were collected. The crumb was air-dried at 50 ° C. to obtain 3 kg of a copolymer (SE1) having a crumb shape of about several mm and having a good crumb shape. The composition ratio of styrene and ethylene is 5 mol% and 95 respectively.
mol%. Table 3 shows the polymerization conditions of Reference Example 4, and Table 4 shows the analysis results of the obtained ethylene-styrene random copolymer.

<Reference Examples 5, 6, 7> Polymerization and post-treatment were carried out in the same manner as in Reference Example 4 under the conditions shown in Table 3. Table 3 shows the polymerization conditions of Reference Examples 5 to 7, and Table 4 shows the analysis results of the obtained styrene-ethylene random copolymer.

[0077]

[Table 3]

[0078]

[Table 4]

[0079]

Examples 1 to 6 and

Comparative Examples 1 to 7 Compounds were added in the proportions shown in Tables 5, 6, 7 and 8, and tetrakis [methylene-3- (3'5'-diene) was used as a heat stabilizer with respect to 100 parts by weight of the composition. -T
-Butyl 4'-hydroxyphenyl) propionate]
Methane (IR made by Ciba Specialty Chemicals)
GANOX1010) 0.1 part by weight was mixed and mixed for 3 minutes with a super mixer manufactured by Kawada Manufacturing Co., Ltd., and then kneaded and granulated at a set temperature of 210 ° C. with a twin-screw kneader (PCM30) manufactured by Ikegai Kikisha Co., Ltd. A resin composition was obtained. The measurement was performed according to the above various measurement methods. Table 5 shows the evaluation results.
6, 7 and 8.

[0080]

[Table 5]

[0081]

[Table 6]

[0082]

[Table 7]

[0083]

[Table 8]

As shown in Tables 5, 6, 7 and 8, compared with the olefin-aromatic vinyl compound random copolymer,
The composition containing the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer is an olefin resin composition having excellent rigidity and excellent heat resistance.

[0085]

The olefin resin composition of the present invention contains an olefin polymer and a novel cross-copolymerized olefin-aromatic vinyl compound-diene copolymer, is excellent in rigidity, heat resistance, etc., and is injection molded. It is a novel resin composition suitably used for applications such as articles and extruded articles.

[Brief description of the drawings]

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

FIG. 2 is a conceptual diagram showing the structure of a conventional grafted copolymer.

Continuation of the front page F term (reference) 4F071 AA12 AA12X AA13 AA13X AA15 AA15X AA20 AA20X AA21 AA21X AA22 AA22X AA76 AA77 AA84 BB05 BC01 BC07 4J002 BB031 BB051 BB061 A11 PCA AA13 AA14 AA16 AA17 AA18 AA21 AA64 AA68 AA69 AA71 AA72 BA01 BA02 BA03 BA04 BA05 BA07 BA08 BA45 BA46 BA47 BA49 BB04 DA02 DA05 DA08 DA17 DB02 DB07 DB09 DB17 GA06 GA09

Claims (20)

[Claims] An olefin resin composition containing the following components (A) and (B). Component (A): 50 to 95% by weight of olefin polymer. Component (B): The aromatic vinyl compound content is 1 mol% or more and 9
6 mol% or less, diene content is 0.0001 mol% or more, 3
Olefin-aromatic vinyl compound-diene copolymer in which the content of aromatic vinyl compound differs from the olefin-aromatic vinyl compound-diene copolymer by 5 mol% or less as compared with the copolymer, And / or 5% by weight or more and less than 50% by weight of a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer, wherein the olefin-aromatic vinyl compound-diene copolymer is cross-copolymerized. Here, the total of the components (A) and (B) is 100% by weight. 2. An olefin resin composition comprising the following components (A) and (B). Component (A): 50 to 95% by weight of olefin polymer. Component (B): The aromatic vinyl compound content is 1 mol% or more and 9
6 mol% or less, diene content is 0.0001 mol% or more, 3
Mol% or less, and the olefin-aromatic vinyl compound-diene copolymer whose balance is olefin is cross-copolymerized with the olefin-aromatic vinyl compound copolymer and / or the olefin-aromatic vinyl compound-diene copolymer. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer characterized by comprising an olefin-aromatic vinyl compound-diene copolymer having an aromatic vinyl compound content before cross-copolymerization. A cross-copolymerized olefin characterized by a difference of at least 5 mol%
Aromatic vinyl compound-diene copolymer 5% by weight or more 50
Less than weight%. Here, the total of the components (A) and (B) is 100% by weight. 3. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) is obtained by using a coordination polymerization catalyst as a first polymerization step to obtain an aromatic vinyl compound monomer, an olefin monomer and a diene copolymer. A monomer is copolymerized to synthesize an olefin-aromatic vinyl compound-diene copolymer, and then, as a second polymerization step having different polymerization conditions therefrom, the olefin-aromatic vinyl compound-diene copolymer and at least an olefin The olefin resin composition according to claim 1, wherein the olefin resin composition is produced by using at least a two-stage polymerization method in which polymerization is performed using a coordination polymerization catalyst in the presence of a monomer and an aromatic vinyl compound monomer. object. 4. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) comprising 10 to 90% by weight of the polymer produced in the first polymerization step, and second polymer. 90% by weight to 10% by weight of polymer produced in the process
The olefin resin composition according to claim 3, wherein Here, the total of the polymer produced in the first polymerization step and the polymer produced in the second polymerization step is 100% by weight. 5. The gel content of the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) is 10.
The olefin-based resin composition according to any one of claims 1 to 4, wherein the amount is less than 5% by weight. 6. The cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) is produced by a single-site coordination polymerization catalyst comprising a transition metal compound and a co-catalyst. The olefin resin composition according to any one of claims 1 to 5. 7. A coordination polymerization catalyst for producing a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) comprises a transition metal compound represented by the following chemical formula (1): The olefin resin composition according to claim 6, which is a polymerization catalyst comprising a catalyst. Embedded image In the formula, A and B represent an unsubstituted or substituted cyclopentaphenanthryl group, an unsubstituted or substituted benzoindenyl group,
It is a group selected from an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group, and an unsubstituted or substituted fluorenyl group. Y has a bond to A and B, and further contains a hydrogen or a hydrocarbon group having 1 to 20 carbon atoms (this group has 1 to 3 nitrogen, boron, silicon, phosphorus, selenium, oxygen or sulfur atom. (Which may be included) as a substituent. The substituents may be different or the same. Further, Y may have a cyclic structure such as a cyclohexylidene group and a cyclopentylidene group. X is each independently hydrogen, halogen, carbon number 1
An alkyl group having 15 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 a hydrocarbon substituent having 1 to 4 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or It is an amide group having hydrogen or a hydrocarbon substituent having 1 to 22 carbon atoms. n is an integer of 0, 1 or 2. M is zirconium, hafnium, or titanium. 8. The olefin of the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) is ethylene or two or more olefins containing ethylene. 7. The olefin-based resin composition according to any one of 7. 9. The olefin resin according to claim 8, wherein the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) has a crystal structure derived from an ethylene chain structure. Composition. 10. An aromatic vinyl compound of the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) is styrene.
9. The olefin resin composition according to any one of 9 above. 11. The cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)), wherein the diene is divinylbenzene.
The olefin-based resin composition according to any one of the preceding claims. 12. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) having an aromatic vinyl compound content of 5 to 50 mol% and a diene content of 0.0001 mol%. The olefin-based resin composition according to any one of claims 1 to 11, wherein at least 3 mol% and the balance is ethylene or two or more olefins containing ethylene. 13. An olefin of the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) is ethylene or two or more olefins containing ethylene, and the cross-copolymerized olefin-aromatic is used. The aromatic vinyl compound-diene copolymer (component (B)) has a crystal structure derived from an ethylene chain structure, and the cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) 13. A DSC, wherein at least one melting point of 65 ° C. or more and 140 ° C. or less is observed, and a heat of crystal fusion corresponding to the melting point is 10 J / g or more and 150 J / g or less. The olefin-based resin composition according to the above item. 14. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) having an aromatic vinyl compound content of 5 to 50 mol% and a diene content of 0.0001 mol%. Not less than 3 mol%, the balance being ethylene or two or more olefins containing ethylene, having a crystal structure derived from an ethylene chain structure, characterized in that it is a cross-copolymerized olefin-aromatic vinyl compound-diene copolymer. The content of the aromatic vinyl compound in the union and the cross-copolymerized olefin-aromatic vinyl compound-
The heat of crystal fusion corresponding to the crystal structure derived from the ethylene chain structure observed by DSC measurement of the diene copolymer (component (B)) is 10 J / g or more and 150 J / g or less. The olefin resin composition according to any one of claims 1 to 13, which satisfies a relationship. (5 ≦ St ≦ 20) −3 · St + 125 ≦ Tm ≦ 140 (20 <St ≦ 50) 65 ≦ Tm ≦ 140 Tm; heat of crystal fusion measured by DSC is 10 J / g or more;
Melting point (° C.) of 150 J / g or less St: Content of aromatic vinyl compound (mol%) 15. A cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) having an aromatic vinyl compound content of 5 to 20 mol% and a diene content of 0.0001 mol. The olefin-based resin composition according to any one of claims 1 to 14, wherein the olefin-based resin composition comprises at least 2% by mole of at least 3% by mole, and the balance is ethylene or two or more olefins containing ethylene. 16. The cross-copolymerized olefin-aromatic vinyl compound-diene copolymer (component (B)) has an aromatic vinyl compound content of 5 to 20 mol% and a diene content of 0.0001 mol. The olefin-based resin according to claim 15, wherein the content of the aromatic vinyl compound and the Vicat softening point satisfy the following relationship. Composition. (5 ≦ St ≦ 20) −3 · St + 120 ≦ Tvicat ≦ 140 Tvicat; Vicat softening point (° C.) St; Aromatic vinyl compound content (mol%) 17. An ethylene-α-olefin wherein the olefin polymer (component (A)) comprises high-density polyethylene, low-density polyethylene, ethylene and an α-olefin having 3 to 8 carbon atoms.
Olefin copolymer, ethylene-vinyl acetate copolymer,
The olefin resin composition according to any one of claims 1 to 16, wherein the composition is one or two or more olefin polymers selected from homopolypropylene and a propylene-ethylene copolymer. 18. The olefin resin composition according to claim 17, wherein the olefin polymer (component (A)) is a propylene-ethylene copolymer. 19. An olefin-based polymer (component (A)) comprising a propylene-ethylene copolymer, ethylene and C3-C3.
The olefin resin composition according to claim 17, comprising at least one ethylene-α-olefin copolymer comprising α-olefin of No. 8 above. 20. A molded article obtained by molding the olefin resin composition according to claim 1.