JP6959724B2 - Resin composition and its manufacturing method - Google Patents

Description

The present invention relates to a resin composition having excellent softness, heat resistance, cold resistance, and mechanical characteristics, and a method for producing the same.

<New thermoplastic elastomer>
Soft thermoplastic elastomers (hereinafter referred to as TPE) are used for various purposes, but it is generally difficult to achieve both softness and heat resistance. In the case of an olefin-based random copolymer, the softer the polymer, the lower the crystallinity. In the case of a TPE having an A hardness of about 50 to 80, for example, an ethylene-α-olefin copolymer or an ethylene-vinyl acetate copolymer, its practical heat resistant temperature is equal to its melting point, and is about 50 ° C to 80 ° C. Therefore, a resin composition (compound) containing a hydrogenated block copolymer having excellent softness and heat resistance, polypropylene, and oil is generally used. Hydrogenated block copolymers are relatively soft in themselves, have excellent heat resistance, and have excellent compatibility with oil, and are therefore suitable for this application.

<Hydrogenated block copolymer>
Hydrogenated block copolymers are produced by using styrene and diene such as butadiene and isoprene as raw materials, and performing anion living polymerization and subsequent hydrogenation treatment. However, the market for diene, which is a raw material, often changes drastically, and the supply companies for isoprene are limited. Further, the polybutadiene chain and the polyisoprene chain contain a double bond, and if they are left as they are, their durability and heat resistance will be insufficient, so that they need to be hydrogenated. The hydrogenation process causes an increase in the cost of hydrogenated block copolymers.

By the way, the hydride diene chain, which is a soft segment of a hydrogenated block copolymer, is a copolymer chain of ethylene and α-olefin (propylene or 1-butene). It can also be regarded as a soft copolymer chain. Therefore, attempts have been made to produce similar block copolymers directly from ethylene, α-olefin and styrene monomers by living polymerization without using diene, but the technical difficulty is high and one block copolymer is used. Due to the living polymerization in which only one polymer molecule can be obtained from the catalyst, the cost of the single-site coordination polymerization catalyst (initiator), which is a complex transition metal compound, is extremely high and impractical.

Therefore, research is being actively conducted to produce block copolymers by a non-living process by utilizing a single-site-coordinated polymerization catalyst having high polymerization activity for olefins. For example, in the case of a cross-polymer production technique, a divinylbenzene-containing olefin-aromatic vinyl compound copolymer is synthesized using a single-site coordination polymerization catalyst, and then vinyl such as styrene is synthesized in the coexistence of this copolymer. The compound is polymerized, and the divinylbenzene unit in the copolymer is copolymerized to produce a cross copolymer having both block chains of an olefin-aromatic vinyl compound copolymer chain and a vinyl compound polymer chain in the molecular structure. The technology is disclosed (Patent Documents 1 to 3). However, there is no description about the cross copolymer of the present invention.

The divinylbenzene-containing olefin-based copolymer preferably used for the cloth copolymer secures a pendant vinyl group sufficient for producing the cloth copolymer by reducing the self-crosslinking of a relatively small amount of the divinylbenzene unit contained therein. Moreover, it is necessary to have a sufficient molecular weight as a soft segment. Patent Document 4 describes a method for efficiently producing a copolymer containing a small amount of divinylbenzene in a copolymer chain of ethylene and α-olefin similar to a hydrogenated diene chain suitable for the present invention, and a catalyst used. There is. However, Patent Document 4 does not disclose the oil, nor does it disclose the cross-polymer of the present invention.

A method for producing a cross copolymer including a coordination polymerization step and a subsequent radical polymerization step. In the coordination polymerization step, an aromatic polyene copolymer macromer is synthesized using a single-site coordination polymerization catalyst, and then the aromatic polyene copolymer macromer is synthesized. Discloses a technique for producing a cross-polymer characterized by copolymerizing an aromatic polyene copolymer macromer, an aromatic vinyl compound and an imidized unsaturated dicarboxylic acid anhydride in a radical polymerization step (Patented). Document 5). Patent Document 5 exemplifies an ethylene-olefin-aromatic polyene copolymer as an aromatic polyene copolymer macromer, but its structure is different from that of the cross copolymer of the present invention. Patent Document 5 exemplifies epoxidized soybean oil and epoxidized flaxseed oil as epoxy-based plasticizers. However, Patent Document 5 does not disclose the amount of polypropylene-based resin used.

WO2000 / 037517 WO2007 / 139116 US6414102 Gazette Japanese Unexamined Patent Publication No. 2010-43246 JP-A-2009-167387

An object of the present invention is to provide a resin composition having excellent softness, heat resistance, cold resistance, and mechanical characteristics, and a method for producing the same.

The present invention is a resin composition containing 100 parts by mass of a cloth copolymer, 10 to 100 parts by mass of a polypropylene resin, and 20 to 200 parts by mass of an oil.
Here, the cross copolymer is a copolymer obtained by a polymerization step consisting of a coordination polymerization step and a crossing step, and as a coordination polymerization step, an ethylene monomer and 3 carbon atoms are used using a single-site coordination polymerization catalyst. Copolymerization of olefin monomers of ~ 12 and aromatic polyene is carried out to synthesize an ethylene-olefin-aromatic polyene copolymer, and then, as a crossing step, this ethylene-olefin-aromatic polyene copolymer and aromatic are carried out. It is a copolymer obtained by a production method of polymerizing using an anionic polymerization initiator or a radical polymerization initiator in the coexistence of a vinyl compound monomer.
Further, the resin composition contains 100 parts by mass of the cloth copolymer, 10 to 100 parts by mass of the polypropylene resin, and 20 to 200 parts by mass of the oil.
The cross-polymer is a copolymer having an ethylene-olefin-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain, and includes a graft through, and is an ethylene-olefin-aromatic polyene copolymer chain. And an aromatic vinyl compound polymer chain is a copolymer bonded via an aromatic polyene unit.
The cross-polymer is the resin composition that further satisfies the following conditions.
(1) The composition of the ethylene-olefin-aromatic polyene copolymer obtained in the coordination polymerization step is such that the olefin content is 15% by mass or more and 50% by mass or less, the aromatic polyene content is 0.01% by mass or more and 1% by mass or less. The rest is ethylene content,
(2) The weight average molecular weight of the ethylene-olefin-aromatic polyene copolymer obtained in the coordination polymerization step is 100,000 or more and 600,000 or less.
(3) The mass ratio of the ethylene-olefin-aromatic polyene copolymer obtained in the coordination polymerization step to the cloth copolymer obtained in the crossing step is 60 to 95% by mass.
The resin composition having a storage elastic modulus of −40 ° C. of 7 × 10 ⁸ Pa or less and a storage elastic modulus of 140 ° C. of 1 × 10 ⁵ Pa or more.
The resin composition having a tensile elastic modulus of 1 to 30 MPa, a breaking elongation of 300 to 2000%, and a breaking strength of 1 to 50 MPa.
The resin having an ethylene-olefin-aromatic polyene copolymer having an olefin content of 20% by mass or more and 35% by mass or less, an aromatic polyene content of 0.01% by mass or more and 0.3% by mass or less, and a balance of ethylene content. It is a composition
The resin composition having a tensile elastic modulus of 1 to 30 MPa, a breaking elongation of 700 to 2000%, and a breaking strength of 5 to 50 MPa.
The oil is a resin composition of paraffinic oil,
A method for producing the resin composition, which is a mixture of 100 parts by mass of a cloth copolymer, 10 to 100 parts by mass of a polypropylene resin, and 20 to 200 parts by mass of an oil.
Here, the cross-polymer is a copolymer obtained by a polymerization step consisting of a coordination polymerization step and a crossing step, and as a coordination polymerization step, an ethylene monomer using a single-site coordination polymerization catalyst and having 3 to 3 carbon atoms. Copolymerization of 12 olefin monomers and aromatic polyene is carried out to synthesize an ethylene-olefin-aromatic polyene copolymer, and then, as a crossing step, this ethylene-olefin-aromatic polyene copolymer and aromatic vinyl are used. It is a copolymer obtained by a production method of polymerizing using an anionic polymerization initiator or a radical polymerization initiator in the coexistence of a compound monomer.

The present invention has excellent softness, heat resistance, cold resistance, and mechanical characteristics.

Hereinafter, embodiments of the present invention will be described in detail. In the present specification, the symbol "~" means a range of values "greater than or equal to" and "less than or equal to" at both ends. For example, "A to B" means that it is greater than or equal to A and less than or equal to B. Further, in this specification, the exponential notation may be described as follows. For example, it indicates that 7.0E + 08 is 7.0 × 10 ^8.

<Cross copolymer>
The cross-polymer of the present invention is a copolymer obtained by a polymerization step consisting of a coordination polymerization step and a crossing step, and as a coordination polymerization step, an ethylene monomer and carbon are used using a single-site coordination polymerization catalyst. The ethylene-olefin-aromatic polyene copolymer is synthesized by copolymerizing the olefin monomer of the number 3 to 12 and the aromatic polyene, and then, as a crossing step, the ethylene-olefin-aromatic polyene copolymer is combined with the ethylene-olefin-aromatic polyene copolymer. It is a copolymer obtained by a production method of polymerizing using an anionic polymerization initiator or a radical polymerization initiator in the coexistence of an aromatic vinyl compound monomer.

In the cross-polymer, the olefin is an olefin monomer having 3 to 12 carbon atoms, and is, for example, an α-olefin, a cyclic olefin such as norbornene or vinylcyclohexane. The number of olefin monomers used may be one or more. It is preferably an α-olefin having 4 to 12 carbon atoms, and is one or more selected from 1-butene, 1-hexene and 1-octene. Most preferably, 1-hexene and / or 1-octene. Multiple olefin monomers dominated by 1-hexene and / or 1-octene are also most preferred.

In the cross copolymer, the aromatic polyene is not particularly limited, and conventionally known aromatic polyenes can be used. It has 10 or more and 30 or less carbon atoms, has a plurality of double bonds (vinyl groups) and a single or a plurality of aromatic groups, and is coordinated in terms of promoting the polymerization reaction and various physical properties of the obtained polymer. It is a polymerizable aromatic polyene, and the double bond left in the polymerized state in which one of the double bonds (vinyl groups) is used for the coordination polymerization is preferably anion-polymerizable or radically polymerizable aromatic polyene. .. Preferred is divinylbenzene. As the divinylbenzene, one or more selected from orthodivinylbenzene, paradivinylbenzene and metadivinylbenzene are preferable.

In the cross-polymer, as the aromatic vinyl compound monomer, styrene and various substituted styrenes, for example, p-methylstyrene, m-methylstyrene, o-methylstyrene, ot-butylstyrene, mt-butyl Examples thereof include styrene, pt-butyl styrene, p-chloro styrene, o-chloro styrene and the like. Among these, one or more selected from styrene, p-methylstyrene and p-chlorostyrene are preferable, and styrene is more preferable. A general method for producing a cross copolymer is as described in WO2000 / 037517.

Hereinafter, the details of the method for producing the cross copolymer used in the resin composition of the present invention will be described.
The composition of the ethylene-olefin-aromatic polyene copolymer in this coordination polymerization step can be controlled by selecting a catalyst or the monomer concentration in the polymerization solution under predetermined polymerization conditions. The monomer concentration in the polymerization solution can generally be controlled by the partial pressure of ethylene gas, the partial pressure of the olefin monomer, or the introduction of the measured monomer into the polymerization can. The molecular weight and molecular weight distribution of the ethylene-olefin-aromatic polyene copolymer can generally be controlled by selecting a catalyst or polymerization temperature, or by adding an appropriate chain transfer agent.

The single-site coordination polymerization catalyst used in the coordination polymerization step is composed of a transition metal compound and a co-catalyst. A known single-site coordination polymerization catalyst can be used in the present invention. The single-site coordination polymerization catalyst, particularly the transition metal compound, may be used alone or in combination of two or more. For example, the single-site coordination polymerization catalyst described in WO2000 / 037517 and WO2007 / 139116 can be used. Preferably, as the transition metal compound, one or more transition metal compounds selected from the following general formulas (1), (2) and (3) are used.

一般式（１）中、Ｆｌｕは、フルオレニル基又は置換フルオレニル基を示し、Ｃｐはシクロペンタジエニル基又は置換シクロペンタジエニル基を示す。尚、上記の置換フルオレニル基は、置換可能な水素の少なくとも１つ以上が炭素数１〜４の炭化水素基で置き換えられているもので、隣り合う置換基は一体となって４〜８員環の環状構造を有しても良い。
又、上記の置換シクロペンタジエニル基は、置換可能な水素の少なくとも１つ以上が炭素数１〜２の炭化水素基で置き換えられているものであり、隣り合う置換基は一体となった環状構造を有さない。又、Ｙは、Ｆｌｕ及びＣｐに対して結合を有する置換メチレン基であり、メチレン基の置換基は、水素、炭素数１〜１０の炭化水素基である。又、Ｍはジルコニウム、ハフニウム、又はチタンから選ばれる金属である。又、Ｘは、ハロゲン、炭素数１〜１５の炭化水素基、炭素数１〜１５のアルコキシド基、炭素数１〜１５のアミド基、炭素数３〜１５のアルキルシラン基である。ｎは１又は２の整数である。尚、Ｘが複数の場合、複数のＸは互いに結合を有していても良い。一般式（１）で示されるような遷移金属化合物は、特開２０１０−４３２４６号公報に記載されている。

In the general formula (1), Flu represents a fluorenyl group or a substituted fluorenyl group, and Cp represents a cyclopentadienyl group or a substituted cyclopentadienyl group. In the above-mentioned substituted fluorenyl group, at least one or more of the substitutable hydrogen is replaced with a hydrocarbon group having 1 to 4 carbon atoms, and the adjacent substituents are integrally 4 to 8 membered rings. May have an annular structure of.
Further, in the above-mentioned substituted cyclopentadienyl group, at least one or more of the substitutable hydrogen is replaced with a hydrocarbon group having 1 to 2 carbon atoms, and the adjacent substituents are an integral cyclic ring. Has no structure. Further, Y is a substituted methylene group having a bond to Flu and Cp, and the substituent of the methylene group is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. Further, M is a metal selected from zirconium, hafnium, or titanium. Further, X is a halogen, a hydrocarbon group having 1 to 15 carbon atoms, an alkoxide group having 1 to 15 carbon atoms, an amide group having 1 to 15 carbon atoms, and an alkylsilane group having 3 to 15 carbon atoms. n is an integer of 1 or 2. When there are a plurality of Xs, the plurality of Xs may have a bond with each other. A transition metal compound as represented by the general formula (1) is described in JP-A-2010-43246.

一般式（２）中、Ａ、Ｂはそれぞれ独立に存在するベンゾインデニル基又は置換ベンゾインデニル基であるか、又はインデニル基、置換インデニル基から選ばれる基である。Ｙ^ａは、Ａ、Ｂと結合を有し、置換基として水素或いは炭素数１〜２０の炭化水素基を有する置換硼素基である。Ｙ^ａの置換基は、１〜３個の窒素、硼素、珪素、燐、セレン、酸素又は硫黄原子を含んでいても良く、又、環状構造を有していても良い。Ｘ^ａは、それぞれ独立に水素、ハロゲン、炭素数１〜１５のアルキル基、炭素数３〜１５のアルケニル基、炭素数６〜１０のアリール基、炭素数８〜１２のアルキルアリール基、炭素数１〜４の炭化水素置換基を有するシリル基、炭素数１〜１０のアルコキシ基、又は水素若しくは炭素数１〜２２の炭化水素置換基を有するアミド基又はアミノ基である。ｎは１又は２の整数である。又、Ｘ^ａが複数である場合、複数のＸ^ａは結合を有していてもよい。Ｍ^ａはジルコニウム、ハフニウム又はチタンである。一般式（２）で示されるような遷移金属化合物は、ＷＯ２００１／０６８７１９号公報に記載されている。

In the general formula (2), A and B are independently existing benzoindenyl groups or substituted benzoindenyl groups, or groups selected from indenyl groups and substituted indenyl groups. Y ^a is, A, B and have a bond, a substituted boron group having a hydrocarbon group of hydrogen or 1 to 20 carbon atoms as a substituent. Substituent Y ^a is 1 to 3 nitrogen, boron, silicon, phosphorus, selenium, may contain an oxygen or sulfur atom may, or may have a cyclic structure. X ^a is independently hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 3 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 8 to 12 carbon atoms, and a carbon number of carbon atoms. It is a silyl group having 1 to 4 hydrocarbon substituents, an alkoxy group having 1 to 10 carbon atoms, or an amide group or an amino group having hydrogen or a hydrocarbon substituent having 1 to 22 carbon atoms. n is an integer of 1 or 2. Further, when X ^a is plural, the plurality of X ^a may have a bond. M ^a is zirconium, hafnium or titanium. Transition metal compounds as represented by the general formula (2) are described in WO2001 / 068719A.

一般式（３）中、Ｃｐ¹は非置換若しくは置換シクロペンタフェナンスリル基、非置換若しくは置換ベンゾインデニル基、非置換若しくは置換シクロペンタジエニル基、非置換若しくは置換インデニル基、又は非置換若しくは置換フルオレニル基から選ばれる基である。ここで置換シクロペンタフェナンスリル基、置換ベンゾインデニル基、置換シクロペンタジエニル基、置換インデニル基、又は置換フルオレニル基とは、置換可能な水素の１個以上が炭素数１〜２０のアルキル基、炭素数６〜１０のアリール基、炭素数７〜２０のアルキルアリール基、ハロゲン原子、ＯＳｉＲ_３基、ＳｉＲ_３基又はＰＲ_２基（Ｒは何れも炭素数１〜１０の炭化水素基を表す）で置換されたシクロペンタフェナンスリル基、ベンゾインデニル基、シクロペンタジエニル基、インデニル基、又はフルオレニル基である。Ｙ^ｂは、Ｃｐ¹、Ｚと結合を有し、他に水素若しくは炭素数１〜１５の炭化水素基を有するメチレン基、シリレン基、エチレン基、ゲルミレン基、又は硼素基である。置換基は互いに異なっていても同一でもよい。又、Ｙ^ｂは環状構造を有していてもよい。Ｚは窒素原子、酸素原子又は硫黄原子を含み、窒素原子、酸素原子、又は硫黄原子でＭ^ｂに配位する配位子でＹ^ｂと結合を有し、他に水素若しくは炭素数１〜１５の置換基を有する基である。Ｍ^ｂはジルコニウム、ハフニウム、又はチタンである。Ｘ^ｂは、水素、ハロゲン、炭素数１〜１５のアルキル基、炭素数６〜１０のアリール基、炭素数８〜１２のアルキルアリール基、炭素数１〜４の炭化水素置換基を有するシリル基、炭素数１〜１０のアルコキシ基、又は炭素数１〜６のアルキル置換基を有するジアルキルアミド基である。ｎは１又は２の整数である。一般式（３）で示されるような遷移金属化合物は、ＷＯ１９９９／０１４２２１号公報、ＥＰ４１６８１５Ａ２号公報、ＵＳ６２５４９５６号公報に記載されている。高分子量かつ自己架橋の少ない共重合体を活性よく与える点で、一般式（１）及び／又は（２）の遷移金属化合物が好ましい。

In the general formula (3), Cp ¹ is an unsubstituted or substituted cyclopentaphenanthryl group, an unsubstituted or substituted benzoindenyl group, an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group, or an unsubstituted. Alternatively, it is a group selected from the substituted fluorenyl groups. Here, the substituted cyclopentaphenanthryl group, the substituted benzoindenyl group, the substituted cyclopentadienyl group, the substituted indenyl group, or the substituted fluorenyl group is an alkyl having one or more substitutable hydrogens having 1 to 20 carbon atoms. Group, aryl group with 6 to 10 carbon atoms, alkylaryl group with 7 to 20 carbon atoms, halogen atom, ₃ OsiR groups, ₃ SiR groups or ₂ PR groups (R is a hydrocarbon group with 1 to 10 carbon atoms. A cyclopentaphenanthryl group, a benzoindenyl group, a cyclopentadienyl group, an indenyl group, or a fluorenyl group substituted with (represented). Y ^b is a methylene group, a silylene group, an ethylene group, a gelmilene group, or a boron group having a bond with ^{Cp 1 and Z and another hydrocarbon group having hydrogen or a hydrocarbon group having 1 to 15 carbon atoms.} The substituents may be different or the same. Further, Y ^b may have an annular structure. Z contains a nitrogen atom, an oxygen atom or a sulfur atom, is a ligand that coordinates ^{M b with a nitrogen atom, an oxygen atom, or a sulfur atom and has a bond with Y b,} and also has hydrogen or 1 to 15 carbon atoms. It is a group having a substituent of. ^Mb is zirconium, hafnium, or titanium. X ^b is 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, and a silyl group having a hydrocarbon substituent having 1 to 4 carbon atoms. , An alkoxy group having 1 to 10 carbon atoms, or a dialkylamide group having an alkyl substituent having 1 to 6 carbon atoms. n is an integer of 1 or 2. Transition metal compounds as represented by the general formula (3) are described in WO1999 / 014221A, EP416815A2, and US6254956. The transition metal compounds of the general formulas (1) and / or (2) are preferable in that they actively give a copolymer having a high molecular weight and a small amount of self-crosslinking.

The co-catalyst used together with the transition metal compound is not particularly limited, and a known co-catalyst used in combination with a conventionally known transition metal compound can be used. As such a co-catalyst, an alumoxane and / or a boron compound such as methylaluminoxane (hereinafter, also referred to as methylalmoxane or MAO) is preferable in terms of high activity against a polymerization reaction. Examples of the co-catalyst include the co-catalysts described in EP0872492A2, JP-A-11-130808, JP-A-9-309925, WO2000 / 0.2426, EP0985689A2, and JP-A-6-184179. Examples include alkylaluminum compounds. In the co-catalyst such as alumoxane, the molar ratio of aluminum atom / transition metal atom to the metal of the transition metal compound is preferably 0.1 to 100,000, and more preferably 10 to 10,000. If it is 0.1 or more, the transition metal compound can be effectively activated, and if it is 100,000 or less, the amount of the co-catalyst added can be suppressed, which is economically advantageous.

On the other hand, when a boron compound is used as the co-catalyst, the ratio of the boron atom / transition metal atom is preferably 0.01 to 100, more preferably 0.1 to 10, and most preferably 1.0 in terms of molar ratio. If it is 0.01 or more, the transition metal compound can be effectively activated, and if it is 100 or less, the amount of the co-catalyst added can be suppressed, which is economically advantageous. Regardless of which material is used as the co-catalyst, the transition metal compound and the co-catalyst may be mixed and prepared outside the polymerization facility, or may be mixed in the facility during polymerization.

In producing an ethylene-olefin-aromatic polyene copolymer in the coordination polymerization step of producing a cross-polymer, each of the monomers, transition metal compounds and co-catalysts exemplified above are brought into contact with each other, but in the order of contact and contact. Any known method can be used as the method.

As a method of these copolymerization, a method of polymerizing in a liquid monomer without using a solvent, or a method of pentane, hexane, heptane, cyclohexane, benzene, toluene, ethylbenzene, xylene, chloro-substituted benzene, chloro-substituted toluene, methylene chloride , Benzene, etc., and methods using a single solvent or a mixed solvent of saturated aliphatic, aromatic hydrocarbons, and halogenated hydrocarbons can be mentioned. Among these, one or more selected from alkane-based solvents, cyclohexane, toluene, and ethylbenzene are preferable. The polymerization form may be either solution polymerization or slurry polymerization. If necessary, known methods such as batch polymerization, continuous polymerization, prepolymerization, and multistage polymerization can be used.

It is also possible to use a single tank type polymerization can, a plurality of connected tank type polymerization cans, and a pipe polymerization facility in which one or more linear or loops are connected. For the pipe-shaped polymerization can, various known mixers such as a dynamic or static mixer and a static mixer that also serves as heat remover, and various known coolers such as a cooler equipped with a thin tube for heat removal are used. You may have a vessel. Further, it may have a batch type prepolymerized can. The polymerization temperature is preferably −78 to 200 ° C., more preferably 0 to 160 ° C., and most preferably 30 to 160 ° C. If the temperature is lower than −78 ° C., it may be industrially disadvantageous, and if the temperature exceeds 200 ° C., the transition metal compound may be decomposed. The pressure at the time of polymerization is preferably 0.1 to 100 atm, more preferably 1 to 30 atm, and most preferably 1 to 10 atm.

In the crossing step of the production method of the present invention, an anionic polymerization initiator or a radical polymerization initiator is used in the coexistence of the ethylene-olefin-aromatic polyene copolymer obtained in the coordination polymerization step and the aromatic vinyl compound monomer. Polymerize. In the crossing step of the present invention, in addition to the above aromatic vinyl compound monomer, an aromatic polyene that remains in a small amount in the polymerization solution without being polymerized in the coordination polymerization step may be polymerized.

The crossing step of the present invention is carried out after the above-mentioned coordination polymerization step. At this time, the copolymer obtained in the coordination polymerization step can be obtained by using an arbitrary polymer recovery method such as a crumb forming method, a steam stripping method, a devolatilization tank, a direct desolvation method using a devolatilization extruder, or the like. , It may be separated from the polymer solution, purified and used in the crossing step. However, it is economically preferable to use the residual olefin after the pressure release from the polymerization liquid after the coordination polymerization or without releasing the pressure in the next crossing step. One of the features of the present invention is that the polymer solution containing the polymer can be used in the crossing step without separating the polymer from the polymer solution.

When an anionic polymerization initiator is used in the crossing step, that is, when anionic polymerization is carried out, a mixed alcan-based solvent that does not cause inconveniences such as chain transfer during anionic polymerization, for example, a solvent such as cyclohexane or benzene is used. Preferably, other solvents such as toluene and ethylbenzene can be used as long as the polymerization temperature is 150 ° C. or lower. As the polymerization form, any known method used for anionic polymerization can be used. In the present invention, the order in which the aromatic vinyl compound monomer and the anionic polymerization initiator are added is arbitrary. That is, the aromatic vinyl compound monomer may be added to the polymerization solution, and the anionic polymerization initiator may be added after stirring, or the aromatic vinyl compound monomer may be added after the anionic polymerization initiator is added. The former is the polymerization that has better reproducibility and is industrially preferable. The cloth copolymer of the present invention is "a production method including a polymerization step including a coordination polymerization step and a crossing step, and as a coordination polymerization step, an ethylene monomer and a carbon number of carbons are used by using a single-site coordination polymerization catalyst. Copolymerization of 3 to 12 olefin monomers and aromatic polyene is carried out to synthesize an ethylene-olefin-aromatic polyene copolymer, and then, as a crossing step, this ethylene-olefin-aromatic polyene copolymer and aromatic are aromatic. A copolymer obtained by a production method of polymerizing with an anionic polymerization initiator or a radical polymerization initiator in the coexistence of a group vinyl compound monomer and further satisfying specific conditions ", and a copolymer weight obtained by a specific production method. Since it is a coalescence, its structure is arbitrary. The polymerization temperature is preferably −78 to 200 ° C., more preferably 0 to 200 ° C., and most preferably 30 to 150 ° C. If it is less than −78 ° C., it may be industrially disadvantageous, and if it exceeds 150 ° C., chain transfer or the like may occur, which may be unfavorable. The pressure at the time of polymerization is preferably 0.1 to 100 atm, more preferably 1 to 30 atm, and most preferably 1 to 10 atm.

A known anionic polymerization initiator can be used in the crossing step of the present invention. Among these, one or more selected from lithium salts such as biphenyl, naphthalene and pyrene, sodium salts and alkyllithium compounds are preferable, and alkyllithium compounds are most preferable. Among the alkyllithium compounds, one or more selected from sec-butyllithium and n (normal) -butyllithium are preferable. Moreover, you may use a polyfunctional initiator, a dilithium compound, and a trilithium compound. Further, if necessary, a known anionic polymerization terminal coupling agent may be used. When methylalmoxane is used as an auxiliary catalyst of the polymerization catalyst in the coordination polymerization step, the amount of the anionic polymerization initiator used is preferably equal to or more than the equivalent of oxygen atoms contained therein, and more preferably 2 equivalents or more. .. When a boron compound is used as a co-catalyst of the polymerization catalyst in the coordination polymerization step, the amount thereof is sufficiently smaller than the oxygen atom equivalent in methylarmoxane, so that the amount of the anionic polymerization initiator used should be reduced. Is possible.

When a radical polymerization initiator is used in the crossing step, that is, as a condition for performing radical polymerization, the method described in WO2000 / 037517 is adopted. In carrying out the crossing step of the present invention, anionic polymerization is preferable in that a high monomer conversion rate can be obtained in a short time and a substantially 100% conversion rate can be easily obtained because the polymerization rate is high.

Hereinafter, the cross copolymer used in the present invention will be described. This cross copolymer has an ethylene-olefin-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain, and the ethylene-olefin-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain are composed of the ethylene-olefin-aromatic polyene copolymer chain and the aromatic vinyl compound polymer chain. It is a polymer having a structure bonded via an aromatic polyene unit and containing a grafting through and / or a graft from structure. The fact that the ethylene-olefin-aromatic polyene copolymer chain and the aromatic vinyl compound polymer chain are bonded via the aromatic polyene unit can be proved by the following observable phenomenon. Here, a typical example in which an ethylene-1-hexene-divinylbenzene copolymer chain and a polystyrene chain are bonded via a divinylbenzene unit will be shown. That is, 1H-NMR (proton) of the ethylene-1-hexene-divinylbenzene copolymer obtained in the coordination polymerization step and the cross-polymer obtained by anion polymerization in the presence of the present copolymer and the styrene monomer. NMR) is measured, and the peak intensities of vinyl group hydrogen (proton) of both divinylbenzene units are compared using an appropriate internal standard peak (appropriate peak derived from an ethylene-1-hexene-divinylbenzene copolymer). do. Here, the peak intensity (area) of the vinyl-based hydrogen (proton) of the divinylbenzene unit of the cross-polymer is compared with the peak intensity (area) of the divinylbenzene unit of the ethylene-1-hexene-divinylbenzene copolymer. It is less than 50%, preferably less than 20%. During anionic polymerization (crossing step), the divinylbenzene unit is also copolymerized at the same time as the styrene monomer is polymerized, and the ethylene-1-hexene-divinylbenzene copolymer chain and the polystyrene chain are bonded via the divinylbenzene unit. In addition, in the cross copolymer after anionic polymerization, the peak intensity of hydrogen (proton) of the vinyl group of the divinylbenzene unit is greatly reduced. In reality, the hydrogen (proton) peak of the vinyl group of the divinylbenzene unit is substantially eliminated in the cross-polymer after anionic polymerization.

From another point of view, in this cloth copolymer, the ethylene-olefin-aromatic polyene copolymer chain and the aromatic vinyl compound polymer chain are bonded via the aromatic polyene unit (ethylene-1-as an example). It can be proved by the following observable phenomenon that the hexene-divinylbenzene copolymer chain and the polystyrene chain are bonded via the divinylbenzene unit). That is, even if the cloth copolymer is subjected to solvent separation using an appropriate good solvent and poor solvent, the contained ethylene-1-hexene-divinylbenzene copolymer chain and polystyrene chain are separated as their respective homopolymers. Can not do it. An example is shown below.
400 ml of acetone and a stirrer were placed in a large container, and the mixture was stirred while taking an ice bath on a magnetic stirrer. Toluene (40 ml) and cloth copolymer (4 g) were added to a separate container, and the mixture was heated and stirred to completely dissolve it. After dissolution, the hot solution was sucked up with a syringe and slowly added dropwise to the stirred cold acetone. After completion of the dropping, the precipitated acetone suspension containing the polymer was filtered under reduced pressure, and the cold acetone-insoluble polymer remaining on the filter was naturally dried and then vacuum dried at 60 ° C. overnight. The filtrate was transferred to an eggplant-shaped flask for an evaporator, the solvent was removed under reduced pressure with a rotary evaporator, and about 10 ml of a concentrated solution was taken out. The eggplant flask was washed several times with a small amount of acetone, and the washing liquid was added to the concentrated liquid. This was poured into about 1 L of vigorously stirred methanol to precipitate a cold acetone-soluble polymer, filtered under reduced pressure, and the polymer on the filter was naturally dried and then vacuum dried at 60 ° C. overnight. The amount of the cold acetone-soluble polymer is relatively small (about several mass% to 20 mass% with respect to the cloth copolymer used), and it can be confirmed by 1H-NMR measurement that it is a polystyrene homopolymer. On the other hand, the cold acetone insoluble content accounts for the majority (more than half), and when 1H-NMR of the cold acetone insoluble polymer is measured, both the ethylene-1-hexene-divinylbenzene copolymer chain and the polystyrene chain can be observed. , It is shown that the contained ethylene-1-hexene-divinylbenzene copolymer chain and polystyrene chain cannot be separated as their respective homopolymers. The following operation was performed to verify that the solvent was completely separated. Using the cold acetone insoluble polymer, the solvent was separated again according to the above procedure, the cold acetone insoluble polymer was recovered, and 1H-NMR measurement was carried out. It can be confirmed that the obtained composition (composition of ethylene-1-hexene-divinylbenzene copolymer chain and polystyrene chain) is substantially unchanged. In reality, the solvent separation is substantially completed by one solvent separation.

From the above, as an expression defining the cross polymer used in the present invention, the cross copolymer has an ethylene-olefin-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain, and the cloth copolymer has an ethylene-olefin. -A polymer having a structure in which an aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain are bonded via an aromatic polyene unit, and includes a grafting through and / or a graft from structure. be. More preferably, it is a copolymer that satisfies all of the following conditions (1) to (3).
(1) The composition of the ethylene-olefin-aromatic polyene copolymer obtained in the coordination polymerization step is such that the olefin content is 15% by mass or more and 50% by mass or less, the aromatic polyene content is 0.01% by mass or more and 1% by mass or less. The rest is ethylene content,
(2) The weight average molecular weight of the ethylene-olefin-aromatic polyene copolymer obtained in the coordination polymerization step is 100,000 or more and 600,000 or less.
(3) The mass ratio of the ethylene-olefin-aromatic polyene copolymer obtained in the coordination polymerization step to the cloth copolymer obtained in the crossing step is 60 to 95% by mass.

From yet another point of view, the present cloth copolymer will be described. This cloth copolymer is obtained by a production method including a polymerization step consisting of a coordination polymerization step and a crossing step, and as a coordination polymerization step, an ethylene monomer, an olefin monomer and an aromatic are used using a single-site coordination polymerization catalyst. Polyene copolymerization is carried out to synthesize an ethylene-olefin-aromatic polyene copolymer, and then as a crossing step, an anion is produced in the coexistence of this ethylene-olefin-aromatic polyene copolymer and an aromatic vinyl compound monomer. A copolymer produced by polymerization using a polymerization initiator or a radical polymerization initiator. As the aromatic vinyl compound monomer used in the crossing step, an unreacted monomer remaining in the polymerization solution in the coordination polymerization step may be used, or an aromatic vinyl compound monomer may be newly added thereto. Anionic polymerization or radical polymerization is initiated by the addition of an anionic polymerization initiator or a radical polymerization initiator to the polymerization solution. In this case, the aromatic polyene unit of the ethylene-olefin-aromatic polyene copolymer is contained in the polymerization solution. Compared with The polymerization proceeds while the vinyl group of the group polyene unit is also copolymerized. Therefore, many of the obtained cross copolymers have a structure (cross-bonding) in which an ethylene-olefin-aromatic polyene copolymer as a main chain and an aromatic vinyl compound polymer chain as a cross chain are bonded in a graft-through format. It is considered to be included.

From the above, as an expression defining the cross polymer used in the present invention, the cross copolymer has an ethylene-olefin-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain, and the cloth copolymer has an ethylene-olefin. -A polymer having a structure in which an aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain are bonded via an aromatic polyene unit, and includes a graft-through and / or a graft from structure. The cloth copolymer may contain a relatively small amount of aromatic vinyl compound (polystyrene) homopolymer. Further, it is preferable that the copolymer satisfies all of the following conditions (1) to (3).
(1) The composition of the ethylene-olefin-aromatic polyene copolymer obtained in the coordination polymerization step is such that the olefin content is 15% by mass or more and 50% by mass or less, the aromatic polyene content is 0.01% by mass or more and 1% by mass or less. The rest is ethylene content,
(2) The weight average molecular weight of the ethylene-olefin-aromatic polyene copolymer obtained in the coordination polymerization step is 100,000 or more and 600,000 or less.
(3) The mass ratio of the ethylene-olefin-aromatic polyene copolymer obtained in the coordination polymerization step to the cloth copolymer obtained in the crossing step is 60 to 95% by mass.

The cloth copolymer has good compatibility with polypropylene-based resins and oils. Therefore, the resin composition of the present invention has good compatibility with the components, and there is no oil bleeding out. It shows the feature that its softness can be adjusted in a wide range according to the purpose. Furthermore, it is possible to maintain a constant softness even at a low temperature and maintain a constant mechanical strength even at a high temperature.

When the cloth copolymer satisfies all the conditions (1) to (3) above, the cloth copolymer is basically soft and has good compatibility with polypropylene resins and oils. It can be suitably used as a raw material for the resin composition of the present invention.

If the weight average molecular weight of the ethylene-olefin-aromatic polyene copolymer exceeds the above range, the molding processability may decrease. If the aromatic polyene content of the ethylene-olefin-aromatic polyene copolymer obtained in the coordination polymerization step is less than the above range, the mechanical properties of the resin composition of the present invention may deteriorate. If the aromatic polyene content of the ethylene-olefin-aromatic polyene copolymer obtained in the coordination polymerization step exceeds the above range, the molding processability may decrease. The molecular weight distribution (Mw / Mn) of the ethylene-olefin-aromatic polyene copolymer obtained in the coordination polymerization step is preferably 1.5 or more and 6 or less, more preferably 1.5 or more and 4 or less, and 1.8 or more. 3 or less is most preferable. If the olefin content of the ethylene-olefin-aromatic polyene copolymer obtained in the coordination polymerization step is less than the above range, the crystallinity of the cross-polymer becomes high, the compatibility with the polypropylene-based resin decreases, and the resin The softness of the composition may decrease. If the olefin content of the ethylene-olefin-aromatic polyene copolymer obtained in the coordination polymerization step exceeds the above range, the mechanical properties of the obtained resin composition may decrease.

The mass ratio of the ethylene-olefin-aromatic polyene copolymer obtained in the coordination polymerization step to the cloth copolymer finally obtained through the crossing step is preferably 60 to 95% by mass. If the mass ratio of the ethylene-olefin-aromatic polyene copolymer obtained in the coordination polymerization step with respect to the cloth copolymer is less than the above range, the compatibility with the polypropylene resin or oil is lowered, and the resin composition is soft. The property may be reduced and the oil may bleed out. If the mass ratio of the ethylene-olefin-aromatic polyene copolymer obtained in the coordination polymerization step with respect to the cross copolymer exceeds the above range, the mechanical properties of the obtained resin composition may decrease.

In the cross-polymer, the composition of the ethylene-olefin-aromatic polyene copolymer obtained in the coordination polymerization step is such that the olefin content is 20% by mass or more and 35% by mass or less, and the aromatic polyene content is 0.01% by mass or more and 0. It is more preferable that the content is 3% by mass or less and the balance is ethylene content. By satisfying this condition, the resin composition of the present invention can exhibit higher heat resistance and mechanical characteristics. If the olefin content in the cloth copolymer is less than the above range, it becomes hard at a low temperature, and the above-mentioned storage elastic modulus condition of −40 ° C. may not be satisfied. If the olefin content of the cloth copolymer is less than the above range, the crystallinity derived from the ethylene chain increases, the compatibility with the polypropylene resin decreases, and the storage elastic modulus of 140 ° C. cannot be satisfied. In some cases.

Further, the total heat of fusion of crystals observed in the range of 40 to 140 ° C. from the DSC measurement of the cloth copolymer is preferably 70 J / g or less. The molecular weight of the aromatic vinyl compound polymer chain of the cross chain can be appropriately changed according to the purpose and is not particularly limited, but the weight average molecular weight (Mw) is preferably 10,000 or more and 150,000 or less, and 20,000 or more and 100,000 or less. Is more preferable. The molecular weight distribution (Mw / Mn) is preferably 1.0 or more and 6.0 or less. Since it is difficult to directly determine the molecular weight of the cross chain, in the present specification, it is assumed that the molecular weight is the same as that of the non-cross-copolymerized aromatic vinyl compound homopolymer, and a known appropriate method such as solvent separation is used. The molecular weight of the cross-chain is defined by using the molecular weight of the aromatic vinyl compound homopolymer obtained by separation.

When the mass ratio of the ethylene-olefin-aromatic polyene copolymer obtained in the coordination polymerization step with respect to the finally obtained cloth copolymer is less than the above range, the obtained cloth copolymer with polypropylene resin or oil Since the compatibility of the resin composition is lowered, the softness of the resin composition is lost, and the oil bleeds out, the above-mentioned condition of storage elasticity at −40 ° C. may not be satisfied.

<Polypropylene resin>
The polypropylene-based resin is a polymer mainly composed of propylene. Preferably, it is homopolypropylene (homoPP), block polypropylene (blockPP), random polypropylene or a mixture thereof. Homopolypropylene is preferable in terms of heat resistance and rigidity of the resin composition. The stereoregularity may be isotactic or syndiotactic, but isotactic is preferable in terms of heat resistance and rigidity of the resin composition. As the homopolypropylene and block polypropylene, for example, those described in JP-A-11-29690 and JP-A-11-29669 can also be preferably used.

<Oil>
As the oil, paraffin-based oil, naphthen-based oil, mineral oil-based oil such as aromatic oil and liquid paraffin, silicon oil, castor oil, flaxseed oil, olefin-based wax, and mineral-based wax are preferable. Among the oils, paraffin-based and / or naphthenic-based oils are preferable. These are available as Diana process oils from Idemitsu Kosan Co., Ltd.

The amount of the polypropylene-based resin used is preferably 10 to 100 parts by mass, more preferably 20 to 90 parts by mass with respect to 100 parts by mass of the cloth copolymer. The amount of oil used is preferably 20 to 200 parts by mass, preferably 40 to 180 parts by mass, and most preferably 110 to 160 parts by mass with respect to 100 parts by mass of the cloth copolymer. If the polypropylene-based resin is more than this, or if the oil is less than this, the softness of the obtained resin composition may be lost. If the amount of polypropylene-based resin is less than this, or if the amount of oil is more than this, the heat resistance and mechanical characteristics of the obtained resin composition may decrease, or the oil may bleed out.

Hereinafter, the above provisions will be described from the viewpoints of softness, heat resistance, cold resistance, and mechanical characteristics of the finally obtained resin composition of the present invention. Since the resin composition of the present invention has softness, cold resistance, and heat resistance, it is extremely useful as a thermoplastic elastomer. Specifically, it has the characteristic of a soft cold-resistant elastomer that maintains a certain degree of softness even at low temperatures. In the resin composition of the concrete to the present invention, it is preferable that the storage modulus obtained in viscoelasticity measurement is not more than 7 × 10 8 ^Pa at -40 ° C.. This is because the cloth copolymer of the present invention itself has a low glass transition temperature and also has good compatibility with oil. The resin composition of the present invention has the characteristics of a soft heat-resistant elastomer, which maintains an elastic modulus and strength of a certain level or higher even at a high temperature and is unlikely to melt or flow. Specifically in the resin composition of the present invention, it is preferable that the storage modulus obtained in viscoelasticity measurement is 1 × 10 5 ^Pa or more at 140 ° C.. It is considered that this is because the cloth copolymer used has good compatibility with the polypropylene resin.

The resin composition of the present invention is soft but has good mechanical characteristics. Specifically, it is preferable that the tensile elastic modulus is 1 to 30 MPa, the breaking elongation is 300 to 2000%, and the breaking strength is 1 to 50 MPa.

Heat-resistant resin composition of the present invention is more preferably specifically storage modulus obtained in viscoelasticity measurement is 3 × 10 5 ^Pa or more at 140 ° C.. The mechanical properties of the resin composition of the present invention are more preferably 1 to 30 MPa in tensile elastic modulus, 700 to 2000% in elongation at break, and 5 to 50 MPa in strength at break.

If necessary, other resins, elastomers, and rubbers can be added to the resin composition of the present invention as long as the object of the present invention is not impaired. In addition, known fillers and stabilizers, anti-aging agents, light-resistant improvers, ultraviolet absorbers, softeners, lubricants, processing aids, colorants, antistatic agents, and anti-fog agents, which are generally added to resin compositions. Anti-fog agents, anti-blocking agents, crystal nucleating agents, foaming agents and the like can be used.

In order to produce the resin composition of the present invention, a known suitable kneading method can be used. For example, melt mixing can be performed with a single-screw or twin-screw screw extruder, a Banbury type mixer, a plast mill, a conider, a heating roll, or the like. Before performing melt mixing, each raw material may be uniformly mixed with a Henschel mixer, a ribbon blender, a super mixer, a tumbler, or the like. The melt-kneading temperature is not particularly limited, but is preferably 100 to 300 ° C, more preferably 150 to 250 ° C.

As a molding method for the resin composition of the present invention, known molding methods such as vacuum forming, injection molding, blow molding, and extrusion molding can be used.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted.

Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto.

[Analysis and evaluation method]
The analysis of the copolymer obtained in the examples was carried out by the following means.

( ^{1 1} H-NMR spectrum)
The content of each unit of the olefin and the aromatic vinyl compound in the copolymer was determined by ¹ H-NMR, and α-500 manufactured by JEOL Ltd. and AC-250 manufactured by BRUCKER were used as instruments. When it was dissolved in 1,1,2,2-tetrachloroethane and dissolved at room temperature, it was measured at room temperature, and when it was not dissolved at room temperature, it was measured at 80 to 100 ° C. The content and composition of each unit were determined by comparing the area of the peaks derived from each of the obtained units by a known method. The mass ratio of the ethylene-olefin-aromatic polyene copolymer obtained in the coordination polymerization step contained in the cloth copolymer finally obtained through the crossing step is also the ethylene-olefin-aromatic polyene copolymer. It was determined by comparing the composition of the above and the composition of the cross copolymer. The mass% of the aromatic vinyl polymer obtained in the crossing step was also determined in the same manner.

(Gas chromatography analysis)
The content of the aromatic polyene polymer in the resin was determined from the difference between the amount of unreacted divinylbenzene in the polymerization solution determined by gas chromatography analysis and the amount of divinylbenzene used for the polymerization.

(Molecular weight measurement)
For the molecular weight, GPC (gel permeation chromatography) was used to determine the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene. The measurement was performed under the following conditions.
Column: TSK-GEL Multipore HXL-M φ7.8 × 300 mm (manufactured by Tosoh Corporation) was used by connecting two in series.
Column temperature: 40 ° C
Detector: RI
Solvent: THF
Liquid flow rate: 1.0 ml / min.
Sample concentration: 0.1 wt / vol%
Sample injection volume: 100 μL
For the molecular weight of the polymer insoluble in the THF solvent at room temperature, the weight average molecular weight in terms of standard polystyrene was determined using high temperature GPC (gel permeation chromatography). Using HLC-8121GPC / HT manufactured by Tosoh Corporation, the column was measured at 140 ° C. using TSKgelGMHHR-H (20) HT, 3 φ7.8 × 300 mm, ortodichlorobenzene or trichlorobenzene as a solvent.
Detector: RI
Sample concentration: 0.1 mass / volume%
Sample injection volume: 100 μL
Liquid flow rate: 1.0 ml / min.

(DSC measurement)
The DSC measurement was performed using a DSC6200 manufactured by Seiko Electronics Co., Ltd. under a nitrogen air flow. That is, 10 mg of resin was used, 10 mg of alumina was used as a reference, and an aluminum pan was used. The temperature was raised from room temperature to 240 ° C. at a heating rate of 10 ° C./min and then cooled to −120 ° C. at 20 ° C./min. .. After that, DSC measurement was performed while raising the temperature to 240 ° C. at a heating rate of 10 ° C./min to determine the melting point, heat of fusion of crystals, and glass transition point.

(MFR measurement)
The MFR at 200 ° C. was measured according to JIS K7210. The load was measured under the condition of 98N.

(Preparation of sample sheet)
As the sample for physical property evaluation, sheets of various thicknesses (0.3, 1.0, 2.0 mm) formed by a heating press method (temperature 250 ° C., time 5 minutes, pressure 50 kg / cm ^{2) were used.}

(Viscoelasticity measurement: storage elastic modulus)
A measurement sample (8 mm x 50 mm) was cut out from a film having a thickness of about 0.3 mm obtained by the heat press method, and a dynamic viscoelasticity measuring device (Reometrics RSA-III) was used to measure the frequency at 1 Hz and the temperature range at -50. The storage elastic modulus was determined by measuring in the range of ° C. to + 250 ° C.
Other measurement parameters related to the measurement are as follows.
Measurement frequency 1Hz
Temperature rise rate 4 ° C / min Sample measurement length 10 mm
Test Type = Dynamic Temperature Ramp (DTempRamp)
Initial Static Force 5.0g
Auto Tension Sensitivity 1.0g
Max Auto Tension Rate 0.033mm / s
Max Applied Strain 1.5%
Min Allowed Force 1.0g

(Tensile test: tensile elastic modulus, breaking point elongation (breaking elongation), breaking point strength (breaking strength))
In accordance with JIS K6251, a 1.0 mm thick sheet is cut into a No. 2 1/2 type test piece shape, and a tensile speed of 500 mm is used under the conditions of 23 ± 1 ° C using a Shimadzu AGS-100D type tensile tester. Measured at / min.

[Adjustment of raw materials]
(I) Catalyst A
Diphenylmethylene (fluorenyl) (cyclopentadienyl) zirconium dichloride (see general formula (4) below) is described by J. Mol. Am. Chem. Soc. , 110, 6255 (1988), and diphenylfulvene and fluorene were synthesized as ligand raw materials with reference to the production method.

[Example A] (Production of cross copolymer)
A catalyst A (diphenylmethylene (fluorenyl) (cyclopentadienyl) zirconium dichloride) was used as a catalyst, and the procedure was carried out as follows.

Under the polymerization conditions shown in Table 1, a stirrer and a 50 L first polymerization can with a jacket for heating and cooling were used, 21.3 kg of cyclohexane solvent, 1.8 kg of 1-hexene monomer (Linearene manufactured by Idemitsu Kosan Co., Ltd.) and divinylbenzene (DVB). 79 mmol was charged, and the mixture was heated and stirred at an internal temperature of 40 ° C. About 100 L of dry nitrogen gas was bubbled to purge the water content in the system and the polymer solution. Next, the internal temperature was raised to about 60 ° C., 30 mmol of triisobutylaluminum was added, 50 mmol of MAO (modified MAO: MMAO manufactured by Tosoh Finechem Co., Ltd.) was further added, and ethylene was immediately introduced. After the polymerization can pressure was stabilized at 0.85 MPa (0.75 MPaG), 30 ml of a toluene solution containing 1 mmol of triisobutylaluminum and 70 μmol of diphenylmethylene (fluorenyl) (cyclopentadienyl) zirconium dichloride from a catalyst tank installed on an autoclave. A catalyst solution consisting of the above was added to the autoclave to start the coordination polymerization step. Polymerization was carried out while maintaining the internal temperature at 65 ° C. and the pressure at 0.85 MPa. The ethylene supply was stopped at a predetermined ethylene integrated flow rate (1100 L), and the internal temperature of the autoclave was maintained at 65 ° C. while releasing the pressure. A small amount (several tens of ml) of the polymerization solution was sampled and mixed with methanol to precipitate a polymer, thereby obtaining a polymer sample in the coordination polymerization step. From this sampling solution, the polymer yield, composition, and molecular weight in the coordination polymerization step were determined. The polymerization solution was transferred to a 50 L second polymerization can with a stirrer and a jacket for heating and cooling, 1.0 kg of styrene monomer was added to the polymerization can, and the mixture was sufficiently stirred and mixed, and then 180 mmol of n-butyllithium (BuLi) was added to 65. A cross copolymer was synthesized by performing a crossing step (anionic polymerization step) while maintaining ~ 70 ° C., and the yield of the cross copolymer was determined. The obtained polymerization solution was poured little by little into a large amount of methanol solution that was vigorously stirred to recover the cross copolymer. The cloth copolymer was air-dried at room temperature for one day and night, and then dried at 80 ° C. in vacuum until no change in mass was observed.

[Examples B and C]
Polymerization was carried out under the polymerization conditions shown in Table 1 in the same procedure as in Example A.

Table 2 shows the analysis results of the ethylene-olefin-aromatic polyene copolymer obtained in the coordination polymerization step of each example and the cross copolymer obtained through the crossing step. The evaluation results are shown in Table 3. All of the cross copolymers obtained in Examples A to C satisfy the conditions of the cross copolymer of the present invention. The vinyl group hydrogen (proton) peak intensity (area) of the divinylbenzene unit of the cross-polymers obtained in Examples A to C is that of the ethylene-styrene-divinylbenzene copolymer obtained in the coordination polymerization step. It was less than 20% as compared with the same peak intensity (area) of the divinylbenzene unit. In reality, the hydrogen (proton) peak of the vinyl group of the divinylbenzene unit was substantially eliminated in the cross-polymer after anionic polymerization.

(Examples 1 to 6, Comparative Examples 1 to 3)
A resin composition containing a cloth copolymer, polypropylene, and oil was obtained as follows.
Using Brabender-Plasticcoder (PL2000 type manufactured by Brabender Co., Ltd.), the cross copolymers, homopolypropylene (J106G manufactured by Prime Polymer Co., Ltd.) and oils (paraffin-based oil, Idemitsu Kosan Co., Ltd.) obtained in Examples A to C were used. PW-100) manufactured by Co., Ltd. was prepared with the formulation (part by mass) shown in Table 4. A total of about 45 g of the resin composition was kneaded at 200 ° C. and a rotation speed of 100 times / minute for 10 minutes to prepare a sample. The oil was previously absorbed into an amorphous crumb-shaped cloth copolymer at room temperature for 24 hours and then used for kneading. As the antioxidant, a hindered phenolic antioxidant (Irg1076 manufactured by BASF) was used.

As a comparative example, instead of the cloth copolymer of the present invention, commercially available SEBS (polystyrene-poly (ethylene / propylene) block-polystyrene, Asahi Kasei Co., Ltd., H-1053, styrene content 29 wt%) and the cloth described in known literature are used. Polymer (cross-polymer obtained according to WO2007 / 139116 (main chain ethylene-styrene-divinylbenzene copolymer, main chain styrene content 24 mol%, divinylbenzene content 0.05 mol%, cross chain polystyrene, Using a polystyrene content of 26% by mass, MFR at 200 ° C. and a weight of 98N, 23 g / 10 min.)), A resin composition was obtained in the same manner as in Examples. The oil was absorbed in these amorphous crumb-shaped resins at room temperature for a whole day and night as in the examples, and then used for kneading.

Table 4 shows the physical characteristics of the resin compositions obtained in Examples and Comparative Examples. In the table, for example, 3.2E + 08 indicates a 3.2 × 10 ^8, 5.2E + 06 indicates a 5.2 × 10 ^6.

The resin composition of the present invention had good softness, heat resistance, cold resistance, and mechanical characteristics. When a commercially available hydrogenated block copolymer (SEBS) or a cloth copolymer described in a known document is used, the oil bleeds out severely and no further measurement of physical properties is performed. (Comparative Examples 4 to 6).

In particular, the most preferable conditions for the present invention, that is, the composition of the ethylene-olefin-aromatic polyene copolymer obtained in the coordination polymerization step is 20% by mass or more and 35% by mass or less of the olefin content, and 0.01% by mass of the aromatic polyene content. Resin compositions using the cross-polymers of Examples A and C (Examples 1 to 4 and 6), which are cross-polymers having an ethylene content of 0.3% by mass or less and the balance being ethylene content, have higher heat resistance. sex, specifically storage modulus is obtained by viscoelasticity measurement indicates 3 × ¹⁰ 5 or more Pa at 140 ° C., mechanical properties are the tensile modulus 1 to 30 MPa, elongation at break from 700 to 2000%, a breaking strength 5 The range of 50 MPa was satisfied.

Since the resin composition of the present invention has good compatibility with the cloth copolymer, polypropylene resin, and oil, the mechanical properties and heat resistance are improved, and the oil does not bleed out. There was a problem of doing things. Since the cross-polymer of the present invention has a relatively low glass transition temperature in the soft segment, it does not harden at a low temperature and does not easily bleed out even when kneaded with oil.

Claims (7)

A resin composition containing 100 parts by mass of a cloth copolymer, 10 to 100 parts by mass of a polypropylene resin, and 110 to 200 parts by mass of an oil.
Here, the cross-polymer is a copolymer having an ethylene-olefin-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain, and is an ethylene-olefin-aromatic polyene copolymer chain and an aromatic. A polymer in which a vinyl compound polymer chain is bonded via an aromatic polyene unit.
The conditions for the cross copolymer are as follows: (1) The composition of the ethylene-olefin-aromatic polyene copolymer is 15% by mass or more and 50% by mass or less, and the aromatic polyene content is 0.01% by mass or more and 1% by mass. Below, the balance is the ethylene content,
(2) The weight average molecular weight of the ethylene-olefin-aromatic polyene copolymer is 100,000 or more and 600,000 or less.
(3) Satisfy that the mass ratio of the ethylene-olefin-aromatic polyene copolymer to the cross copolymer obtained in the crossing step is 60 to 95% by mass. The storage elastic modulus at −40 ° C. is 7 × 10 ⁸ Pa or less, and the storage elastic modulus at 140 ° C. is 1 × 10 ⁵ Pa or more.
The storage elastic modulus is determined by the following conditions:
Measurement sample; 8 mm × 50 mm obtained by heat-pressing method from the resin composition, Thickness 0. 3 mm film temperature range; -50 ° C to + 250 ° C
Measurement frequency: 1Hz
Temperature rise rate: 4 ° C / min Sample measurement length: 10 mm
Test Type; Dynamic Temperature Ramp (DTempRamp)
Initial Static Force; 5.0g
Auto Tension Sensitivity; 1.0g
Max Auto Tension Rate; 0.033mm / s
Max Applied Strain; 1.5%
Min Allowed Force; 1.0g
The resin composition according to claim 1, which is measured in. The tensile elastic modulus is 1 to 30 MPa, the breaking elongation is 300 to 2000%, and the breaking strength is 1 to 50 MPa.
The tensile elastic modulus, elongation at break and strength at break are in accordance with JIS K6251, and the following conditions are:
Thickness of sheet produced from the resin composition; 1.0 mm
Test piece shape of the sheet; No. 2 1/2 type temperature; 23 ± 1 ° C
Tensile rate; 500 mm / min
The resin composition according to claim 1 or 2, which is measured in. Claims that the composition of the ethylene-olefin-aromatic polyene copolymer is 20% by mass or more and 35% by mass or less of the olefin content, 0.01% by mass or more and 0.3% by mass or less of the aromatic polyene content, and the balance is the ethylene content. The resin composition according to item 1 of 1-3. The tensile elastic modulus is 1 to 30 MPa, the breaking elongation is 700 to 2000%, and the breaking strength is 5 to 50 MPa.
The tensile elastic modulus, elongation at break and strength at break are in accordance with JIS K6251, and the following conditions are:
Thickness of sheet produced from the resin composition; 1.0 mm
Test piece shape of the sheet; No. 2 1/2 type temperature; 23 ± 1 ° C
Tensile rate; 500 mm / min
The resin composition according to claim 1, wherein the resin composition is measured in 1. The resin composition according to claim 1, wherein the oil is a paraffinic oil. The method for producing a resin composition according to claim 1, wherein 100 parts by mass of the cloth copolymer, 10 to 100 parts by mass of the polypropylene resin, and 110 to 200 parts by mass of the oil are kneaded.
Here, the cross-polymer is a copolymer obtained by a polymerization step consisting of a coordination polymerization step and a crossing step, and as a coordination polymerization step, an ethylene monomer using a single-site coordination polymerization catalyst and having 3 to 3 carbon atoms. Copolymerization of 12 olefin monomers and aromatic polyene is carried out to synthesize an ethylene-olefin-aromatic polyene copolymer, and then, as a crossing step, this ethylene-olefin-aromatic polyene copolymer and aromatic vinyl are used. A copolymer obtained by a production method in which an anionic polymerization initiator or a radical polymerization initiator is used to polymerize in the coexistence of a compound monomer.
The conditions for the cross copolymer are as follows: (1) The composition of the ethylene-olefin-aromatic polyene copolymer is 15% by mass or more and 50% by mass or less, and the aromatic polyene content is 0.01% by mass or more and 1% by mass. Below, the balance is the ethylene content,
(2) The weight average molecular weight of the ethylene-olefin-aromatic polyene copolymer is 100,000 or more and 600,000 or less.
(3) A production method satisfying that the mass ratio of the ethylene-olefin-aromatic polyene copolymer to the cross copolymer obtained in the crossing step is 60 to 95% by mass.