JP2011213822A - Ethylene/butene/nonconjugated polyene copolymer, rubber composition including the copolymer and use of the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ethylene/butene/nonconjugated polyene copolymer that can be used in various applications.SOLUTION: The ethylene/butene/nonconjugated polyene copolymer is synthesized using a catalyst represented by formula (I). In formula (1), M is Ti; Y is -NR-; Zis -SiR-; X' is 1,4-diphenyl-1,3-butadiene or 1,3-pentadiene; and X is 2-(N, N-dimethylamino)benzyl.

Description

  The present invention relates to an ethylene / butene / non-conjugated polyene copolymer, a rubber composition containing the copolymer, and uses of the composition.

  Ethylene / α-olefin copolymer rubber and ethylene / α-olefin / non-conjugated polyene copolymer rubber do not have unsaturated bonds in the main chain, so they have better weather resistance and heat resistance than conjugated diene rubbers. Excellent ozone resistance. A rubber composition containing these copolymer rubbers, a crosslinked product of the composition, and a foamed product of the composition utilize the above properties, and are used for automobile industrial parts, industrial rubber products, electrical insulation materials, civil engineering materials, Widely used in rubber products such as rubberized cloth.

  Various catalysts have been proposed as catalysts capable of obtaining an ethylene / α-olefin / non-conjugated polyene copolymer rubber (see, for example, Patent Document 1).

JP-T-2001-522398

  An object of the present invention is to provide a rubber composition that can be used in various applications, and an ethylene / butene / non-conjugated polyene copolymer contained in the rubber composition.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that the rubber composition containing the following ethylene / butene / non-conjugated polyene copolymer can be used in various applications. As a result, the present invention was completed.

  That is, the ethylene / butene / non-conjugated polyene copolymer of the present invention is synthesized using a catalyst having a structure represented by the following formula (I).

（式（Ｉ）中、Ｒ’およびＲ’’はそれぞれ独立に、水素原子または炭素数１〜２０のヒドロカルビル基であり、Ｍはチタンであり、Ｙは−ＮＲ^*−であり、Ｚ^*は−ＳｉＲ^* ₂−であり、前記Ｒ^*は、それぞれ独立に、水素原子または炭素数１〜２０のヒドロカルビル基であり、ｐおよびｑのうち一方は０であり、他方は１であり、
ｐが０かつｑが１である場合には、Ｍは＋２の酸化状態であり、Ｘ’は１，４−ジフェニル−１，３−ブタジエンまたは、１，３−ペンタジエンであり、
ｐが１かつｑが０である場合には、Ｍは＋３の酸化状態であり、Ｘは２−（Ｎ，Ｎ−ジメチルアミノ）ベンジルである。）

(In the formula (I), R ′ and R ″ are each independently a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, M is titanium, Y is —NR ^* —, and Z ^* is -SiR ^* _2- , wherein each R ^* is independently a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, one of p and q is 0, and the other is 1.
when p is 0 and q is 1, M is in the +2 oxidation state, X ′ is 1,4-diphenyl-1,3-butadiene or 1,3-pentadiene;
When p is 1 and q is 0, M is in the +3 oxidation state and X is 2- (N, N-dimethylamino) benzyl. )

  The ethylene / butene / non-conjugated polyene copolymer is derived from 50 to 95 mol% of structural units derived from ethylene, 4.9 to 49.9 mol% of structural units derived from butene, and non-conjugated polyene. It is preferable to contain 0.1 to 5 mol% of structural units (however, the total of structural units derived from ethylene, structural units derived from butene, and structural units derived from non-conjugated polyene is 100 mol%). .

  It is preferred that the non-conjugated polyene is at least one non-conjugated polyene selected from 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB).

The rubber composition of the present invention contains the ethylene / butene / non-conjugated polyene copolymer.
The crosslinked rubber of the present invention can be obtained by crosslinking the rubber composition.
The cross-linked foam of the present invention is obtained by cross-linking and foaming the rubber composition.

  The rubber composition containing the ethylene / butene / non-conjugated polyene copolymer of the present invention can be suitably used for various applications.

Next, the present invention will be specifically described.
[Ethylene / Butene / Nonconjugated Polyene Copolymer]
The ethylene / butene / non-conjugated polyene copolymer of the present invention is synthesized using a catalyst having a structure represented by the following formula (I).

（式（Ｉ）中、Ｒ’およびＲ’’はそれぞれ独立に、水素原子または炭素数１〜２０のヒドロカルビル基であり、Ｍはチタンであり、Ｙは−ＮＲ^*−であり、Ｚ^*は−ＳｉＲ^* ₂−であり、前記Ｒ^*は、それぞれ独立に、水素原子または炭素数１〜２０のヒドロカルビル基であり、ｐおよびｑのうち一方は０であり、他方は１であり、
ｐが０かつｑが１である場合には、Ｍは＋２の酸化状態であり、Ｘ’は１，４−ジフェニル−１，３−ブタジエンまたは、１，３−ペンタジエンであり、
ｐが１かつｑが０である場合には、Ｍは＋３の酸化状態であり、Ｘは２−（Ｎ，Ｎ−ジメチルアミノ）ベンジルである。）

(In the formula (I), R ′ and R ″ are each independently a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, M is titanium, Y is —NR ^* —, and Z ^* is -SiR ^* _2- , wherein each R ^* is independently a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, one of p and q is 0, and the other is 1.
when p is 0 and q is 1, M is in the +2 oxidation state, X ′ is 1,4-diphenyl-1,3-butadiene or 1,3-pentadiene;
When p is 1 and q is 0, M is in the +3 oxidation state and X is 2- (N, N-dimethylamino) benzyl. )

  The ethylene / butene / nonconjugated polyene copolymer of the present invention is a copolymer having ethylene, butene, and a nonconjugated polyene as monomers and having a structural unit derived from the raw material. The ethylene / butene / non-conjugated polyene copolymer of the present invention may be a random copolymer or a block copolymer, but is preferably a random copolymer.

  As the non-conjugated polyene, a cyclic or chain non-conjugated polyene is used. Examples of the cyclic non-conjugated polyene include 5-ethylidene-2-norbornene (ENB), dicyclopentadiene, 5-vinyl-2-norbornene (VNB), norbornadiene and methyltetrahydroindene. Examples of the chain non-conjugated polyene include 1,4-hexadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4-ethylidene-1,7-undecadiene, and the like. Is mentioned.

  Among these, as the non-conjugated polyene, 5-ethylidene-2-norbornene (ENB), dicyclopentadiene, 5-vinyl-2-norbornene (VNB) is preferably used, and 5-ethylidene-2-norbornene (ENB), 5- Vinyl-2-norbornene (VNB) is particularly preferably used. These non-conjugated polyenes are preferable from the viewpoints of availability and excellent mechanical properties of the crosslinked rubber. Moreover, a nonconjugated polyene may be used individually by 1 type, and may use 2 or more types.

  The ethylene / butene / non-conjugated polyene copolymer of the present invention preferably contains 50 to 95 mol% of structural units derived from ethylene and 4.9 to 49.9 mol% of structural units derived from butene, More preferably, it contains 70 to 95 mol% of structural units derived from ethylene and 4.9 to 29.9 mol% of structural units derived from butene. Furthermore, the structural unit derived from the non-conjugated polyene is preferably contained in an amount of 0.1 to 5 mol%, more preferably 0.1 to 3 mol%. However, the total of the structural unit derived from ethylene, the structural unit derived from butene, and the structural unit derived from non-conjugated polyene is 100 mol%.

  The amount of each structural unit contained in the ethylene / butene / non-conjugated polyene copolymer of the present invention is to adjust the ratio of the amount of each monomer supplied when producing the ethylene / butene / non-conjugated polyene copolymer. Thus, the above range can be obtained.

The ethylene / butene / non-conjugated polyene copolymer of the present invention is synthesized using the catalyst having the structure represented by the formula (I) as described above.
Examples of the hydrocarbyl group having 1 to 20 carbon atoms include linear alkyl groups such as a methyl group, an ethyl group, and a butyl group, and branched alkyl groups such as a t-butyl group and a neopentyl group.

  R ′ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. The R ″ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

The catalyst having the structure represented by the formula (I) is (t-butylamido) dimethyl (η ⁵ -2-methyl-s) from the viewpoint of suppressing fogging and solids due to low molecular weight components of the obtained crosslinked rubber. -Indacene-1-yl) silane titanium (II) 1,3-pentadiene (also known as: (t-butylamido) dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silane titanium (II) 1,3 -Pentadiene) (a catalyst having a structure represented by the formula (II)) is particularly preferred. In addition, the catalyst which has a structure represented by Formula (II) can be obtained by the method described in the Japanese translations of PCT publication No. 2001-522398, for example.

前記式（Ｉ）で表わされる構造を有する触媒は、非共役ポリエンの重合性に優れている。また、前記触媒を用いて合成される本発明のエチレン・ブテン・非共役ポリエン共重合体は、分子量分布および組成分布が狭く、均一な分子構造を有する共重合体である。このため、本発明のエチレン・ブテン・非共役ポリエン共重合体を含むゴム組成物、該組成物から得られる架橋ゴム、架橋発泡体は、表面外観に優れる傾向がある。

The catalyst having the structure represented by the formula (I) is excellent in the polymerizability of the nonconjugated polyene. The ethylene / butene / non-conjugated polyene copolymer of the present invention synthesized using the catalyst is a copolymer having a narrow molecular weight distribution and composition distribution and a uniform molecular structure. For this reason, the rubber composition containing the ethylene / butene / non-conjugated polyene copolymer of the present invention, and the crosslinked rubber and crosslinked foam obtained from the composition tend to be excellent in surface appearance.

  The ethylene / butene / non-conjugated polyene copolymer of the present invention uses a catalyst having the structure represented by the formula (I) as a main catalyst, and uses a boron compound and / or an organoaluminum compound such as trialkylaluminum as a cocatalyst. It can be synthesized by a continuous method or a batch method using an aliphatic hydrocarbon such as hexane as a solvent and a reactor equipped with a stirrer.

  Examples of boron compounds include trityltetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (pentafluorophenyl) borate, di (hydrogenated tallowalkyl) methylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluoro). Phenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (s-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethyl Anilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium n-butyltris (pentafluoro Phenyl) borate, N, N-dimethylanilinium benzyltris (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4- (t-butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl ) Borate, N, N-dimethylanilinium tetrakis (4- (triisopropylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium pentafluorophenoxytris (pentafluorophenyl) Borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4, 6-teto Fluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate and N, N-dimethyl-2,4,6- Trimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate; di (isopropyl) ammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (2,3,4,6-tetra Fluorophenyl) borate, di Dialkylammonium salts such as methyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate and dicyclohexylammonium tetrakis (pentafluorophenyl) borate; triphenylphosphonium tetrakis (pentafluorophenyl) borate; Trisubstituted phosphonium salts such as tri (o-tolyl) phosphonium tetrakis (pentafluorophenyl) borate and tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate; diphenyloxonium tetrakis (pentafluorophenyl) ) Borate, di (o-tolyl) oxonium tetrakis (pentafluorophenyl) borate, and di (2,6-dimethylphenyl) oxoniu Disubstituted oxonium salts such as tetrakis (pentafluorophenyl) borate; diphenylsulfonium tetrakis (pentafluorophenyl) borate, di (o-tolyl) sulfonium tetrakis (pentafluorophenyl) borate, and bis (2,6-dimethylphenyl) ) Disubstituted sulfonium salts such as sulfonium tetrakis (pentafluorophenyl) borate.

An example of the organoaluminum compound is triisobutylaluminum (TIBA).
The reaction temperature for synthesizing the ethylene / butene / non-conjugated polyene copolymer of the present invention is usually -20 to 200 ° C, preferably 0 to 150 ° C. The polymerization pressure is usually in the range of more than 0 MPa to 8 MPa (gauge pressure), preferably more than 0 MPa to 5 MPa (gauge pressure). The reaction time (average residence time when copolymerization is carried out in a continuous process) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 10 minutes to 3 hours. . Furthermore, molecular weight regulators such as hydrogen can be used.

  There is no particular limitation on the charged amount (supply amount) of each monomer when synthesizing the ethylene / butene / non-conjugated polyene copolymer of the present invention, but the amount ratio of raw materials used for polymerization is as follows: Usually, 0.1 to 1 mol of butene, 0.01 to 0.1 mol of non-conjugated polyene, preferably 0.1 to 0.5 mol of butene, and 0.01 to 0.06 mol of non-conjugated polyene. is there. By supplying each monomer within the above range, the ethylene / butene / non-conjugated polyene copolymer of the present invention can be suitably obtained.

  The ethylene / butene / non-conjugated polyene copolymer of the present invention has a melt flow rate (MFR) of usually from 0.1 to 10 g / 10 at 190 ° C. and a load of 2.16 kg measured by the method described in ASTM D1238. Minutes, preferably 0.5 to 5 g / 10 minutes. Within the above range, the ethylene / butene / non-conjugated polyene copolymer and the composition containing the copolymer are excellent in moldability, which is preferable.

  In the ethylene / butene / non-conjugated polyene copolymer of the present invention, the upper limit of Mooney viscosity [ML (1 + 4) 100 ° C.] measured at 100 ° C. is 200, preferably 100, more preferably 90, particularly preferably 80, Most preferably, it is 60, and the lower limit is 5, preferably 10. More specifically, the Mooney viscosity [ML (1 + 4) 100 ° C.] measured at 100 ° C. is 5 to 200, preferably 5 to 90, more preferably 5 to 80, and most preferably 10 to 60. Within this range, a highly foamed product can be obtained using the composition containing the ethylene / butene / non-conjugated polyene copolymer of the present invention. Excellent kneading stability when mixed with other ingredients.

The Mooney viscosity can be measured according to JIS K 6300, for example, using a Mooney viscometer (SMV202 type manufactured by Shimadzu Corporation).
The ethylene / butene / non-conjugated polyene copolymer of the present invention preferably has a density measured according to JIS K 7112 of 800 to 1000 kg / m ³ , and preferably 850 to 950 kg / m ^3. More preferred. Within the said range, since the mechanical property of the obtained crosslinked rubber is excellent, it is preferable.

  The intrinsic viscosity [η] of the ethylene / butene / non-conjugated polyene copolymer of the present invention is usually 0.5 to 5.0 dl / g, preferably 1.0 to 3.0 dl / g, more preferably 1. 0.0 to 2.0 dl / g. When the intrinsic viscosity is less than 0.5 dl / g, the viscosity is too low and the workability tends to deteriorate or the strength is insufficient. When the intrinsic viscosity exceeds 5.0 dl / g, the viscosity becomes too high and the workability tends to deteriorate. .

  The glass transition temperature (Tg) of the ethylene / butene / non-conjugated polyene copolymer of the present invention is preferably −30 to −60 ° C., and more preferably −35 to −55 ° C. Tg within the above range is preferable because the mechanical properties of the resulting crosslinked rubber are excellent.

(Rubber composition)
The rubber composition of the present invention comprises the ethylene / butene / non-conjugated polyene copolymer.

  The component other than the ethylene / butene / non-conjugated polyene copolymer contained in the rubber composition of the present invention is not particularly limited. For example, an ethylene polymer (however, the ethylene / butene / non-conjugated polyene copolymer) Resin) such as a propylene polymer, and other components.

  Examples of the ethylene-based polymer include ethylene homopolymer, ethylene / C3-C20 α-olefin copolymer, ethylene / C3-20 α-olefin / non-conjugated polyene copolymer (however, the ethylene -Excluding butene / non-conjugated polyene copolymers), ethylene / polar monomer copolymers, and the like. Examples of the ethylene / C3-C20 α-olefin / non-conjugated polyene copolymer include an ethylene / propylene / ENB copolymer and an ethylene / propylene / VNB copolymer. Examples of the ethylene / propylene / ENB copolymer include Mitsui EPT4045M (trade name; manufactured by Mitsui Chemicals, Inc.).

Examples of the propylene polymer include propylene homopolymer, propylene / α-olefin copolymer having 4 to 20 carbon atoms, and the like.
When the rubber composition of the present invention contains resins (other resins) other than the ethylene / butene / non-conjugated polyene copolymer, the ethylene / butene / non-conjugated polyene copolymer is usually 5 -95 parts by weight and other resins are blended in the range of 5 to 95 parts by weight (provided that the total of the ethylene / butene / non-conjugated polyene copolymer and other resins is 100 parts by weight).

  Other components include foaming agents, foaming aids, vulcanizing agents, vulcanization accelerators, vulcanizing aids, reinforcing agents, inorganic fillers, softeners, anti-aging agents (stabilizers), processing aids, activity Agents, hygroscopic agents, and the like, and are blended in the rubber composition according to the use and purpose of the rubber composition.

  Examples of the foaming agent include inorganic foaming agents such as sodium bicarbonate and sodium carbonate; nitroso compounds such as N, N′-dinitrosopentamethylenetetramine and N, N′-dinitrosotephthalamide; azodicarbonamide and azo Azo compounds such as bisisobutyronitrile; hydrazide compounds such as benzenesulfonyl hydrazide and 4,4′-oxybis (benzenesulfonyl hydrazide); organic foams such as azide compounds such as calcium azide and 4,4′-diphenyldisulfonyl azide Agents. Moreover, as a commercial item, for example, VINYHALL AC-2F (trade name; manufactured by Eiwa Kasei Kogyo Co., Ltd.), VINYHALL AC # LQ (trade name; manufactured by Eiwa Kasei Kogyo Co., Ltd., azodicarbonamide (abbreviated as ADCA)), neoselbon N # 1000 SW (trade name; manufactured by Eiwa Kasei Kogyo Co., Ltd., 4,4′-oxybis (benzenesulfonylhydrazide (abbreviation: OBSH)), cellular D (trade name; manufactured by Eiwa Kasei Kogyo Co., Ltd., N, N′-dinitrosopentamethylenetetramine ( Abbreviation DPT)) and the like.

The blending amount of the foaming agent is usually 1 to 70 parts by weight with respect to 100 parts by weight of the ethylene / butene / non-conjugated polyene copolymer.
In addition to the foaming agent, a foaming aid may be added to the rubber composition of the present invention as necessary. The foaming aid exhibits actions such as lowering the decomposition temperature of the foaming agent, promoting decomposition, or uniforming the bubbles.

  Examples of the foaming aid include organic acids such as salicylic acid, phthalic acid, stearic acid, oxalic acid and citric acid or salts thereof; urea or derivatives thereof. Examples of commercially available products include cell paste K5 (trade name; manufactured by Eiwa Kasei Kogyo Co., Ltd., urea) and FE-507 (trade name: manufactured by Eiwa Kasei Kogyo Co., Ltd., baking soda).

The blending amount of the foaming aid is usually 0.1 to 5 parts by weight with respect to 100 parts by weight of the ethylene / butene / non-conjugated polyene copolymer.
Examples of the vulcanizing agent include sulfur compounds, organic peroxides, phenol resins, and oxime compounds.

  As the sulfur compound, sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, selenium dithiocarbamate, and the like are preferable, and sulfur and tetramethylthiuram disulfide are more preferable.

  The compounding amount of the sulfur compound is usually 0.1 to 10 parts by weight with respect to 100 parts by weight of the ethylene / butene / non-conjugated polyene copolymer. When the blending amount is within the above range, it is preferable because the mechanical properties of the resulting crosslinked rubber are excellent.

  As the organic peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5 -Dimethyl-2,5-di (t-butylperoxy) hexyne-3, di-t-butylperoxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-dibutylhydroperoxide and the like are preferable, More preferred are dicumyl peroxide, di-t-butyl peroxide and di-t-butylperoxy-3,3,5-trimethylcyclohexane.

  The compounding amount of the organic peroxide is usually 0.001 to 0.05 mol with respect to 100 g of the ethylene / butene / non-conjugated polyene copolymer. When the amount of the organic peroxide is within the above range, it is preferable because the mechanical properties of the resulting crosslinked rubber are excellent.

When a sulfur compound is used as the vulcanizing agent, it is preferable to use a vulcanization accelerator in combination.
Examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazole sulfenamide, N, N′-diisopropyl-2-benzothiazole sulfenamide, 2-mercapto Benzothiazole (for example, Sunseller M (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.), 2- (4-morpholinodithio) benzothiazole (for example, Noxeller MDB-P (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)) 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole and dibenzothiazyl disulfide (for example, Sunseller DM (trade name; Sanshin Chemical Industry) Thiazoles such as diphenylguanidine, triphenylguanidine And guanidines such as diorthotolyl guanidine; aldehyde amines such as acetaldehyde / aniline condensate and butyraldehyde / aniline condensate; imidazolines such as 2-mercaptoimidazoline; thioureas such as diethylthiourea and dibutylthiourea; tetramethylthiuram Monosulfide (for example, Sunceller TS (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetramethylthiuram disulfide (for example, Sunceller TT (trade name; manufactured by Sanshin Chemical Industries)), tetraethylthiuram disulfide (for example, Sunceller TET) (Trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetrabutyl thiuram disulfide (for example, Sunseller TBT (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)) and dipentamethylene thiuram tetrasulfide (for example, Thiuram series such as Nseller TRA (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.); zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate (for example, Sunseller PZ, Sunseller BZ and Sunseller EZ (trade names; Sanshin) Dithioates such as tellurium diethyldithiocarbamate; ethylenethiourea (for example, Sunseller BUR (trade name; manufactured by Sanshin Chemical Co., Ltd.), Sunseller 22-C (trade name; Sanshin Chemical Industry Co., Ltd.) )) And thioureas such as N, N′-diethylthiourea; xanthates such as zinc dibutylxatogenate; and others, zinc white (for example, META-Z102 (trade name; manufactured by Inoue Lime Industry Co., Ltd., zinc oxide)) Etc.

The amount of the vulcanization accelerator is usually 0.1 to 20 parts by weight with respect to 100 parts by weight of the ethylene / butene / non-conjugated polyene copolymer.
When the blending amount of the foaming agent, foaming aid, vulcanizing agent, and vulcanization accelerator is within the above range, it is preferable because the mechanical properties of the resulting crosslinked rubber are excellent.

  Vulcanization aids include quinone dioxime such as p-quinone dioxime; acrylic such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; diallyl phthalate and triallyl isocyanurate (for example, M-60 (trade name) And other maleimides; divinylbenzene; zinc oxide, magnesium oxide / zinc flower (for example, META-Z102 (trade name; manufactured by Inoue Lime Industry Co., Ltd.)), and the like. It can select suitably according to a use. A vulcanization auxiliary may be used individually by 1 type, and may be used in combination of 2 or more types.

The amount of the vulcanization aid is usually 1 to 50 parts by weight with respect to 100 parts by weight of the ethylene / butene / non-conjugated polyene copolymer.
The rubber composition of the present invention may contain a reinforcing agent or an inorganic filler for the purpose of improving mechanical properties such as tensile strength, tear strength, and abrasion resistance.

  As reinforcing agents, carbon such as Asahi # 55G, Asahi # 50HG and Asahi # 60G (trade name; manufactured by Asahi Carbon Co., Ltd.) and seast (SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, MT, etc.) Black (manufactured by Tokai Carbon Co., Ltd.); those obtained by surface-treating these carbon blacks with a silane coupling agent; silica; activated calcium carbonate; fine talc and fine silicate. Of these, Asahi # 55G, Asahi # 50HG, Asahi # 60G, Seast FEF and the like are preferable.

  Examples of the inorganic filler include light calcium carbonate, heavy calcium carbonate, talc and clay, and talc is particularly preferable. Moreover, as talc, for example, commercially available MISTRON VAPOR (manufactured by Nippon Mystron) is used.

The compounding amount of the reinforcing agent or the inorganic filler is usually 30 to 800 parts by weight with respect to 100 parts by weight of the ethylene / butene / non-conjugated polyene copolymer.
When the compounding amount of the reinforcing agent or the inorganic filler is within the above range, the rubber composition of the present invention is excellent in kneading processability, and the resulting cross-linked molded product exhibits mechanical properties such as strength and flexibility and compression set. Excellent.

  Examples of the softener include process oils (for example, Diana process oil PW-380, Diana process oil PS-430 (trade name; manufactured by Idemitsu Kosan Co., Ltd.)), lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, petroleum jelly, and the like. Coal tar softeners such as coal tar and coal tar pitch; fatty oil softeners such as mustard oil, linseed oil, rapeseed oil, soybean oil and coconut oil; waxes such as beeswax, carnauba wax and lanolin Fatty acids or salts thereof such as ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate and zinc laurate; naphthenic acid, pine oil and rosin or derivatives thereof; terpene resins, petroleum resins, atactic polypropylene and coumarone Inden tree Synthetic polymer substances such as fats; ester softeners such as dioctyl phthalate, dioctyl adipate and dioctyl sebacate; other microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, liquid thiocol, hydrocarbon synthetic lubricating oil, tall oil and Sub (Factis) etc. are mentioned. Of these, petroleum softeners are preferable, and process oil is particularly preferable. A softening agent may be used individually by 1 type, and may be used in combination of 2 or more types.

  The blending amount of the softener can be appropriately selected depending on the use. The blending amount of the softening agent is at most 300 parts by weight based on 100 parts by weight of the ethylene / butene / non-conjugated polyene copolymer.

The rubber composition of the present invention can extend the product life by using an anti-aging agent as in the case of a normal rubber composition.
Examples of the anti-aging agent include conventionally known anti-aging agents such as amine-based anti-aging agents, phenol-based anti-aging agents, and sulfur-based anti-aging agents. Specifically, aromatic secondary amine antioxidants such as phenylbutylamine and N, N′-di-2-naphthyl-p-phenylenediamine; dibutylhydroxytoluene and tetrakis [methylene (3,5-di-t Phenolic antioxidants such as -butyl-4-hydroxy) hydrocinnamate] methane; thioethers such as bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl] sulfide Anti-aging agent; dithiocarbamate anti-aging agent such as nickel dibutyldithiocarbamate; zinc salt of 2-mercaptobenzoylimidazole and 2-mercaptobenzimidazole; sulfur type such as dilaurylthiodipropionate and distearylthiodipropionate Such as anti-aging agents The These anti-aging agents may be used alone or in combination of two or more.

The blending amount of the antioxidant is usually 0.3 to 10 parts by weight with respect to 100 parts by weight of the ethylene / butene / non-conjugated polyene copolymer.
When the blending amount of the antioxidant is in the above range, there is no bloom on the surface of the resulting rubber composition, and it is preferable because vulcanization inhibition is not caused.

  As processing aids, those generally blended into rubber as processing aids can be widely used. Specific examples include ricinoleic acid, palmitic acid, lauric acid, stearic acid, stearates, barium stearate, zinc stearate, and calcium stearate. Of these, stearic acid is preferred.

The amount of the processing aid is usually 10 parts by weight or less with respect to 100 parts by weight of the ethylene / butene / non-conjugated polyene copolymer.
A blending amount of the processing aid within the above range is preferable because there is no bloom on the surface of the resulting rubber composition and vulcanization is not inhibited.

  Examples of the activator include amines such as di-n-butylamine, dicyclohexylamine, monoethanolamine, Acting B (trade name; manufactured by Yoshitake Pharmaceutical Co., Ltd.) and Acting SL (trade name; produced by Yoshitake Pharmaceutical Co., Ltd.); diethylene glycol, polyethylene glycol (Eg, PEG # 4000 (trade name; manufactured by Lion)), lecithin, triarylate melitrate and zinc compounds of aliphatic and aromatic carboxylic acids (eg, Struktol activator 73, Struktol IB 531 and Struktol FA 541 (trade name) Active agents such as Scill &Seilacher)); zinc peroxide preparations such as ZEONET ZP (trade name; manufactured by Nippon Zeon); octadecyltrimethylammonium bromide; synthetic hydrotalcite; special quaternary ammonium compounds (eg, Arcard 2HF) (Trade name; manufactured by Lion Akzo)) . Among these, polyethylene glycol (for example, PEG # 4000 (trade name; manufactured by Lion Corporation)) and Arcade 2HF are preferable. This activator may be used individually by 1 type, and may be used in combination of 2 or more types.

The compounding amount of the activator is usually 0.2 to 10 parts by weight with respect to 100 parts by weight of the ethylene / butene / non-conjugated polyene copolymer.
Examples of the hygroscopic agent include calcium oxide (for example, VESTA-18 (trade name; manufactured by Inoue Lime Industry Co., Ltd.), silica gel, sodium sulfate, molecular sieve, zeolite, white carbon, etc. Among these, calcium oxide is preferable. The hygroscopic agent can be appropriately selected depending on the application, and can be used alone or in combination of two or more.
The amount of the hygroscopic agent is usually 0.5 to 15 parts by weight with respect to 100 parts by weight of the ethylene / butene / non-conjugated polyene copolymer.

[Use]
The rubber composition of the present invention can be used for various applications. The rubber composition may be used for various purposes, but is usually obtained by crosslinking and foaming a crosslinked rubber obtained by crosslinking the rubber composition or the rubber composition. As a crosslinked foam, it is used for various applications.

[Crosslinked rubber]
The crosslinked rubber of the present invention can be obtained, for example, by crosslinking the rubber composition by the following two methods.

  In the first method, a rubber composition containing at least the ethylene / butene / non-conjugated polyene copolymer and a vulcanizing agent is usually used as an extruder, a calender roll, a press, an injection molding machine, a transfer molding machine, Pre-formed into a desired shape by various forming methods such as hot air, glass bead fluidized bed, UHF (ultra-high frequency electromagnetic wave), steam and heating baths such as LCM (hot molten salt bath), and simultaneously with or pre-forming This is a method (i) in which an object is introduced into a vulcanizing tank and heated.

  In the case of the method (i), the vulcanizing agent described above is used, and if necessary, a vulcanization accelerator and / or a vulcanization auxiliary is also used. Moreover, as temperature at the time of heating, it is 140-300 degreeC generally, Preferably it is 150-270 degreeC, and is heated for 0.5 to 30 minutes normally, Preferably it is 0.5 to 20 minutes.

When the rubber composition is molded and vulcanized, a mold may or may not be used. When no mold is used, the rubber composition is usually molded and vulcanized continuously.
The second method is a method (ii) in which the rubber composition is preformed by the molding method and irradiated with an electron beam.

  In the case of the method (ii), an electron beam of 0.1 to 10 MeV is irradiated on the preformed material so that the absorbed dose is, for example, 0.5 to 35 Mrad, preferably 0.5 to 20 Mrad.

(Crosslinked foam)
The crosslinked foam of the present invention is obtained by crosslinking and foaming the rubber composition.
In order to obtain the crosslinked foam, a rubber composition containing at least an ethylene / butene / non-conjugated polyene copolymer, a vulcanizing agent, and a foaming agent is crosslinked and foamed. When cross-linking and foaming, for example, the rubber composition is extruded into a die using an extruder equipped with a flat plate die, molded into a plate shape, and simultaneously introduced into a vulcanizing tank and heated. Thus, there is a method of crosslinking and foaming to obtain a plate-like sponge.

  The rubber composition can increase the expansion ratio. When the expansion ratio is large, the obtained crosslinked foam has a small specific gravity and is excellent in shape stability. For this reason, if the cross-linked foam of the present invention is used, a lightweight and flexible highly foamed sponge, heat insulating sponge, dam rubber and the like can be obtained with high productivity.

The crosslinked foam of the present invention is suitably used for automobile exterior materials such as glass run channels and weatherstrip sponges, and radiator hose materials.
The rubber composition, crosslinked rubber, and crosslinked foam of the present invention can be used in various fields. Specifically, automotive parts, marine parts, civil engineering and building parts, medical parts, parts for electrical and electronic equipment, transportation equipment and leisure parts, hoses (radiator hoses, heater hoses, etc.), anti-vibration rubber, It is suitably used for sheets, various belts, various packings, sealing materials, potting materials, coating materials and adhesives.

  Automotive parts include, for example, glass run channels, weatherstrip sponges, door opening trims, seal members, grommets, automotive engine gaskets, electrical components or oil filter sealing materials; igniter H I C or automotive hybrid I C potting Materials: Automotive body, automotive window glass, engine control board coating material; gaskets such as oil pans or timing belt covers, moldings, headlamp lenses, sunroof seals, mirror adhesives, and the like. Examples of weather strip sponges include door weather strips, trunk weather strips, luggage weather strips, roof side rail weather strips, sliding door weather strips, ventilator weather strips, sliding roof weather strips, front window weather strips, rear window weather strips, and quarters. Examples include window weather strips, lock pillar weather strips, door glass outer weather strips, and door glass inner weather strips.

Examples of marine components include wiring connection branch boxes, electrical system components or electric wire sealing materials; electric wires or glass adhesives, and the like.
Civil engineering building parts include, for example, joint joints for glass screens in commercial buildings, joints around glass with sashes, interior joints in toilets, washrooms or showcases, joints around bathtubs, and for prefabricated houses Sealant for building materials used for joints for outer wall expansion joints and sizing boards; Sealant for double-glazed glass; Sealant for civil engineering used for road repairs; Paints and adhesives for metal, glass, stone, slate, concrete or tile An adhesive sheet, a waterproof sheet or a vibration-proof sheet.

Examples of the medical part include a medical rubber stopper, a syringe gasket, and a decompression blood vessel rubber stopper.
Examples of parts for electrical / electronic equipment include heavy electrical parts, weak electrical parts, electrical / electronic equipment circuits and circuit board sealing materials, potting materials, coating materials or adhesives; electric wire covering repair materials; electric wire joint parts insulation Examples include sealing materials; rolls for OA equipment; vibration absorbers; grommets; or gel or capacitor encapsulating materials.

Examples of the parts for transport aircraft include automobiles, ships, airplanes, and railway vehicles.
Examples of leisure parts include swimming members such as swimming caps, diving masks, earplugs, and gel cushioning members such as sports shoes and baseball gloves.

  Anti-vibration rubber includes, for example, automotive anti-vibration rubber (engine mount, liquid seal engine mount, damper pulley, chain damper, carburetor mount, torsional damper, strut mount, rubber bush, bumper rubber, helper rubber, spring seat, Shock absorber, air spring, body mount, bumper guard, muffler support, rubber coupling, center bearing support, clutch rubber, differential mount, suspension bush, sliding bush, cushion strut bar, stopper, handle damper, radiator supporter or muffler hanger) Anti-vibration rubber for railways (slab mat, ballast mat or track mat), anti-vibration rubber for industrial machinery (expansion joint, flexible Joint, bush, mount), and the like.

Examples of the sheet include a roofing sheet and a water stop sheet.
Various belts include power transmission belts (V belts, flat belts, toothed belts, timing belts), transport belts (light transport belts, cylindrical belts, rough top belts, transport belts with flanges, transport with U-shaped guides) Belt, V-type guided conveyor belt) and the like.

  The sealing material is suitably used as a sealing material for, for example, a refrigerator, a freezer, a washing machine, a gas meter, a microwave oven, a steam iron, and an electric leakage breaker. The sealing material refers to a material to be sealed (sealed or sealed). Further, in various industries such as machinery, electricity, chemistry, etc., a material used for the purpose of watertightness and airtightness of the joint portion and the contact portion is also a broad meaning sealing material.

  The potting material is suitably used for potting, for example, a transformer high-voltage circuit, a printed circuit board, a high-voltage transformer with a variable resistance section, an electrical insulation component, a semiconductive component, a conductive component, a solar battery, or a television flyback transformer. .

  Examples of coating materials include various circuit elements such as high voltage thick film resistors or hybrid ICs; H IC, electrical insulation components; semiconductive components; conductive components; modules; printed circuits; ceramic substrates; Alternatively, it is suitably used for coating a buffer material such as a bonding wire; a semiconductive element; or an optical fiber for optical communication.

As the adhesive, for example, it is suitably used for bonding a cathode ray tube wedge, a neck, an electrically insulating component, a semiconductive component or a conductive component.
In addition to the above, the rubber composition, crosslinked rubber, and crosslinked foam of the present invention are used for automotive cup / sealant (master cylinder piston cup, wheel cylinder piston cup, constant velocity joint boot, pin boot, dust cover, piston seal, packing , O-rings, diaphragms, dam window shields, door mirror brackets, seal headlamps, seal cowl tops), industrial sealing materials (capacitor packing, O-rings, packings), foams (hose protection sponges, cushion sponges, heat insulation) Sponges, insulation pipes), coated electric wires, electric wire joints, electrical insulation parts, semiconductive rubber parts, OA equipment rolls (charging rolls, transfer rolls, developing rolls, paper feed rolls), industrial rolls (rolls for iron making, papermaking) Roll, printing wire low ), Anode cap, plug cap, ignition cable, lamp socket cover, terminal cover, wiper blade, various tubes (vacuum tube, tire tube), air spring, shoe sole, shoe heel, tire sidewall, fabric coating, etc. Is preferably used.

EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these.
The physical properties measured in the following examples and comparative examples were measured by the following methods.

[Melt flow rate (MFR)]
The MFR of the following copolymers (A1) and (A2) was determined according to ASTM D1238 at a temperature of 190 ° C. under a load of 2.16 kg.

[Mooney viscosity [ML (1 + 4) 100 ° C.]]
The Mooney viscosity [ML (1 + 4) 100 ° C.] of the following copolymers (A1) and (A2) and the following compound (Y) is measured according to JIS K 6300 using a Mooney viscometer (SMV202 type manufactured by Shimadzu Corporation). Measured in conformity.

[Density (kg / m ³ )]
The density of the following copolymers (A1) and (A2) was measured according to JIS K 7112 by a density gradient tube method.

[Intrinsic viscosity [η] (dl / g)]
The intrinsic viscosities of the following copolymers (A1) and (A2) were measured using a fully automatic intrinsic viscometer manufactured by Rouai Co., Ltd. at a temperature of 135 ° C. and a measurement solvent decalin.

[Glass transition temperature (Tg) (° C)]
The glass transition temperatures of the following copolymers (A1) and (A2) were measured with RDC220 manufactured by SII.

[ ¹ H-NMR spectrum]
¹ H-NMR spectra of the following copolymers (A1) and (A2) are obtained under the following conditions. The amount of structural units derived from ethylene, the amount of structural units derived from butene, and the structure derived from ENB in each polymer The unit amount was determined from the integrated intensity of the ¹ H-NMR spectrum.
Apparatus: ECX400P type nuclear magnetic resonance apparatus (manufactured by JEOL Ltd.)
Measurement conditions Frequency: 400MHz
Pulse width: 6.00 μsec (45 °)
Repeat time: 7.0 seconds Integration count: 512 times Measurement solvent: ODCB-d ₄
Measurement temperature: 120 ° C

[Minimum viscosity (Vm) and scorch time (t5, min)]
The minimum viscosity (Vm) and scorch time of the following rubber compositions (X) and (Z) were measured according to JIS K6300. Specifically, using a Mooney viscometer (SMV202 type manufactured by Shimadzu Corporation), the change in Mooney viscosity is measured at 125 ° C. to determine the minimum viscosity (Vm), and the minimum viscosity Vm The time until the point was raised by 5 points was determined, and this was defined as the scorch time (t5, min).

〔hardness〕
The hardness of the following crosslinked rubber was measured with Type A Durometer.
[Tensile breaking stress and tensile breaking elongation]
The tensile strength at break (TB) and the elongation at break (EB) of the following crosslinked rubber were measured by performing a tensile test in accordance with JIS K6251 at a measurement temperature of 23 ° C. and a tensile speed of 500 mm / min.

(Compression set)
As a compression set of the following crosslinked rubber, a sample was extracted from the rubber molded body in accordance with JIS K6250 6.5, treated at 100 ° C. for 22 hours, and treated at −20 ° C. for 22 hours according to JIS K6262 (1997). The compression set after the treatment at 150 ° C. for 72 hours or after the treatment at 70 ° C. for 22 hours was measured.

[Example 1]
(Production of copolymer (A1))
A terpolymer composed of ethylene, butene, and 5-ethylidene-2-norbornene (ENB) was continuously polymerized at a temperature of 95 ° C. using a polymerization vessel equipped with a stirring blade having a volume of 300 liters.

  As a polymerization solvent, hexane is fed at a feed rate of 27 kg / h, ethylene is fed at a feed rate of 6.0 kg / h, butene is fed at a feed rate of 3.3 kg / h, ENB is fed at a feed rate of 860 g / h, hydrogen is fed at a feed rate of 28 normal liters / h, The polymerizer was continuously fed.

(T-Butylamido) dimethyl (η ⁵ -2-methyl-s-indacene-1) is a catalyst having a structure represented by the above formula (II) as a main catalyst while maintaining the polymerization pressure at 1.6 MPa-G. -Il) Silane Titanium (II) 1,3-pentadiene was continuously fed to the polymerization vessel so that the feed amount was 0.035 mmol / h. (C ₆ H ₅ ) ₃ CB (C ₆ F ₅ ) ₄ is 0.18 mmol / h as a cocatalyst and triisobutylaluminum (TIBA) is 10 mmol / h as an organoaluminum compound. Supplied.

Thus, a polymerization solution containing 17.5% by weight of a copolymer (A1) composed of ethylene, butene, and ENB was obtained. The obtained polymerization solution was poured into a large amount of methanol to precipitate a copolymer (A1) composed of ethylene, butene, and ENB, and then dried under reduced pressure at 80 ° C. for 24 hours.
Table 1 shows the physical properties of the obtained copolymer (A1).

[Example 2]
(Production of copolymer (A2))
A terpolymer composed of ethylene, butene, and 5-ethylidene-2-norbornene (ENB) was continuously polymerized at a temperature of 95 ° C. using a polymerization vessel equipped with a stirring blade having a volume of 300 liters.

  As a polymerization solvent, hexane is fed at a feed rate of 27 kg / h, ethylene is fed at a feed rate of 6.0 kg / h, butene is fed at a feed rate of 3.3 kg / h, ENB is fed at a feed rate of 860 g / h, hydrogen is fed at a feed rate of 15 normal liters / h, The polymerizer was continuously fed.

(T-Butylamido) dimethyl (η ⁵ -2-methyl-s-indacene-1) is a catalyst having a structure represented by the above formula (II) as a main catalyst while maintaining the polymerization pressure at 1.6 MPa-G. -Il) Silane Titanium (II) 1,3-pentadiene was continuously fed to the polymerization vessel so that the feed amount was 0.035 mmol / h. (C ₆ H ₅ ) ₃ CB (C ₆ F ₅ ) ₄ is 0.18 mmol / h as a cocatalyst and triisobutylaluminum (TIBA) is 10 mmol / h as an organoaluminum compound. Supplied.

  Thus, a polymerization solution containing 16.7% by weight of a copolymer (A2) composed of ethylene, butene, and ENB was obtained. The obtained polymerization solution was put into a large amount of methanol to precipitate a copolymer (A2) composed of ethylene, butene, and ENB, and then dried under reduced pressure at 80 ° C. for 24 hours.

  Table 1 shows the physical properties of the obtained copolymer (A2).

〔実施例３〕
ＭＩＸＴＲＯＮ ＢＢ ＭＩＸＥＲ（神戸製鋼所社製、 ＢＢ−２型、容積１．７リットル）を用いて、実施例１で得られた共重合体（Ａ１）を１００重量部、加硫助剤として酸化亜鉛を５重量部、加工助剤としてステアリン酸を１重量部、補強剤として「旭♯６０Ｇ」（商品名）（旭カーボン社製）を１００重量部、軟化剤として「ダイアナプロセスオイル ＰＷ−３８０」（商品名）（出光興産社製）を３０重量部配合して混連した。混連条件は、ローター回転数を前方７６．８ｒｐｍおよび後方６８．３ｒｐｍ、フローティングウェイト圧力３ｋｇ／ｃｍ²、混連時間５分間であり、混連排出温度は１５０℃であった。

Example 3
100 parts by weight of the copolymer (A1) obtained in Example 1 using MIXRON BB MIXER (manufactured by Kobe Steel, BB-2 type, volume 1.7 liters) as a vulcanization aid, zinc oxide 5 parts by weight, stearic acid 1 part by weight as a processing aid, "Asahi # 60G" (trade name) (manufactured by Asahi Carbon Co., Ltd.) as a reinforcing agent, and "Diana Process Oil PW-380" as a softening agent 30 parts by weight (trade name) (made by Idemitsu Kosan Co., Ltd.) was blended and mixed. The mixing conditions were a rotor rotational speed of 76.8 rpm forward and 68.3 rpm backward, a floating weight pressure of 3 kg / cm ² , a mixing time of 5 minutes, and a mixed discharge temperature of 150 ° C.

  Next, 1.0 part by weight of "Sunseller DM" (trade name) (manufactured by Sanshin Chemical Industry) as a vulcanization accelerator and "Sunseller BZ" (trade name) (manufactured by Sanshin Chemical Industry Co., Ltd.) ) 0.5 parts by weight, “Sunseller TRA” (trade name) (manufactured by Sanshin Chemical Industry Co., Ltd.) 0.5 parts by weight and 1.0 part by weight of sulfur as a vulcanizing agent, After mixing for 10 minutes at a gap of 2 mm and a roll surface temperature of 60 ° C. to obtain a rubber composition (X), it was molded into a sheet.

The obtained sheet was filled in a press die (length 150 mm × width 150 mm × thickness 2 mm) and crosslinked by heating at a temperature of 100 t and 170 ° C. for 10 minutes to obtain a crosslinked rubber.
Table 2 shows the physical properties of the crosslinked rubber.

Example 4
A crosslinked rubber was obtained in the same manner as in Example 3 except that the copolymer (A1) was replaced with the copolymer (A2).
Table 2 shows the physical properties of the crosslinked rubber.

[Comparative Example 1]
Copolymer (A1) is converted into copolymer (B) (ethylene / propylene / ENB copolymer, 67.2% by weight of structural units derived from ethylene, 27.7% by weight of structural units derived from propylene, ENB A crosslinked rubber was obtained in the same manner as in Example 3, except that the derived structural unit was 5.1% by weight and the Mooney viscosity [ML (1 + 4) 125 ° C.] 22) was used.

  Table 2 shows the physical properties of the crosslinked rubber.

表２より、実施例３、４で得られた架橋ゴムは、比較例１で得られた架橋ゴムと比べて、硬度、引張破断点応力（ＴＢ）、引張破断点伸び（ＥＢ）等の成形体の強度に関する物性が良好であり、また、圧縮永久歪も小さかった。すなわち共重合体（Ａ１）および（Ａ２）は、高い強度が求められる分野に使用することが可能である。

From Table 2, the crosslinked rubber obtained in Examples 3 and 4 is molded with hardness, tensile breaking stress (TB), tensile breaking elongation (EB), etc., compared with the crosslinked rubber obtained in Comparative Example 1. The physical properties relating to the strength of the body were good, and the compression set was small. That is, the copolymers (A1) and (A2) can be used in fields where high strength is required.

Example 5
30 parts by weight of the copolymer (A1) obtained in Example 1 and “Mitsui EPT4045M” (trade name) using MIXTRON BB MIXER (manufactured by Kobe Steel, BB-2 type, volume 1.7 liters) ) (Mitsui Chemicals Co., Ltd.) (45% by weight of structural units derived from ethylene, 47.4% by weight of structural units derived from propylene, 7.6% by weight of structural units derived from ENB, Mooney viscosity [ML (1 + 4) 100 [° C] 45) 70 parts by weight, 5 parts by weight of zinc oxide as a vulcanization aid, 1 part by weight of stearic acid as a processing aid, and “PEG # 4000” (trade name) (manufactured by Lion) as an activator 2 parts by weight, 100 parts by weight of “MISTORON VAPOR” (trade name) (manufactured by Nippon Mystron) as an inorganic filler, and “Diana Process Oil PW-380” (trade name) (as a softener) And kneading by an optical Kosan Co., Ltd.) were blended 20 parts by weight. The mixing conditions were a rotor rotational speed of 76.8 rpm forward and 68.3 rpm backward, a floating weight pressure of 3 kg / cm ² , a mixing time of 5 minutes, and a mixed discharge temperature of 150 ° C.

  Next, 6.8 parts by weight of dicumyl peroxide (DCP-40C) as an organic peroxide and 2 parts by weight of triallyl isocyanurate (TAIC) as a vulcanization aid are blended into the resulting blend (Y). The mixture was mixed with a 6-inch roll at a roll gap of 2 mm and a roll surface temperature of 60 ° C. for 10 minutes, and then formed into a sheet shape.

The obtained sheet was filled in a press die (length 150 mm × width 150 mm × thickness 2 mm), and crosslinked by heating at a temperature of 100 t and 170 ° C. for 20 minutes to obtain a crosslinked rubber.
Table 3 shows the physical properties of the crosslinked rubber.

Example 6
A crosslinked rubber was obtained in the same manner as in Example 5 except that the copolymer (A1) was replaced with the copolymer (A2).
Table 3 shows the physical properties of the crosslinked rubber.

[Comparative Example 2]
Copolymer (A1) is converted into copolymer (B) (ethylene / propylene / ENB copolymer, 67.2% by weight of structural units derived from ethylene, 27.7% by weight of structural units derived from propylene, ENB A crosslinked rubber was obtained in the same manner as in Example 5 except that the derived structural unit was 5.1% by weight and the Mooney viscosity [ML (1 + 4) 125 ° C.] 22) was used.

  Table 3 shows the physical properties of the crosslinked rubber.

表３より、実施例５、６で得られた架橋ゴムは、比較例２で得られた架橋ゴムと比べて、引張破断点応力（ＴＢ）が良好であった。すなわち共重合体（Ａ１）および（Ａ２）は、共重合体（Ｂ）よりも優れた樹脂改質性能を有する。

From Table 3, the crosslinked rubbers obtained in Examples 5 and 6 had better tensile breaking stress (TB) than the crosslinked rubber obtained in Comparative Example 2. That is, the copolymers (A1) and (A2) have better resin modification performance than the copolymer (B).

Example 7
20 parts by weight of the copolymer (A1) obtained in Example 1 and “Mitsui EPT4045M” (trade name) using MIXTRON BB MIXER (manufactured by Kobe Steel, BB-2 type, volume 1.7 liters) ) (Mitsui Chemicals Co., Ltd.) (45% by weight of structural units derived from ethylene, 47.4% by weight of structural units derived from propylene, 7.6% by weight of structural units derived from ENB, Mooney viscosity [ML (1 + 4) 100 [° C] 45) 80 parts by weight, "META-Z102" (trade name) (manufactured by Inoue Lime Industry Co., Ltd.) as a vulcanization aid, 5 parts by weight of stearic acid as a processing aid, and " 125 parts by weight of “Asahi # 60G” (trade name) (manufactured by Asahi Carbon Co., Ltd.) and 47 parts by weight of “Diana Process Oil PW-100” (trade name) (manufactured by Idemitsu Kosan Co., Ltd.) as a softener were mixed together. . The mixing conditions were a rotor rotational speed of 76.8 rpm forward and 68.3 rpm backward, a floating weight pressure of 3 kg / cm ² , a mixing time of 5 minutes, and a mixed discharge temperature of 150 ° C.

  Next, 0.5 parts by weight of "Sunseller DM" (trade name) (manufactured by Sanshin Chemical Industry) as a vulcanization accelerator and "Sunseller TBT" (trade name) (manufactured by Sanshin Chemical Industry Co., Ltd.) ) 0.5 parts by weight, “Sunseller BZ” (trade name) (manufactured by Sanshin Chemical Industries) 1.0 part by weight, “Sunseller 22-C” (trade name) (manufactured by Sanshin Chemical Industries) 1. 0 part by weight, 1.0 part by weight of sulfur as a vulcanizing agent, and 5 parts by weight of “VESTA-18” (trade name) (manufactured by Inoue Lime Industry Co., Ltd.) as a hygroscopic agent are blended, and a roll gap is obtained by a 6-inch roll. After mixing for 2 minutes at a roll surface temperature of 60 ° C. for 10 minutes to obtain a rubber composition (Z), it was molded into a sheet.

The obtained sheet was filled in a press die (length 150 mm × width 150 mm × thickness 2 mm), and crosslinked by heating at a temperature of 100 t and 170 ° C. for 20 minutes to obtain a crosslinked rubber.
Table 4 shows the physical properties of the crosslinked rubber.

Example 8
A crosslinked rubber was obtained in the same manner as in Example 7 except that the copolymer (A1) was replaced with the copolymer (A2).
Table 4 shows the physical properties of the crosslinked rubber.

[Comparative Example 3]
Copolymer (A1) is converted into copolymer (B) (ethylene / propylene / ENB copolymer, 67.2% by weight of structural units derived from ethylene, 27.7% by weight of structural units derived from propylene, ENB A crosslinked rubber was obtained in the same manner as in Example 7 except that the derived structural unit was 5.1% by weight and the Mooney viscosity [ML (1 + 4) 125 ° C.] 22) was used.

  Table 4 shows the physical properties of the crosslinked rubber.

表４より、実施例７、８で得られた架橋ゴムは、比較例３で得られた架橋ゴムと比べて、引張破断点応力（ＴＢ）が良好であった。すなわち共重合体（Ａ１）および（Ａ２）は、共重合体（Ｂ）よりも優れた樹脂改質性能を有する。

From Table 4, the crosslinked rubbers obtained in Examples 7 and 8 had better tensile break stress (TB) than the crosslinked rubber obtained in Comparative Example 3. That is, the copolymers (A1) and (A2) have better resin modification performance than the copolymer (B).

Claims (6)

An ethylene / butene / non-conjugated polyene copolymer synthesized using a catalyst having a structure represented by the following formula (I).

(In the formula (I), R ′ and R ″ are each independently a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, M is titanium, Y is —NR ^* —, and Z ^* is -SiR ^* _2- , wherein each R ^* is independently a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, one of p and q is 0, and the other is 1.
when p is 0 and q is 1, M is in the +2 oxidation state, X ′ is 1,4-diphenyl-1,3-butadiene or 1,3-pentadiene;
When p is 1 and q is 0, M is in the +3 oxidation state and X is 2- (N, N-dimethylamino) benzyl. )   50 to 95 mol% of structural units derived from ethylene, 4.9 to 49.9 mol% of structural units derived from butene, and 0.1 to 5 mol% of structural units derived from non-conjugated polyene (provided that 2. The ethylene / butene / nonconjugated polyene copolymer according to claim 1, which contains 100 mol% of a total of structural units derived from ethylene, structural units derived from butene, and structural units derived from nonconjugated polyene. .   The ethylene butene according to claim 1 or 2, wherein the non-conjugated polyene is at least one non-conjugated polyene selected from 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB). -Non-conjugated polyene copolymer.   A rubber composition comprising the ethylene / butene / non-conjugated polyene copolymer according to claim 1.   A crosslinked rubber obtained by crosslinking the rubber composition according to claim 4.   A cross-linked foam obtained by cross-linking and foaming the rubber composition according to claim 4.