JP2016030810A - Composition, crosslinked body and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition containing EPDM capable of providing a crosslinked body excellent in mechanical properties such as hardness.SOLUTION: There is provided a composition which comprises: an ethylene-α-olefin-nonconjugated polyene copolymer (A); at least one ethylenic copolymer (B) selected from an ethylene-α-olefin copolymer (B-1) and a modified ethylene-α-olefin copolymer (B-2); and an inorganic filler (C) having a polar group (provided that a carbon-based inorganic filler is excluded as an inorganic filler (C) having a polar group), where the mass ratio between (A) and (B) is 95:5 to 50:50 and 80 to 200 pts.mass of the filler (C) is contained based on the total 100 pts.mass of (A) and (B).SELECTED DRAWING: None

Description

  The present invention relates to a composition, a crosslinked product, and a use, and more particularly to a composition, a crosslinked product obtained by crosslinking the composition, and a use of the crosslinked product.

  Ethylene / α-olefin / non-conjugated polyene copolymer rubber represented by ethylene / propylene / diene copolymer rubber is excellent in strength properties, heat aging resistance, weather resistance, etc. Widely used in applications such as electrical insulation and civil engineering materials.

  In addition, in the case of imparting flame retardancy, generally known is a non-halogen flame retardant rubber in which a flame retardant filler such as aluminum hydroxide is added to an ethylene / α-olefin / non-conjugated polyene copolymer rubber. .

  For example, an abrasion-resistant flame-retardant resin composition containing ethylene propylene rubber, ethylene-vinyl acetate copolymer, maleic acid-modified linear low density polyethylene, aluminum hydroxide and a crosslinking agent is known (for example, Patent Document 1).

  Further, as another example in which aluminum hydroxide is blended with EPDM, rubber compositions containing EPDM, aluminum hydroxide, decabromodiphenyl ether and ammonium polyphosphate, EPDM, aluminum hydroxide, chlorinated paraffin, three A rubber composition containing antimony oxide is known as a rubber composition having both wear resistance and flame resistance (see, for example, Patent Document 2).

  The wear-resistant flame-retardant resin composition disclosed in Patent Document 1 and the rubber composition disclosed in Patent Document 2 are disclosed to be excellent in flame retardancy and wear resistance. Improvement was still desired from the viewpoint.

JP 2012-82277 A JP 2006-176659 A

  Since the ethylene / α-olefin / non-conjugated polyene copolymer rubber itself has no flame retardancy, it is necessary to add a large amount of a flame retardant to impart flame retardancy. However, since flame retardants generally do not have reinforcing properties, there is a problem that mechanical properties such as hardness decrease and the crosslinking density does not increase as the addition amount increases.

  As a result of intensive studies to solve the above problems, the present inventors have found that ethylene / α-olefin / non-conjugated polyene copolymer rubber, a specific (modified) ethylene / α-olefin copolymer, and polarity The present inventors have found that a crosslinked product obtained by crosslinking a composition containing a specific amount of an inorganic filler having a group is excellent in mechanical properties such as hardness and has a high crosslinking density, thereby completing the present invention.

  That is, the composition of the present invention comprises an ethylene / α-olefin / nonconjugated polyene copolymer rubber (A) composed of ethylene, an α-olefin having 3 to 20 carbon atoms and a nonconjugated polyene, ethylene, and carbon 3 By modifying the ethylene / α-olefin copolymer (B-1) composed of ˜20 α-olefin and the ethylene / α-olefin copolymer (B-1) with a compound containing a polar group At least one ethylene copolymer (B) selected from the resulting modified ethylene / α-olefin copolymer (B-2) and an inorganic filler (C) having a polar group (however, an inorganic having a polar group) The filler (C) includes a carbon-based inorganic filler having a polar group), and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and the ethylene copolymer. The mass ratio [(A) / (B)] to the body (B) is 95/5 to 50/50, and the ethylene / α-olefin / nonconjugated polyene copolymer rubber (A) and the ethylene copolymer are 80-200 mass parts of said fillers (C) are included with respect to 100 mass parts of total amounts with a polymer (B).

The composition of the present invention preferably contains substantially no ethylene-vinyl acetate copolymer.
The ethylene copolymer (B) has (i) a density of 0.840 to 0.920 g / cm ³ , and (ii) a melt flow rate (MFR) at 190 ° C. and 2.16 kg of 0.1 to 0.1. It is preferable that it is 50 g / 10min.

The ethylene / α-olefin copolymer (B) preferably contains 1-butene as the α-olefin having 3 to 20 carbon atoms.
It is preferable that the ethylene copolymer (B) is the modified ethylene / α-olefin copolymer (B-2).

  The filler (C) preferably contains a metal hydroxide, and more preferably contains at least one metal hydroxide selected from aluminum hydroxide and magnesium hydroxide.

  The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) has (i) a molar ratio of ethylene to an α-olefin having 3 to 20 carbon atoms (ethylene / α-olefin) of 50/50 to 90. / 10, (ii) the iodine value is 1 to 50 g / 100 g, and (iii) the intrinsic viscosity [η] measured in decalin at 135 ° C. is preferably 0.5 to 7.0 dl / g. .

The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) preferably contains 5-ethylidene-2-norbornene as the non-conjugated polyene.
The composition of the present invention preferably further contains a crosslinking agent.

The crosslinked product of the present invention is obtained by crosslinking the composition.
The laminated body of this invention has a layer formed from the said crosslinked body.
The railway vehicle component of the present invention is obtained from the cross-linked body or the laminated body.
The hood for a railway vehicle of the present invention is obtained from the cross-linked body or the laminated body.

  A crosslinked product obtained by crosslinking the composition of the present invention has a high crosslinking density and excellent mechanical properties such as hardness.

Next, the present invention will be specifically described.
The composition of the present invention comprises an ethylene / α-olefin / nonconjugated polyene copolymer rubber (A) composed of ethylene, an α-olefin having 3 to 20 carbon atoms, and a nonconjugated polyene, ethylene, and 3 to 20 carbon atoms. It can be obtained by modifying the ethylene / α-olefin copolymer (B-1) comprising the α-olefin and a compound containing a polar group with the ethylene / α-olefin copolymer (B-1). At least one ethylene-based copolymer (B) selected from the modified ethylene / α-olefin copolymer (B-2) and an inorganic filler (C) having a polar group (however, an inorganic filler having a polar group ( C), excluding carbon-based inorganic fillers having polar groups), and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and the ethylene copolymer (B). The mass ratio [(A) / (B)] is 95/5 to 50/50, and the ethylene / α-olefin / nonconjugated polyene copolymer rubber (A) and the ethylene copolymer (B). The filler (C) is included in an amount of 80 to 200 parts by mass with respect to 100 parts by mass in total.

  The composition of the present invention comprises an ethylene / α-olefin / non-conjugated polyene copolymer rubber (A), an ethylene copolymer (B), and an inorganic filler (C) having a polar group. The composition of the present invention contains not only an ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) but also an ethylene copolymer (B), thereby containing an inorganic filler (C) having a polar group. In spite of the inclusion, a crosslinked product having excellent mechanical properties such as strength can be obtained.

  The present inventor presumed that the cross-linked product obtained by cross-linking the composition of the present invention is excellent in mechanical properties such as strength because the cross-linked product has a high cross-linking density. Although the reason why the cross-linked product obtained by cross-linking the composition of the present invention has a high cross-linking density is not clear, the present inventors have good dispersibility of each component during kneading with the ethylene-based copolymer (B). By using an inorganic filler (C) having a polar group as a filler, the polar group contributes to the formation of some network-like structure by physical interaction such as hydrogen bonding. Presumed to be.

(Ethylene / α-olefin / non-conjugated polyene copolymer rubber (A))
The composition of the present invention contains an ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) comprising ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene. The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) is also simply referred to as copolymer rubber (A).

The copolymer rubber (A) is a copolymer rubber having a structural unit derived from ethylene, a structural unit derived from an α-olefin having 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene.
In the composition of the present invention, the copolymer rubber (A) is used alone or in combination of two or more.

  Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1- Decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyl-1-decene, 11-methyl- Examples include 1-dodecene and 12-ethyl-1-tetradecene.

  The α-olefin having 3 to 20 carbon atoms is preferably propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene, and particularly preferably propylene.

The said C3-C20 alpha olefin is used individually or in combination of 2 or more types.
Specific examples of the non-conjugated polyene include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5 Chain non-conjugated dienes such as dimethyl-1,4-hexadiene and 7-methyl-1,6-octadiene; methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropyl Liden-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2 -Cyclic non-conjugated dienes such as norbornene, cyclopentadiene and norbornadiene; 8-methyl-4- Tylidene-1,7-nonadiene, 4-ethylidene-1,7-undecadiene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2 -Triborns such as norbornadiene and 4-ethylidene-8-methyl-1,7-nonadiene. Of these, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene are preferable.

These non-conjugated polyenes are used alone or in combination of two or more.
Examples of the copolymer rubber (A) include an ethylene / propylene / 5-ethylidene-2-norbornene random copolymer and an ethylene / propylene / 5-ethylidene-2-norbornene / 5-vinyl-2-norbornene random copolymer. Etc. can be illustrated.

  The copolymer rubber (A) is a molar ratio of ethylene to an α-olefin having 3 to 20 carbon atoms (ethylene / α-olefin), in other words, a structural unit derived from ethylene and an α olefin having 3 to 20 carbon atoms. The molar ratio with the derived structural unit is usually 50/50 to 90/10, preferably 50/50 to 85/15.

Further, the structural unit derived from non-conjugated polyene is usually contained in an amount of 1.0 to 25.0 wt%, preferably 3.0 to 20 wt%, more preferably 4.0 to 15 wt%.
The iodine value of the copolymer rubber (A) is preferably 1 to 50 g / 100 g, more preferably 3.0 to 40.0 g / 100 g, and further preferably 5.0 to 35.0 g / 100 g. It is. It is preferable for the iodine value to be in the above range because a crosslinked product having a high crosslinking density can be obtained, and the hardness of the crosslinked product can be increased.

The iodine value can be measured by the method described in the examples.
The copolymer rubber (A) usually has an intrinsic viscosity [η] measured in decalin at 135 ° C., preferably 0.5 to 7.0 dl / g, more preferably 1.0 to 5. It is 0 dl / g, More preferably, it is 1.0-4.0 dl / g. It is preferable that the intrinsic viscosity is within the above range because the balance between physical properties and workability is good.

The intrinsic viscosity can be measured by the method described in the examples.
As the copolymer rubber (A), commercially available rubber may be used, or a polymer obtained by synthesis may be used.

  The method of synthesizing the copolymer rubber (A) is not particularly limited, but a method of synthesizing using a metallocene catalyst is preferable from the viewpoint that a polymer satisfying the physical properties can be easily obtained.

An example of a method for synthesizing the copolymer rubber (A) using a metallocene catalyst is shown below.
The copolymer rubber (A) can be obtained by polymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene using the following metallocene catalyst.

  The metallocene catalyst has, for example, a structure represented by the following formula (α) or (β), preferably a structure represented by the following general formula (i), more preferably the following formulas (ii), (iii) ), (Iv), (v) or (vi). Among these, a metallocene catalyst having a structure represented by (iii) is particularly preferable.

（式（α）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子または炭素数１〜６のアルキル基であり、Ｒ¹およびＲ²の少なくとも１つは水素原子ではない。

(In Formula (α), R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and at least one of R ¹ and R ² is not a hydrogen atom.

R ^{3 to} R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ^{1 to} R ⁶ may be bonded to each other to form a ring.
M is titanium.

Y is -O-, -S-, -NR ^* -, -PR ^* -.
Z ^{* _{is, SiR * 2, CR * 2}} , SiR * 2 SiR * 2, CR * 2 CR * 2, CR * = CR *, a CR ^* ₂ SiR ^* _2, or GeR ^* _2.

Each R ^* is independently a hydrogen atom, a hydrocarbyl group, a hydrocarbyloxy group, a silyl group, a halogenated alkyl group, or a halogenated aryl group, and when R ^* is not hydrogen, R ^* is up to 20 It has atoms other than hydrogen atoms. May be two R where Z has ^* (when R ^* is not hydrogen atom) may form a ring, R ^* may form a ring having the R ^* and Y having the Z ^*.

p is 0, 1 or 2.
q is zero or one.
However, when p is 2, q is zero, M is in the +4 oxidation state, and each X is independently methyl or benzyl.

  When p is 1, q is zero, M is in the +3 oxidation state, X is 2- (N, N-dimethyl) aminobenzyl, or M is in the +4 oxidation state, and X is 1,3-butadienyl.

  When p is 0, q is 1, M is a formal oxidation state of +2, and X ′ is 1,4-diphenyl-1,3-butadiene, 2,4-hexadiene, or 1,3-pentadiene. It is. )

（式（β）中、Ｒは、それぞれ独立に、ヒドロカルビル、ハロヒドロカルビル、シリル、ゲルミルおよびこれらの組み合わせから選択される基または水素原子であり、該基が含有する水素原子以外の原子の数は２０個以下である。

(In the formula (β), each R is independently a group or hydrogen atom selected from hydrocarbyl, halohydrocarbyl, silyl, germyl and combinations thereof, and the number of atoms other than hydrogen atoms contained in the group is 20 or less.

M is titanium, zirconium or hafnium.
Y is -O-, -S-, -NR ^* -or -PR ^* -.
R ^* is a hydrogen atom, hydrocarbyl group, hydrocarbyloxy group, silyl group, halogenated alkyl group or halogenated aryl group, and when R ^* is not hydrogen, R ^* represents up to 20 non-hydrogen atoms. contains.

Z is a divalent group containing boron or a group 14 element and containing nitrogen, phosphorus, sulfur or oxygen, and the divalent group has 60 or less atoms other than hydrogen atoms. is there.
X is independently an anionic ligand having 60 or less atoms (excluding a cyclic ligand having a delocalized π bond) when a plurality of X are present.

X ′ is a neutral linking compound having 20 or less atoms.
p is 0, 1 or 2;
q is 0 or 1.

  However, when p is 2 and q is 0, M is in the +4 oxidation state, X is halide, hydrocarbyl, hydrocarbyloxy, di (hydrocarbyl) amide, di (hydrocarbyl) phosphide, hydrocarbyl sulfide, silyl group, An anionic ligand selected from a halo-substituted derivative, a di (hydrocarbyl) amino-substituted derivative, a hydrocarbyloxy-substituted derivative and a di (hydrocarbyl) phosphino-substituted derivative, wherein the number of atoms other than the hydrogen atom of X is 20 or less It is.

  When p is 1 and q is 0, M is in the +3 oxidation state and X is selected from allyl, 2- (N, N-dimethylaminomethyl) phenyl and 2- (N, N-dimethyl) aminobenzyl. Or M is in the +4 oxidation state and X is a divalent derivative of a conjugated diene, and M and X together form a metallocyclopentene group.

  And when p is 0 and q is 1, M is in the +2 oxidation state, X ′ is a neutral conjugated or non-conjugated diene optionally substituted with one or more hydrocarbyl groups; Has no more than 40 carbon atoms and forms a π complex with M. )

式（ｉ）中、Ｒ' は、水素原子、ヒドロカルビル基、ジ（ヒドロカルビルアミノ）基またはヒドロカルビレンアミノ基を表し、それらの基は２０までの炭素原子を有する。

In formula (i), R ′ represents a hydrogen atom, a hydrocarbyl group, a di (hydrocarbylamino) group or a hydrocarbyleneamino group, which groups have up to 20 carbon atoms.

R ″ represents a hydrocarbyl group having 1 to 20 carbon atoms or a hydrogen atom.
M represents titanium.
Y is, -O -, - S -, - NR * -, - PR * -, - NR 2 * or -PR ₂ ^* (provided that when Y is -NR ₂ ^*, or -PR ₂ ^*, M- Y bond is a coordination bond.

Z ^{* _{is, -SiR * 2 -, - CR}} * 2 -, - SiR * 2 SiR * 2 -, - CR * 2 CR * 2 -, - CR * = CR * -, - CR * 2 SiR * 2 - Or -GeR ^* _2- .
R ^* each independently represents a hydrogen atom or at least one group selected from the group consisting of a hydrocarbyl group, a hydrocarbyloxy group, a silyl group, a halogenated alkyl group, and a halogenated aryl group. represents the R ^* may contain atoms up to atomic number 2 to 20, Z ^* 2 one R ^* which has (when R ^* is not hydrogen) is optionally may form a ring, Z ^* is a is R ^* having R ^* and Y have, may form a optionally ring.

X represents a monovalent anionic ligand group having atoms up to 60 atoms excluding the class of ligands that are cyclic delocalized π-bonded ligand groups.
X ′ represents a neutral linking group having an atom having up to 20 atoms.

X ″ represents a divalent anionic ligand group having an atom having up to 60 atoms.
p represents 0, 1 or 2, q represents 0 or 1, and r represents 0 or 1.
However, when p is 2, q and r are 0 and M is in the +4 oxidation state (or when Y represents -NR ^* ₂ or -PR ^* ₂ , M is in the +3 oxidation state) X) is a halide group, hydrocarbyl group, hydrocarbyloxy group, di (hydrocarbyl) amide group, di (hydrocarbyl) phosphide group, hydrocarbyl sulfide group and silyl group, groups in which these groups are halogen-substituted, these groups Represents an anionic ligand selected from di (hydrocarbyl) amino substituted groups, groups in which these groups are hydrocarbyloxy substituted, and groups in which these groups are di (hydrocarbyl) phosphino substituted, and up to 30 It has atoms other than hydrogen atoms.

  However, when r is 1, p and q represent 0, M is an oxidation state of +4, and X ″ is selected from the group consisting of a hydrocarbazyl group, an oxyhydrocarbyl group, and a hydrocarbylene dioxy group. And has atoms other than hydrogen atoms up to 30 atoms.

  However, when p is 1, q and r represent 0, M is an oxidation state of +3, X is allyl, 2- (N, N-dimethylamino) phenyl, 2- (N, N- Represents a stabilizing anionic ligand group selected from the group consisting of (dimethylaminomethyl) phenyl and 2- (N, N-dimethylamino) benzyl.

Provided that when p and r are 0, q represents 1, M is an oxidation state of +2, and X ′ is a neutral conjugated diene or neutral, optionally substituted with one or more hydrocarbyl groups Wherein X ′ has a carbon atom having up to 40 atoms and forms a π-complex with M. )
In the general formula (i), any one of the following (1) to (4) is preferable.

(1) p is 2, q and r are 0, M is an oxidation state of +4, and X independently represents methyl, benzyl or halide.
(2) p and q are 0, r is 1, M is a +4 oxidation state, and X ″ represents a 1,4-butadienyl group that forms a metallocyclopentene ring with M.

(3) p is 1, q and r are 0, M is an oxidation state of +3, and X represents 2- (N, N-dimethylamino) benzyl.
(4) p and r are 0, q represents 1, M is an oxidation state of +2, and X ′ represents 1,4-diphenyl-1,3-butadiene or 1,3-pentadiene.

  In any of the above embodiments (1) to (4), R ″ more preferably represents a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

上記式（ｉｉ）は、（ｔ−ブチルアミド）ジメチル（η⁵−２−メチル−ｓ−インダセン−１−イル）シランチタニウム（ＩＩ）２，４−ヘキサジエンである。

The above formula (ii) is (t-butylamido) dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silane titanium (II) 2,4-hexadiene.

上記式（ｉｉｉ）は、（ｔ−ブチルアミド）−ジメチル（η⁵−２−メチル−ｓ−インダセン−１−イル）シランチタニウム（II）１，３−ペンタジエン（別名：［Ｎ−（１，１−ジメチルエチル）−１，１−ジメチル−１−［（１，２，３，３Ａ，８Ａ−η）−１，５，６，７−テトラヒドロ−２−メチル−Ｓ−インダセン−１−ｙｌ］シランアミネート（２−）−κＮ］［（１，２，３，４−η）−１，３−ペンタジエン］−チタニウム）である。

The above formula (iii) is obtained from (t-butylamido) -dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silanetitanium (II) 1,3-pentadiene (also known as [N- (1,1 -Dimethylethyl) -1,1-dimethyl-1-[(1,2,3,3A, 8A-η) -1,5,6,7-tetrahydro-2-methyl-S-indacene-1-yl] Silane aminate (2-)-κN] [(1,2,3,4-η) -1,3-pentadiene] -titanium).

上記式（ｉｖ）は、（ｔ−ブチルアミド）−ジメチル（η⁵−２，３−ジメチルインデニル）シランチタニウム（ＩＩ）１，４−ジフェニル−１，３−ブタジエンである。

The above formula (iv) is (t-butylamido) -dimethyl (η ⁵ -2,3-dimethylindenyl) silane titanium (II) 1,4-diphenyl-1,3-butadiene.

上記式（ｖ）は、（ｔ−ブチル−アミド）−ジメチル（η⁵−２，３−ジメチル−ｓ−インダセン−１−イル）シランチタニウム（ＩＶ）ジメチルである。

The above formula (v) is (t-butyl-amido) -dimethyl (η ⁵ -2,3-dimethyl-s-indasen-1-yl) silane titanium (IV) dimethyl.

上記式（ｖｉ）は、（ｔ−ブチルアミド）−ジメチル（η⁵−２−メチル−ｓ−インダセン−１−イル）シラン−チタニウム（ＩＶ）ジメチルである。

The above formula (vi) is (t-butylamido) -dimethyl (η ⁵ -2-methyl-s-indasen-1-yl) silane-titanium (IV) dimethyl.

  When the metallocene catalyst having the structure represented by the above formula (iii) is used, the copolymerization property of the nonconjugated polyene is particularly excellent in the polymerization reaction for obtaining the ethylene / α-olefin / nonconjugated polyene copolymer. For this reason, the ethylene / α-olefin / non-conjugated polyene copolymer polymerized using the metallocene-based catalyst having the structure represented by the formula (iii) is, for example, a 2-vinyl-2-norbornene (VNB) Heavy bonds can be efficiently incorporated into the polymer and long chain branching can be introduced at a high rate. Further, the ethylene / α-olefin / non-conjugated polyene copolymer having a narrow molecular weight distribution and composition distribution and having an extremely uniform molecular structure can be prepared. .

  The metallocene catalyst having the structure represented by the above formulas (i) to (vi) can be prepared using a well-known synthesis method. For example, it is disclosed in International Publication No. 98/49212 pamphlet. If necessary, a lower oxidation state complex (metallocene catalyst) can be produced using a reducing agent. Such a method is disclosed in USSN 8 / 241,523.

The method for producing the ethylene / α-olefin / non-conjugated polyene copolymer preferably has a step of obtaining the following polymerization reaction solution.
The step of obtaining a polymerization reaction liquid means using an aliphatic hydrocarbon as a polymerization solvent, and in the presence of the metallocene catalyst described above, preferably a metallocene catalyst having a structure represented by the above formula (iii), A polymerization reaction liquid obtained by copolymerizing an α-olefin and a non-conjugated polyene and having an ethylene / α-olefin / non-conjugated polyene copolymer concentration of 8 to 18% by mass, preferably 8.5 to 18.0% by mass. It is a process to obtain.

  When the concentration of the ethylene / α-olefin / non-conjugated polyene copolymer with respect to the polymerization solvent exceeds 18% by mass, the viscosity of the polymerization solution is too high, so the solution may not be uniformly stirred, and the polymerization reaction may be difficult. is there.

  Examples of the polymerization solvent include aliphatic hydrocarbons and aromatic hydrocarbons. Examples of the aliphatic hydrocarbon include pentane, hexane, and heptane. Among these, hexane is preferable from the viewpoint of separation and purification from the obtained ethylene / α-olefin / nonconjugated polyene copolymer.

  As such a production method, a reaction with a stirrer using the above catalyst as a main catalyst, an organoaluminum compound such as a boron compound and / or a trialkyl compound as a cocatalyst, and an aliphatic hydrocarbon such as hexane as a solvent. A continuous method or a batch method using a vessel is mentioned.

  Examples of the boron compound include trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluoro). Phenyl) borate, tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium n-butyltris (pentafluorophenyl) borate N, N-dimethylanilinium benzyltris (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis ( -(T-butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4- (triisopropylsilyl) -2,3,5,6-tetrafluoro Phenyl) borate, N, N-dimethylanilinium pentafluorophenoxytris (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethyl Anilinium tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetra Lakis (2,3,4,6-tetrafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) 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; dialkylammonium salts such as di- (isopropyl) ammonium tetrakis (pentafluorophenyl) borate and dimethyl (t- Butyl) ammo Nium tetrakis (2,3,4,6-tetrafluorophenyl) borate; trisubstituted phosphonium salts such as triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (o-tolyl) phosphonium tetrakis (pentafluorophenyl) Borate and tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate; disubstituted oxonium salts such as diphenyloxonium tetrakis (pentafluorophenyl) borate, di- (o-tolyl) oxonium tetrakis (Pentafluorophenyl) borate and di (2,6-dimethylphenyl) oxonium tetrakis (pentafluorophenyl) borate; disubstituted sulfonium salts such as diphenylsulfate Tetrakis (pentafluorophenyl) borate, di (o-tolyl) sulfonium tetrakis (pentafluorophenyl) borate and bis (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, and the like.

Examples of the organoaluminum compound include triisobutylaluminum.
The reaction temperature can be raised to 100 ° C. because the catalyst is not deactivated even at high temperatures.
The polymerization pressure ranges from over 0 to 8 MPa (gauge pressure), preferably over 0 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. It is.

Further, in the copolymerization, a molecular weight regulator such as hydrogen can be used.
The molar ratio [ethylene / α-olefin] of the charge of ethylene and the α-olefin is preferably 25/75 to 95/5, more preferably 25/75 to 90/10.

The molar ratio [ethylene / non-conjugated polyene] of ethylene and non-conjugated polyene is preferably 65/35 to 99/1, more preferably 65/35 to 98/2.
Polymerization using the above catalyst is preferable because non-conjugated polyene and the like are copolymerized at a high conversion rate, and an appropriate amount of long chain branching can be introduced into the resulting copolymer.

(Ethylene copolymer (B))
The composition of the present invention comprises an ethylene / α-olefin copolymer (B-1) comprising ethylene and an α-olefin having 3 to 20 carbon atoms, and the ethylene / α-olefin copolymer (B-1). At least one ethylene-based copolymer (B) selected from a modified ethylene / α-olefin copolymer (B-2) obtained by modifying with a compound containing a polar group.

  The composition of the present invention contains an ethylene copolymer (B), and the ethylene copolymer (B) may contain only an ethylene / α-olefin copolymer (B-1). Only the modified ethylene / α-olefin copolymer (B-2) may be contained. Further, it may contain an ethylene / α-olefin copolymer (B-1) and a modified ethylene / α-olefin copolymer (B-2).

  The composition of the present invention contains an ethylene copolymer (B) together with the copolymer rubber (A), but when the ethylene copolymer (B) is contained, the composition contains the ethylene copolymer (B). Compared with the case where there is no, the melt viscosity at the time of kneading tends to be lowered and the workability tends to be improved, which is preferable. Moreover, when a composition contains an ethylene-type copolymer (B), there exists a tendency for a crosslinking density to improve, and since a crosslinked body is excellent in mechanical physical properties, such as hardness, it is preferable.

  The ethylene-based copolymer (B) is preferably the modified ethylene / α-olefin copolymer (B-2) because of excellent dispersibility during kneading when preparing the composition. When the ethylene copolymer (B) is the modified ethylene / α-olefin copolymer (B-2), the crosslinking density tends to be improved, and the crosslinked product tends to be excellent in mechanical properties such as hardness. It is preferable.

  The ethylene / α-olefin copolymer (B-1) is a copolymer having a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 to 20 carbon atoms. The modified ethylene / α-olefin copolymer (B-2) is a modification of the ethylene / α-olefin copolymer (B-1) with a compound containing a polar group such as maleic anhydride. It is a copolymer obtained by this.

The composition of this invention is used for ethylene-type copolymer (B) individually or in combination of 2 or more types.
Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1- Decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyl-1-decene, 11-methyl- Examples include 1-dodecene and 12-ethyl-1-tetradecene.

  As the C3-C20 α-olefin, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene are preferable, and 1-butene is particularly preferable.

The said C3-C20 alpha olefin is used individually or in combination of 2 or more types.
The ethylene / α-olefin copolymer (B-1) is a molar ratio of ethylene to an α-olefin having 3 to 20 carbon atoms (ethylene / α-olefin), in other words, a structural unit derived from ethylene and a carbon number. The molar ratio with the structural unit derived from 3 to 20 α-olefin is usually 50/50 to 90/10, preferably 50/50 to 85/15.

  As described above, the modified ethylene / α-olefin copolymer (B-2) is obtained by modifying the ethylene / α-olefin copolymer (B-1) with a compound containing a polar group such as maleic anhydride. Is obtained.

  The polar group is a group having at least one hetero atom. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. The polar group preferably has an oxygen atom.

  Examples of polar groups include ester groups, carbonyl groups, carboxyl groups, carboxylic anhydride groups (—CO—O—CO—), nitrile groups, amide groups, hydroxyl groups, ether groups, nitro groups, amino groups, carbonate groups, Examples thereof include a thioester group, a thiocarbonate group, a thioether group, and a thionyl oxide group.

  The method for modifying the tylene / α-olefin copolymer (B-1) with a compound containing a polar group is not particularly limited. For example, an unsaturated carboxylic acid or an unsaturated carboxylic acid derivative is used. Examples of the modification include acrylic modification using glycidyl methacrylate, silane modification using a vinyl silane compound, epoxidation using glycidyl acrylate, amination, and diol formation.

Examples of the compound having a polar group include unsaturated carboxylic acids and unsaturated carboxylic acid derivatives.
Examples of the unsaturated carboxylic acid include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid and nadic acid ^TM (endocis-bicyclo [2,2,1] hept-5 -Ene-2,3-dicarboxylic acid) and the like.

  Specific examples of the unsaturated carboxylic acid derivative include acid halide compounds, amide compounds, imide compounds, acid anhydrides and ester compounds of the above unsaturated carboxylic acids. More specifically, maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like can be mentioned.

As the compound having a polar group, an unsaturated dicarboxylic acid or an acid anhydride thereof is preferable, and maleic acid, nadic acid ^TM or an acid anhydride thereof is particularly preferable.
The ethylene-based copolymer (B) preferably has (i) a density of 0.840 to 0.920 g / cm ³ . The density is more preferably 0.860 to 0.910 g / cm ³ . The density can be measured according to ASTM D1505.

  The ethylene-based copolymer (B) preferably has (ii) a melt flow rate (MFR) at 190 ° C. and 2.16 kg of 0.1 to 50 g / 10 min. The MFR is more preferably 0.5 to 35 g / 10 min. The melt flow rate can be measured according to ASTM D1238.

  The ethylene copolymer (B) preferably has an embrittlement temperature of −60 ° C. or lower, and more preferably less than −70 ° C. The embrittlement temperature can be measured according to ASTM D746.

As said ethylene-type copolymer (B), what is marketed may be used and the polymer obtained by synthesize | combining may be used.
The method for synthesizing the ethylene / α-olefin copolymer (B-1) is not particularly limited. For example, the ethylene / α-olefin copolymer (B-1) is synthesized by a known method using a catalyst such as a vanadium catalyst, a Ziegler catalyst, or a metallocene catalyst. Can do. In the case of synthesizing the ethylene / α-olefin copolymer (B-1) using a metallocene catalyst, for example, compounds exemplified as the metallocene compound used when synthesizing the copolymer rubber (A) described above, for example. Alternatively, it can be synthesized using a metallocene compound disclosed in Japanese Patent Application Laid-Open No. 09-040586.

  The polymerization of the ethylene / α-olefin copolymer (B-1) varies depending on the type of catalyst, but in the presence of the catalyst, the polymerization temperature is usually −20 to 200 ° C., preferably 0 to 150 ° C., more preferably. Is preferably in the range of 0 to 100 ° C., the pressure usually exceeding 0 to ˜8 MPa (gauge pressure), preferably exceeding 0 to ˜5 MPa (gauge pressure).

The polymerization time (average residence time when copolymerization is carried out by a continuous method) 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. .
In the polymerization of the ethylene / α-olefin copolymer (B-1), a molecular weight regulator such as hydrogen may be used.

  Although it does not restrict | limit especially as usage-amount of each raw material in the case of the synthesis | combination of the said ethylene-alpha-olefin copolymer (B-1), The structural unit derived from ethylene in a copolymer obtained, and C3-C20 The amount is preferably such that the molar ratio of the α-olefin-derived structural unit is in the above range. Specifically, the α-olefin having 3 to 20 carbon atoms is preferably 25 to 200 parts by mass, and more preferably 30 to 150 parts by mass with respect to 100 parts by mass of ethylene.

The amount of catalyst used is preferably 1.0 × 10 ^{−6 to} 5.0 × 10 ⁻⁶ with respect to 1 mass of ethylene.
The method for synthesizing the modified ethylene / α-olefin copolymer (B-2) is not particularly limited, but the ethylene / α-olefin copolymer (B-1) has a polar group by a known method. It can be synthesized by modifying with a compound.

Examples of the modification include graft modification.
As an example of a method for synthesizing the modified ethylene / α-olefin copolymer (B-2), a method for synthesizing the modified ethylene / α-olefin copolymer (B-2) by graft modification will be described.

  The modified ethylene / α-olefin copolymer (B-2) is obtained by adding a specific amount of unsaturated carboxylic acid or a derivative thereof (for example, carboxylic acid anhydride) to the ethylene / α-olefin copolymer (B-1). ) Can be obtained by grafting.

  The graft amount of the unsaturated carboxylic acid or derivative thereof in the modified ethylene / α-olefin copolymer (B-2) is 0. 0% with respect to 100% by mass of the ethylene / α-olefin copolymer (B-1). It is 1 to 4.0 mass%, preferably 0.3 to 4.0 mass%, particularly preferably 0.5 to 2.5 mass%.

The modified ethylene / α-olefin copolymer (B-2) can be prepared using various conventionally known methods, for example, the following methods.
(1) A method in which an unsaturated carboxylic acid or a derivative thereof is added to a melted ethylene / α-olefin copolymer (B-1) for graft copolymerization.

(2) A method in which the ethylene / α-olefin copolymer (B-1) is dissolved in a solvent, and an unsaturated carboxylic acid or a derivative thereof is added to the solution to perform graft copolymerization.
In any method, in order to efficiently graft copolymerize the graft monomer such as the unsaturated carboxylic acid, the graft reaction is preferably performed in the presence of a radical initiator.

  As the radical initiator, organic peroxides, organic peresters, azo compounds, and the like can be used. Specific examples of such radical initiators include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (peroxide benzoate) hexyne- 3,1,4-bis (t-butylperoxyisopropyl) benzene, lauroyl peroxide, t-butylperacetate, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexyne-3, 2,5 -Dimethyl-2,5-di (t-butylperoxy) hexane; t-butylperbenzoate, t-butylperphenylacetate, t-butylperisobutyrate, t-butylper-sec-octoate, t-butylperpi Valate, cumylperpivalate and t-butylperdiethyla Tate; azobisisobutyronitrile, dimethyl azoisobutyrate, and the like.

  Among these, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (t Dialkyl peroxides such as -butylperoxy) hexane and 1,4-bis (t-butylperoxyisopropyl) benzene are preferably used.

  These radical initiators are usually 0.01 to 0.10 parts by mass, preferably 0.02 to 0.08 parts by mass with respect to 100 parts by mass of the ethylene / α-olefin copolymer (B-1). More preferably, it is used in the range of 0.02 to 0.05 parts by mass.

  The reaction temperature in the grafting reaction using the radical initiator as described above or in the grafting reaction performed without using the radical initiator is usually set in the range of 60 to 350 ° C, preferably 150 to 300 ° C.

(Inorganic filler having polar group (C))
The composition of the present invention contains an inorganic filler (C) having a polar group (however, the inorganic filler (C) having a polar group excludes a carbon-based inorganic filler having a polar group).

  Although the composition of this invention contains the inorganic filler (C) which has a polar group, the carbon-type inorganic filler which has a polar group is not contained in the inorganic filler (C) which has a polar group. In addition, although the carbon-type inorganic filler which has a polar group is not contained as an inorganic filler (C) which has a polar group in the composition of this invention, components other than (A)-(C) mentioned later and a crosslinking agent. May be included.

In the present invention, the carbon-based inorganic filler having a polar group is an inorganic filler having a polar group and comprising 80% by mass or more of carbon atoms per 100% by mass of the filler. Examples of the carbon-based inorganic filler having a polar group include carbon black. Carbon black has a carboxyl group or a hydroxyl group on the filler surface, and usually 95% by mass or more is composed of carbon atoms.
In the composition of the present invention, carbon black is not contained as the inorganic filler (C) having a polar group, but other components, for example, carbon black may be contained as a reinforcing agent.

  The composition of the present invention contains an inorganic filler (C) having a polar group together with the copolymer rubber (A) and the ethylene copolymer (B). The copolymer rubber (A), the ethylene copolymer It is preferable to use the combination (B) because the melt viscosity at the time of kneading tends to be lowered and the workability tends to be improved as compared with the case where the ethylene copolymer (B) is not used. Moreover, when a composition contains the inorganic filler (C) which has a polar group, a crosslinked body is excellent in mechanical physical properties, such as hardness. The reason why the crosslinked body is excellent in hardness is not clear, but the present inventors have formed a network-like structure due to physical interaction such as hydrogen bonding because the inorganic filler (C) has a polar group. As a result, it was assumed that the crosslinked product was excellent in hardness.

  The polar group is a group having at least one hetero atom. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. The polar group preferably has an oxygen atom.

  Examples of polar groups include ester groups, carbonyl groups, carboxyl groups, carboxylic anhydride groups (—CO—O—CO—), nitrile groups, amide groups, ether groups, nitro groups, amino groups, carbonate groups, thioester groups. , A thiocarbonate group, a thioether group, a thionyl oxide group, and a hydroxyl group. A hydroxyl group is particularly preferable.

Examples of the inorganic filler (C) having a polar group include metal hydroxides and silica.
Examples of the metal hydroxide include aluminum hydroxide and magnesium hydroxide.
The metal hydroxide is an inorganic filler having a hydroxyl group that is a polar group, and silica usually has a hydroxyl group on the particle surface.

The composition of the present invention is used alone or in combination of two or more inorganic fillers (C) having a polar group.
The inorganic filler (C) having a polar group preferably contains a metal hydroxide, and more preferably contains at least one metal hydroxide selected from aluminum hydroxide and magnesium hydroxide.

The metal hydroxide is preferably used in an amount of 80 to 100% by mass, more preferably 85 to 100% by mass, per 100% by mass of the inorganic filler (C) having a polar group.
Moreover, as an inorganic filler (C) which has a polar group, it is preferable to use a metal hydroxide and a silica. When using a metal hydroxide and silica as the inorganic filler (C) having a polar group, 80 to 97% by mass of the metal hydroxide is used per 100% by mass of the inorganic filler (C) having a polar group. Further, it is preferable to use 3 to 20% by mass of silica, more preferably 85 to 95% by mass of metal hydroxide, and more preferably 5 to 15% by mass of silica.
As the inorganic filler (C) having a polar group of the present invention, a commercially available filler may be used, or a filler obtained by synthesis may be used.

(Composition)
The composition of the present invention comprises an ethylene / α-olefin / non-conjugated polyene copolymer rubber (A), an ethylene copolymer (B), and an inorganic filler (C) having a polar group (provided that the polar group is The inorganic filler (C) includes a carbon-based inorganic filler having a polar group), and the ethylene / α-olefin / nonconjugated polyene copolymer rubber (A) and the ethylene copolymer (B). The mass ratio [(A) / (B)] is 95/5 to 50/50, and the ethylene / α-olefin / nonconjugated polyene copolymer rubber (A) and the ethylene copolymer ( 80-200 mass parts of said fillers (C) are included with respect to 100 mass parts of total amounts with B).

  The mass ratio [(A) / (B)] of the ethylene / α-olefin / nonconjugated polyene copolymer rubber (A) and the ethylene copolymer (B) is 95/5 to 5/5 as described above. Although it is 50/50, it is preferable that it is 95 / 5-60 / 40, and it is more preferable that it is 95 / 5-70 / 30.

  The composition of the present invention comprises the filler (C) with respect to a total amount of 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and the ethylene copolymer (B). Although 80-200 mass parts is included, it is preferable that 80-180 mass parts is included, and it is more preferable that 80-160 mass parts is included.

Since the composition of the present invention tends to deteriorate flexibility and rubber elasticity, it is preferable that the composition does not substantially contain an ethylene-vinyl acetate copolymer.
It should be noted that “ethylene-vinyl acetate copolymer is substantially not included” means that the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and the ethylene copolymer (B) are included in the composition. This means that 3 parts by mass or more of ethylene-vinyl acetate copolymer is not included, and preferably 1 part by mass or more of ethylene-vinyl acetate copolymer is not included, and more preferably Is no ethylene-vinyl acetate copolymer in the composition, i.e. 0 parts by weight.

The crosslinked product obtained by crosslinking the composition of the present invention is excellent in mechanical properties such as hardness, and the composition of the present invention preferably further contains a crosslinking agent in order to suitably perform the crosslinking.
Moreover, the composition of this invention may contain components other than said (A)-(C) and a crosslinking agent.

[Crosslinking agent]
The composition of the present invention includes the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A), the ethylene copolymer (B), and an inorganic filler (C) having a polar group (however, a polar group In addition to the carbon-based inorganic filler having a polar group, the inorganic filler (C) having a cross-linking agent may be added. Examples of the crosslinking agent used for crosslinking include vulcanizing agents such as sulfur and sulfur compounds, and organic peroxides.

  As one of the crosslinking agents, sulfur and sulfur compounds can be used as the vulcanizing agent used in vulcanization. Specific examples of sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur and the like.

  Specific examples of the sulfur compound include sulfur chloride, sulfur dichloride, and polymer polysulfide. Also use sulfur compounds that release active sulfur at the vulcanization temperature, such as morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide, selenium dimethyldithiocarbamate. Can do.

As the vulcanizing agent, sulfur is preferably used. These vulcanizing agents are used alone or in combination of two or more.
When a vulcanizing agent is used, it is usually 0.1 to 10 parts by mass, preferably 0.3 to 5 parts by mass with respect to 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A). However, it is desirable to appropriately determine the optimum amount according to the required physical properties. Moreover, when using sulfur and a sulfur compound as a vulcanizing agent, it is preferable to use a vulcanization accelerator together.

  Specific examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazol sulfenamide, N, N-diisopropyl-2-benzothiazol sulfenamide. Sulfenamide compounds such as 2-mercaptobenzothiazole, 2- (2 ′, 4′-dinitrophenyl) mercaptobenzothiazole, 2- (4′-morpholinodithio) benzothiazole, dibenzothiazyl disulfide Compound: Guanidine compound such as diphenylguanidine, diorthotolylguanidine, diorthonitrile guanidine, orthonitrile biguanide, diphenylguanidine phthalate; acetaldehyde-aniline reactant, butyraldehyde-aniline condensate, hexide Aldehyde amines such as methylenetetramine and acetaldehyde ammonia or aldehyde-ammonia compounds; imidazoline compounds such as 2-mercaptoimidazoline; thiourea compounds such as thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea ; Thiuram compounds such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate , Zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, dimethyl Sodium Le dithiocarbamate, dimethyl dithiocarbamate selenium, dithio acid salt-based compounds such as dimethyl dithiocarbamate tellurium; xanthate-based compounds such as dibutyltin xanthate zinc; zinc oxide can be exemplified compounds of (zinc oxide) or the like.

  When a vulcanization accelerator is used, it is usually 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight with respect to 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A). However, it is desirable to appropriately determine the optimum amount according to the required physical properties.

  The organic peroxide that is one of the crosslinking agents may be any one that is usually used for peroxide vulcanization of rubber. Specifically, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butyl hydroperoxide, t-butylcumyl peroxide, benzoyl Peroxide, 2,5-dimethyl-2,5-di (t-butylperoxin) hexyne-3, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2 , 5-mono (t-butylperoxy) -hexane, α, α′-bis (t-butylperoxy-m-isopropyl) benzene, and the like. Of these, dicumyl peroxide, di-t-butyl peroxide, and di-t-butylperoxy-3,3,5-trimethylcyclohexane are preferably used. These organic peroxides are used alone or in combination of two or more.

  When an organic peroxide is used, it is usually 0.0003 to 0.08 mol, preferably 0.001 to 0.05, per 100 g of ethylene / α-olefin / non-conjugated polyene copolymer rubber (A). Although it is used in a molar ratio, it is desirable to appropriately determine the optimum amount according to the required physical properties.

  When using an organic peroxide as a crosslinking agent, it is preferable to use a crosslinking aid in combination. Specific examples of crosslinking aids include sulfur; quinone dioxime compounds such as p-quinone dioxime; methacrylate compounds such as polyethylene glycol dimethacrylate; allyl compounds such as diallyl phthalate and triallyl cyanurate; Maleimide compounds; divinylbenzene and the like. Such a crosslinking assistant is used in an amount of 0.25 to 2 mol, preferably 0.4 to 1.2 mol, with respect to 1 mol of the organic peroxide used.

The composition of this invention may contain components other than said (A)-(C) and a crosslinking agent as mentioned above.
Examples of components other than (A) to (C) and the crosslinking agent include reinforcing agents, activators, processing aids, softeners, anti-aging agents, alkoxysilane compounds, reaction inhibitors, colorants, dispersants, and difficult agents. Flame retardants, plasticizers, antioxidants, scorch inhibitors, ultraviolet absorbers, antistatic agents, lubricants, antifungal agents, peptizers, tackifiers, various dyes such as disperse dyes and acid dyes, inorganic -Organic pigments, surfactants, and paints.

The vulcanization accelerator and the crosslinking aid described in the description of the crosslinking agent are also components other than the components (A) to (C) and the crosslinking agent.
About these components other than said (A)-(C) and a crosslinking agent, it is possible to mix | blend in the quantity of the range which does not impair the objective of this invention.

  The reinforcing agent is not particularly limited as long as it is used as a reinforcing agent for synthetic rubber. Examples of the reinforcing agent include carbon black such as SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, and MT, activated calcium carbonate, light calcium carbonate, heavy calcium carbonate, clay, talc, and silica. It is done. Moreover, an organic filler may be used as the reinforcing agent, and examples of the organic filler include a coumarone resin and a phenol resin. Commercially available carbon blacks include “Asahi # 55G”, “Asahi # 50HG”, “Asahi # 60G” (trade name; manufactured by Asahi Carbon Co., Ltd.), “Seast V”, “Seast SO” (trade name; Tokai Carbon Co., Ltd.).

The specific surface area of such a reinforcing agent is preferably 5 to 120 m ² / g. In the present invention, carbon black is preferably used from the viewpoint of improving the rigidity of the crosslinked body.
When the reinforcing agent is contained in the composition, the content of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and the ethylene copolymer (B) is 100 parts by mass. On the other hand, it is 0-30 mass parts normally, Preferably it is 0-10 mass parts.

The activator is not particularly limited as long as it is used as an activator for synthetic rubber.
Specific examples include zinc white, polyethylene glycol, silane coupling agents, and organic titanate. Of these, zinc white is preferably used.

  When the composition contains an activator, the content of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and the ethylene copolymer (B) is 100 parts by mass. On the other hand, it is usually 20 parts by mass or less, preferably 15 parts by mass or less, more preferably 10 parts by mass or less.

The softener is not particularly limited as long as it is used as a softener for synthetic rubber.
Specifically, petroleum-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and petroleum jelly; coal-tar softeners such as coal tar and coal tar pitch; castor oil, linseed oil, rapeseed oil, Fat oil-based softeners such as coconut oil; tall oil; sub; waxes such as beeswax, carnauba wax and lanolin; fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, barium stearate, calcium stearate and zinc laurate; petroleum Examples thereof include synthetic polymer materials such as resin, atactic polypropylene, and coumarone indene resin. Of these, petroleum softeners are preferably used.

  When the composition contains a softening agent, the total content of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and the ethylene copolymer (B) is 100 parts by mass. On the other hand, it is usually 100 parts by mass or less, preferably 50 parts by mass or less, more preferably 30 parts by mass or less.

The processing aid is not particularly limited as long as it is used as a processing aid for synthetic rubber.
Specifically, higher fatty acids such as ricinoleic acid, stearic acid, palmitic acid and lauric acid, higher fatty acid salts such as barium stearate, zinc stearate and calcium stearate, ricinoleic acid ester, stearic acid ester, palmitic acid ester and lauric acid And higher fatty acid esters such as acid esters.

  When the processing aid is included in the composition, the content of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and the ethylene copolymer (B) is 100 parts by mass. On the other hand, it is usually used in a proportion of 10 parts by mass or less, preferably 5 parts by mass or less, but it is desirable to determine the optimum amount as appropriate in accordance with the required physical property values.

  The method for producing the composition of the present invention is not particularly limited. For example, the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A), the ethylene copolymer (B), and a polar group are included. A composition comprising an inorganic filler (C), preferably a cross-linking agent preferably contained, and components (A) to (C) optionally contained and components other than the cross-linking agent is obtained by a general method for producing a rubber compound. Can be prepared.

  In addition, when the composition of the present invention contains a crosslinking agent, an ethylene / α-olefin / non-conjugated polyene copolymer rubber (A), an ethylene copolymer (B), and an inorganic group having a polar group in advance. After preparing a composition containing a filler (C), it is preferable to further mix a crosslinking agent.

  As a method for producing the rubber composition, for example, an ethylene / α-olefin / non-conjugated polyene copolymer rubber (A), ethylene using an internal mixer (sealed mixer) such as a Banbury mixer, a kneader, or an intermix is used. The system copolymer (B), the inorganic filler (C) having a polar group, and if necessary, a softening agent, a processing aid, a crosslinking aid and the like are kneaded at a temperature of 80 to 170 ° C. for 2 to 20 minutes. Next, the resulting blended product is added with a crosslinking agent, a softening agent, a crosslinking assistant vulcanization accelerator, etc., using a roll such as an open roll, or a kneader, and a vulcanization accelerator if necessary. It can be prepared by further mixing a crosslinking aid, kneading at a roll temperature of 40 to 80 ° C. for 5 to 30 minutes, and dispensing.

  When the kneading temperature in the internal mixers is low, ethylene / α-olefin / non-conjugated polyene copolymer rubber (A), ethylene copolymer (B), inorganic filler having a polar group (C ) And the like may be kneaded with a crosslinking agent at the same time.

(Crosslinked product)
The crosslinked body of the present invention is a crosslinked body obtained by crosslinking the composition.
Since the crosslinked body of the present invention is obtained by crosslinking the composition, it has excellent mechanical properties such as hardness as compared with a crosslinked body obtained by crosslinking a conventional rubber composition.

The method for crosslinking the composition is not particularly limited. For example, a crosslinked product molded into a desired shape can be obtained by molding the composition and then crosslinking.
As a molding method, for example, molding such as compression molding, injection molding, and injection molding is preferable because the composition can be easily molded into a desired shape.

When the molding is performed by mold molding, it is preferable from the viewpoint of productivity that the crosslinking is performed before removing the composition from the mold, that is, with the mold closed.
The conditions for performing the crosslinking vary depending on the type of the crosslinking agent, but are usually performed by heating the composition.

When the crosslinking is carried out by heating, the temperature is usually 120 to 270 ° C, preferably 150 to 180 ° C, and the heating time is usually 30 seconds to 120 minutes, preferably 5 to 30 minutes.
Since the crosslinked product of the present invention is excellent in hardness, it can be used for various applications. Moreover, you may use the crosslinked body of this invention for various uses as a laminated body which has a layer formed from this crosslinked body.

  Although there is no restriction | limiting in particular as a manufacturing method of a laminated body, After shape | molding the composition of this invention by coextrusion etc. with another component, and obtaining the laminated body containing the layer formed from the composition of this invention, Examples thereof include a method of crosslinking the composition of the present invention, and a method of laminating the crosslinked body and a layer formed from other components with heat or an adhesive after preparing the crosslinked body. In the laminate of the present invention, the layer other than the layer formed from the crosslinked body is not particularly limited, and examples thereof include nylon and polyester fabrics. The layer other than the layer formed from the crosslinked body may be a single layer or two or more layers.

Applications of the crosslinked body and laminate of the present invention include automobile parts, railway vehicle parts, home appliance-related parts, civil engineering / building material-related parts, sundries, daily necessities, and the like.
Since the crosslinked body of the present invention is excellent in strength, the crosslinked body and laminate of the present invention can be suitably used for applications that require particularly high strength, such as parts for railway vehicles.
Examples of railway vehicle parts include railcar hoods such as an outer hood and an inner hood (through hood).

EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these.
The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) (EPDM-1 to EPDM-3) used in Examples and Comparative Examples was produced by the following method.

[Production Example 1] (Production of EPDM-1)
Quaternary copolymerization reaction using ethylene, propylene, 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB) continuously using a 300 L polymerization vessel equipped with a stirring blade Was carried out at 95 ° C.

  Using hexane (final concentration: 84.9% by mass) as a polymerization solvent, the ethylene concentration was 3.6% by mass, the propylene concentration was 9.6% by mass, the ENB concentration was 1.9% by mass, and the VNB concentration was 0.8%. The raw material was continuously supplied at 036% by mass.

While maintaining the polymerization pressure at 1.6 MPa (gauge pressure), (t-butylamido) -dimethyl (η ⁵ -2-methyl-s) is a metallocene catalyst having a structure represented by the following formula (iii) as a main catalyst. -Indasen-1-yl) silanetitanium (II) 1,3-pentadiene was continuously supplied to 0.00045 mmol / L. Further, (C ₆ H ₅ ) ₃ CB (C ₆ F ₅ ) ₄ as a cocatalyst was continuously 0.0023 mmol / L, and triisobutylaluminum (TIBA) as an organoaluminum compound was 0.23 mmol / L. Supplied.

  In this way, a polymerization reaction liquid containing 16.8% by mass of a copolymer rubber composed of ethylene, propylene, ENB and VNB was obtained. A small amount of methanol is added to the polymerization reaction liquid extracted from the lower part of the polymerization vessel to stop the polymerization reaction, and the copolymer rubber (EPDM-1) is separated from the solvent by a steam stripping treatment, and then at 80 ° C. all day and night. It was dried under reduced pressure.

[Production Example 2] (Production of EPDM-2)
In Production Example 1, a copolymer rubber (EPDM-2) was produced by adjusting the feed amount of each monomer.

[Production Example 3] (Production of EPDM-3)
In Production Example 1, a copolymer rubber (EPDM-3) was produced by adjusting the feed amount of each monomer.

  The composition and physical property values of the ethylene / α-olefin / nonconjugated polyene copolymer rubber (A) (EPDM-1 to EPDM-3) used in Examples and Comparative Examples were measured by the following methods. The results are shown in Table 1.

[Composition of ethylene / α-olefin / non-conjugated polyene copolymer]
Using an ECX400P type nuclear magnetic resonance apparatus manufactured by JEOL Ltd., using a measurement temperature of 120 ° C., using ODCB-d4 as a measurement solvent and setting the number of integrations to 512 times, the ethylene / α-olefin / non-conjugated obtained in the above production example The ¹ H spectrum of the polyene copolymer rubber (A) was measured to determine the composition.

[Iodine value]
The iodine value of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) is a value determined by a titration method. Specifically, the following method was used.

  Dissolve 0.5 g of ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) in 60 ml of carbon tetrachloride, add a small amount of Wis reagent and 20% potassium iodide solution, and add 0.1 mol / L sodium thiosulfate. The solution was titrated. In the vicinity of the end point, a starch indicator was added, and the mixture was well-stirred until the light purple color disappeared, and the number of g of iodine consumed was calculated as the amount of halogen consumed per 100 g of the sample.

[Intrinsic viscosity]
The intrinsic viscosity [η] of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) is a value measured at 135 ° C. using a decalin solvent.

Specifically, about 20 mg of ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to the decalin solution for dilution, the specific viscosity ηsp was measured in the same manner. This dilution operation was further repeated twice, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity (see the following formula).
[Η] = lim (ηsp / C) (C → 0) ”

実施例および比較例において使用したエチレン系共重合体（Ｂ）としては、以下の市販品を用いた。

As the ethylene-based copolymer (B) used in Examples and Comparative Examples, the following commercially available products were used.

TAFMER MD715, manufactured by Mitsui Elastomers Singapore Pte Ltd, a modified maleic anhydride of ethylene / 1-butene copolymer, MFR (190 ° C., 2.16 kg, ASTM D1238) 1.5 g / 10 min, density (ASTM D1505) 872 kg / m ³ , embrittlement temperature (ASTM D746)-less than 70 ° C. TAFMER DF710, manufactured by Mitsui Elastomers Singapore Pte Ltd, ethylene / 1-butene copolymer, MFR (190 ° C., 2.16 kg, ASTM D1238) 1.2 g / 10 min , density ^{(ASTM D1505) 870kg / m 3} , as the brittleness temperature (ASTM D746) an inorganic filler having a polar group used in less than -70 ° C. examples and Comparative examples (C) is less city Using the goods.

Aluminum hydroxide (manufactured by Showa Denko KK: Heidilite H-42M)
Silica (Tosoh Silica Corporation: Nipsil VN3)
As components other than the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A), the ethylene copolymer (B), and the inorganic filler (C) having a polar group used in Examples and Comparative Examples, The following were used.
Zinc Hana: Zinc Oxide (Hakusui Tech Co., Ltd.) (Activator)
Stearic acid (processing aid)
Carbon black: FEF carbon black: Asahi 60G (Asahi Carbon Co., Ltd.) (reinforcing agent)
Paraffin oil: Diana Process PS-430 (Idemitsu Kosan Co., Ltd.) (softener)
Organic peroxide: Dicumyl peroxide: Kayacumyl D-40C (manufactured by Kayaku Akzo) (crosslinking agent)
Sulfur (crosslinking aid)

[Example 1]
50 parts by mass of EPDM-1, 10 parts by mass of EPDM-2, 30 parts by mass of EPDM-3 using MIXTRON BB MIXER (Kobe Steel Ltd., BB-4 type, volume 2.95 L, rotor 4WH). 10 parts by weight Tafmer MD715, 5 parts by weight zinc white as activator, 1 part by weight stearic acid as processing aid, 4 parts by weight carbon black as reinforcing agent, 130 parts by weight aluminum hydroxide, 20 parts by weight Silica and 10 parts by mass of paraffinic oil as a softening agent were kneaded to obtain a composition.

The kneading conditions were a rotor rotation speed of 50 rpm, a floating weight pressure of 3 kg / cm ² , a kneading time of 5 minutes, and a kneading discharge temperature of 145 ° C.

Next, after confirming that the composition reached a temperature of 40 ° C., using a 14-inch roll, 8.5 parts by mass of an organic peroxide as a crosslinking agent and 0.5 as a crosslinking aid were added to the composition. Mass parts of sulfur were kneaded to obtain a composition containing a crosslinking agent.

  The kneading conditions were as follows: roll temperature: front roll / rear roll = 65 ° C./50° C., roll rotation speed: front roll / rear roll = 13 rpm / 11.5 rpm, roll gap of 5 mm, and kneading time 8 minutes.

Next, the composition containing the crosslinking agent was crosslinked at 180 ° C. for 20 minutes using a press molding machine to prepare a rubber sheet having a thickness of 2 mm (crosslinked sheet).
The obtained crosslinked sheet was measured for hardness, modulus, tensile breaking stress, tensile breaking elongation, and crosslinking density by the following methods.

[hardness]
The hardness of the sheet of the cross-linked product is determined according to JIS K 6253 (2006) “Vulcanized rubber and JIS K 6253 (2006)” according to JIS K7312 (1996), “Physical test method for thermosetting polyurethane elastomer molding”. It was measured in accordance with the description of test type A in “Durometer Hardness Test” in Section 6 of “Thermoplastic Rubber—How to Obtain Hardness”.

[Modulus, tensile breaking stress, tensile breaking elongation]
The modulus, tensile break stress, and tensile break elongation of the crosslinked sheet were measured by the following methods.

  A No. 3 dumbbell test piece described in JIS K 6251 (1993) was prepared by punching out the sheet of the crosslinked body, and measured according to the method defined in JIS K6251 item 3 using this test piece. A tensile test was conducted under the conditions of a temperature of 25 ° C. and a tensile speed of 500 mm / min. Tensile stress when the elongation was 25% (25% modulus (M25)), tensile stress when the elongation was 50% (50 % Modulus (M50)), tensile stress when the elongation is 100% (100% modulus (M100)), tensile stress when the elongation is 200% (200% modulus (M200)), and elongation Tensile stress (300% modulus (M300)), tensile break stress (TB) and tensile break elongation (EB) at 300% were measured.

[Crosslinking density]
The crosslink density ν of the cross-linked sheet was calculated from the Flory-Rehner equation (1) using the following equilibrium swelling.
V _R in formula (1) was obtained by extracting a crosslinked 2 mm sheet with toluene under conditions of 37 ° C. × 72 h.

実施例１で用いた各原料の種類および量、並びに硬度、モジュラス、引張破断点応力、引張破断点伸び、および架橋密度の測定結果を表２に示す。

Table 2 shows the types and amounts of each raw material used in Example 1, and the measurement results of hardness, modulus, tensile breaking stress, tensile breaking elongation, and crosslinking density.

[Examples 2 to 4, Comparative Examples 1 to 5]
A crosslinked sheet was obtained in the same manner as in Example 1 except that the types and amounts of the raw materials were changed as shown in Table 2.

With respect to the obtained crosslinked sheet, hardness, modulus, tensile breaking stress, tensile breaking elongation, and crosslinking density were measured in the same manner as in Example 1.
Table 2 shows the types and amounts of the raw materials used in Examples 2 to 4 and Comparative Examples 1 to 5, and the measurement results of hardness, modulus, tensile breaking stress, tensile breaking elongation, and crosslinking density.

Claims (14)

An ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) composed of ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene, and an ethylene / α-olefin having 3 to 20 carbon atoms. An ethylene / α-olefin copolymer (B-1) and a modified ethylene / α-olefin copolymer obtained by modifying the ethylene / α-olefin copolymer (B-1) with a compound containing a polar group At least one ethylene copolymer (B) selected from the polymer (B-2) and an inorganic filler (C) having a polar group (however, the inorganic filler (C) having a polar group includes a polar group Excluding carbon-based inorganic fillers having
The mass ratio [(A) / (B)] of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and the ethylene copolymer (B) is 95/5 to 50/50. ,
Composition containing 80 to 200 parts by mass of the filler (C) with respect to 100 parts by mass of the total amount of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and the ethylene copolymer (B). object.   The composition of claim 1, substantially free of ethylene-vinyl acetate copolymer. Of the ethylene copolymer (B),
(I) the density is 0.840-0.920 g / cm ³ ;
(Ii) The composition according to claim 1 or 2, wherein a melt flow rate (MFR) at 190 ° C and 2.16 kg is 0.1 to 50 g / 10 min.   The composition according to any one of claims 1 to 3, wherein the ethylene / α-olefin copolymer (B) contains 1-butene as an α-olefin having 3 to 20 carbon atoms.   The composition according to any one of claims 1 to 4, wherein the ethylene copolymer (B) is the modified ethylene / α-olefin copolymer (B-2).   The composition as described in any one of Claims 1-5 in which the said filler (C) contains a metal hydroxide.   The composition according to any one of claims 1 to 6, wherein the filler (C) contains at least one metal hydroxide selected from aluminum hydroxide and magnesium hydroxide. Of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A),
(I) The molar ratio of ethylene to an α-olefin having 3 to 20 carbon atoms (ethylene / α-olefin) is 50/50 to 90/10,
(Ii) The iodine value is 1 to 50 g / 100 g,
(Iii) The composition according to any one of claims 1 to 7, wherein the intrinsic viscosity [η] measured in decalin at 135 ° C is 0.5 to 7.0 dl / g. In the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A),
The composition according to any one of claims 1 to 8, comprising 5-ethylidene-2-norbornene as the non-conjugated polyene.   Furthermore, the composition of any one of Claims 1-9 containing a crosslinking agent.   The crosslinked body obtained by bridge | crosslinking the composition of any one of Claims 1-10.   A laminate having a layer formed from the crosslinked body of claim 11.   A railcar part obtained from the cross-linked product according to claim 11 or the laminate according to claim 12.   A hood for a railway vehicle obtained from the cross-linked body according to claim 11 or the laminate according to claim 12.