JP7256579B2 - Copolymer composition for vibration damping material and vibration damping material comprising the copolymer composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a copolymer composition for a vibration damping material containing an ethylene/α-olefin/nonconjugated polyene copolymer and a vibration damping material comprising the copolymer composition.

Traditionally, vibration damping has been applied to the surface and inside of structural members for the purpose of preventing vibration and accompanying noise in structural members such as ships, vehicles, automobile parts, home appliances, various machines, building materials, and audio equipment. , coating or attaching a material having vibration-proof properties has been carried out. Materials having damping and damping properties include rubber, asphalt, various synthetic resin emulsions and latexes, synthetic resins, etc., as well as graphite, mica, carbon black, vermiculite, calcium carbonate, talc, A powder such as clay or a mixture of natural or synthetic fibers has been used.

However, many of the conventional vibration-damping and vibration-isolating materials described above exhibit vibration-damping and vibration-isolating properties at around room temperature, but the temperature range in which they exhibit vibration-damping and vibration-isolating properties is extremely narrow, and they have poor heat resistance. Due to its inferiority, the mechanical properties are extremely reduced at high temperatures, and its poor weather resistance has limited the range of use.

As a method for improving damping properties, for example, an ethylene/α-olefin/non-conjugated polyene copolymer is added with an α-olefin having 6 to 20 carbon atoms and having a kinematic viscosity of 30 mm ² /s or less at 100°C. Intrinsic viscosity [η] measured in decalin at 135° C. of 0.15 to 0.6 dl/g with at least one polymer and/or hydrogenated product thereof and an ethylene content of 40 to 90 mol % A method of blending an ethylene/α-olefin copolymer (Patent Document 1), wherein at least one peak of loss tangent (tan δ) measured at 100 rad/sec is in the range of -60 to -30 ° C., 0 to 40 ° C. an acrylic copolymer in which an α,β-unsaturated nitrile monomer is copolymerized, and the tan δ peak in the range of -60 to -30 ° C. A rubber composition containing an ethylene/α-olefin copolymer (Patent Document 2), or one or more tan δ peaks determined by dynamic viscoelasticity measurement exist in the temperature range of -50 to -30 ° C. an ethylene/α-olefin/non-conjugated polyene copolymer having one or more tan δ peaks in the temperature range of 0 to 40° C. as determined by dynamic viscoelasticity measurement, a softening agent, A composition containing a reinforcing filler, a vulcanizing agent, and the like has been proposed (Patent Document 3).

JP 2005-029654 A JP 2007-023258 A Retable 2016/143599

The object of the present invention is to further improve the processability of a copolymer composition for vibration damping materials from the viewpoint of productivity and quality improvement. An object of the present invention is to obtain a copolymer composition for a vibration damping material with an improved balance between vibration damping properties and workability.

That is, the present invention relates to the following [1] to [6].
[1] Structural units derived from ethylene [A], structural units derived from α-olefins [B] having 4 to 20 carbon atoms, and structural units derived from non-conjugated polyene [C], the following (1) An ethylene/α-olefin/non-conjugated polyene copolymer that satisfies ~(4), and 100 parts by mass of the copolymer and 1 to 150 parts by mass of hydrophobic silica. Polymer composition.
(1) the molar ratio [[A]/[B]] between structural units derived from ethylene [A] and structural units derived from α-olefin [B] is from 40/60 to 90/10;
(2) The content of the structural units derived from the non-conjugated polyene [C] is 0.1 to 6.0 mol%, with the total of the structural units of [A], [B] and [C] being 100 mol%. and
(3) Mooney viscosity ML at 125°C ₍₁₊₄₎ 125°C is 5 to 100;
(4) The B value represented by the following formula (i) is 1.20 or more.
B value = ([EX] + 2 [Y]) / [2 x [E] x ([X] + [Y])] (i)
[Here, [E], [X] and [Y] respectively represent the mole fractions of ethylene [A], α-olefins having 4 to 20 carbon atoms [B], and non-conjugated polyene [C], [EX] represents ethylene [A]-C4-C20 α-olefin [B] diad chain fraction. ]
[2] The copolymer composition for vibration damping materials according to item [1], wherein the α-olefin [B] having 4 to 20 carbon atoms is 1-butene.
[3] The copolymer composition for vibration damping materials according to item [1] or [2], further comprising 1 to 200 parts by mass of a non-polar hydrocarbon oil per 100 parts by mass of the copolymer.
[4] A crosslinked product containing the copolymer composition according to any one of items [1] to [3].
[5] A damping material containing the crosslinked product according to item [4].
[6] A damping rubber part for automobiles containing the crosslinked product according to [4].

The copolymer composition for vibration damping material of the present invention has improved adhesion to rolls when processed into a vibration damping material, and the obtained vibration damping material has a high tan δ in a wide temperature range, that is, a wide range of It has damping properties and high strength in the temperature range.

<<Ethylene/α-olefin/non-conjugated polyene copolymer>>
The ethylene/α-olefin/non-conjugated polyene copolymer constituting the copolymer composition for vibration damping materials of the present invention (hereinafter sometimes abbreviated as “copolymer composition”) is ethylene [A ], a structural unit derived from an α-olefin [B] having 4 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene [C], satisfying the following (1) to (4) It is an ethylene/α-olefin/non-conjugated polyene copolymer (hereinafter sometimes abbreviated as “copolymer”).
As for the α-olefin [B] having 4 to 20 carbon atoms and the non-conjugated polyene [C], only one kind may be used, or two or more kinds may be used.

That is, the ethylene/α-olefin/non-conjugated polyene copolymer according to the present invention has a structural unit derived from ethylene [A] and a structure derived from at least one α-olefin [B] having 4 to 20 carbon atoms. and structural units derived from at least one non-conjugated polyene [C].
(1) the molar ratio [[A]/[B]] between structural units derived from ethylene [A] and structural units derived from α-olefin [B] is from 40/60 to 90/10;
(2) The content of the structural units derived from the non-conjugated polyene [C] is 0.1 to 6.0 mol%, with the total of the structural units of [A], [B] and [C] being 100 mol%. and
(3) Mooney viscosity ML at 125°C ₍₁₊₄₎ 125°C is 5 to 100;
(4) B value represented by the following formula (i) is 1.20 or more B value = ([EX] + 2 [Y]) / [2 × [E] × ([X] + [Y]) ] (i)

Here, [E], [X] and [Y] respectively represent the mole fractions of ethylene [A], α-olefins having 4 to 20 carbon atoms [B], and non-conjugated polyene [C], [ EX] indicates the ethylene [A]-α-olefin [B] diad chain fraction of 4 to 20 carbon atoms.

Examples of α-olefins [B] having 4 to 20 carbon atoms include 1-butene having 4 carbon atoms, 1-nonene having 9 carbon atoms, and 1-nonene having 10 carbon atoms and having a linear structure without side chains. Via decene, 1-nonadecene with 19 carbon atoms, 1-eicosene with 20 carbon atoms, and 4-methyl-1-pentene, 9-methyl-1-decene, 11-methyl-1-dodecene and 12 having side chains -ethyl-1-tetradecene and the like.

These α-olefins [B] can be used alone or in combination of two or more. Among these, α-olefins having 4 to 10 carbon atoms are preferred, and 1-butene, 1-hexene, 1-octene and the like are particularly preferred, and 1-butene is particularly preferred.

Ethylene-propylene-non-conjugated polyene copolymers in which the α-olefin is propylene tend to have insufficient rubber elasticity at low temperatures, and their applications may be limited. On the other hand, the ethylene-based copolymer A has a structural unit derived from an α-olefin [B] having 4 to 20 carbon atoms, and therefore has excellent rubber elasticity at low temperatures.

Specific examples of the non-conjugated polyene [C] include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl- Chain nonconjugated dienes such as 1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5- Cyclic non-conjugated dienes such as isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5- norbornene, 2-propenyl-2,5-norbornadiene, 1,3,7-octatriene, 1,4,9-decatriene, 4,8-dimethyl-1,4,8-decatriene, 4-ethylidene-8-methyl Trienes such as -1,7-nonadiene can be mentioned.

These non-conjugated polyenes [C] can be used alone or in combination of two or more.
Among these, linear non-conjugated dienes such as 1,4-hexadiene, cyclic non-conjugated dienes such as 5-ethylidene-2-norbornene, 5-ethylidene-2-norbornene, and 5-vinyl-2-norbornene are preferred, and among them Cyclic non-conjugated dienes are preferred, with 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene being particularly preferred.

Copolymers related to the present invention include the following. Ethylene/1-butene/1,4-hexadiene copolymer, Ethylene/1-pentene/1,4-hexadiene copolymer, Ethylene/1-hexene/1,4-hexadiene copolymer, Ethylene/1- ptene/1,4-hexadiene copolymer, ethylene/1-octene/1,4-hexadiene copolymer, ethylene/1-nonene/1,4-hexadiene copolymer, ethylene/1-decene/1,4 - Hexadiene copolymer, ethylene/1-butene/1-octene/1,4-hexadiene copolymer, ethylene/1-butene/5-ethylidene-2-norbornene copolymer, ethylene/1-pentene/5- ethylidene-2-norbornene copolymer, ethylene/1-hexene/5-ethylidene-2-norbornene copolymer, ethylene/1-heptene/5-ethylidene-2-norbornene copolymer, ethylene/1-octene/ 5-ethylidene-2-norbornene copolymer, ethylene/1-nonene/5-ethylidene-2-norbornene copolymer, ethylene/1-decene/5-ethylidene-2-norbornene copolymer, ethylene/1-butene 1-octene/5-ethylidene-2-norbornene copolymer, ethylene/1-butene/5-ethylidene-2-norbornene/5-vinyl-2-norbornene copolymer, ethylene/1-pentene/5-ethylidene -2-norbornene/5-vinyl-2-norbornene copolymer, ethylene/1-hexene/5-ethylidene-2-norbornene/5-vinyl-2-norbornene copolymer, ethylene/1-heptene/5- Ethylene-2-norbornene/5-vinyl-2-norbornene copolymer, Ethylene/1-octene/5-ethylidene-2-norbornene/5-vinyl-2-norbornene copolymer, Ethylene/1-nonene/5- Ethylene-2-norbornene/5-vinyl-2-norbornene copolymer, Ethylene/1-decene/5-ethylidene-2-norbornene/5-vinyl-2-norbornene copolymer, Ethylene/1-butene/1- Octene/5-ethylidene-2-norbornene/5-vinyl-2-norbornene copolymer.

One type or two or more types of copolymers according to the present invention may be used as necessary.
In the copolymer according to the present invention, (1) the molar ratio [[A]/[B]] between structural units derived from ethylene [A] and structural units derived from α-olefin [B] is 40. /60 to 90/10. The lower limit of [A]/[B] is preferably 45/55, more preferably 50/50, and particularly preferably 55/45. The upper limit of [A]/[B] is preferably 80/20, more preferably 75/25, even more preferably 70/30, and particularly preferably 65/35.

When the molar ratio of the structural unit derived from ethylene [A] and the structural unit derived from α-olefin [B] is within the above range, both rubber elasticity at low temperature and tensile strength at room temperature are well balanced. A polymer is obtained.

In the copolymer according to the present invention, (2) the content of structural units derived from non-conjugated polyene [C] is 100 mol% of the total structural units of [A], [B] and [C], It ranges from 0.1 to 6.0 mol %. The lower limit of the content of structural units derived from [C] is preferably 0.5 mol %. The upper limit of the content of structural units derived from [C] is preferably 4.0 mol%, more preferably 3.5 mol%, and still more preferably 3.0 mol%.

When the content of structural units derived from the non-conjugated polyene [C] is within the above range, a copolymer having sufficient crosslinkability and flexibility can be obtained.
The copolymer according to the present invention has (3) a Mooney viscosity ML ₍₁₊₄₎ 125°C at 125°C of 5 to 100, preferably 20 to 95, particularly preferably 50 to 90.

A copolymer having a Mooney viscosity within the above range has good processability and fluidity, exhibits good post-treatment quality (ribbon handleability), and provides a copolymer having excellent rubber physical properties.

The copolymer according to the present invention has (4) a B value of 1.20 or more, preferably 1.20 to 1.80, particularly preferably 1.22 to 1.40.
Copolymers with a B value of less than 1.20 have a large compression set at low temperatures, and there is a risk that a copolymer having an excellent balance between rubber elasticity at low temperatures and tensile strength at room temperature cannot be obtained. .

A copolymer having a B value within the above range has a high degree of alternating monomer units constituting the copolymer and low crystallinity. Improves vibration performance.

The B value in the above (4) is an index indicating the randomness of the copolymerization monomer chain distribution in the copolymer, and the [E], [X], [Y], [ EX] can be obtained by measuring ¹³ C-NMR spectrum and based on reports by JCRandall [Macromolecules, 15, 353 (1982)], J. Ray [Macromolecules, 10, 773 (1977)]. On the other hand, in (1) to (2) above, the molar amounts of structural units derived from ethylene [A], structural units derived from α-olefin [B] and structural units derived from non-conjugated polyene [C] are It can be determined by intensity measurement with a ¹ H-NMR spectrometer.

<<Method for producing ethylene/α-olefin/non-conjugated polyene copolymer>>
The ethylene/α-olefin/non-conjugated polyene copolymer (copolymer) according to the present invention can be obtained by the following production method.

Specifically, (a) a transition metal compound represented by the following general formula [VII] (hereinafter also referred to as a “bridged metallocene compound”), (b) (b-1) an organometallic compound, and (b-2) In the presence of an olefin polymerization catalyst containing an organoaluminumoxy compound and (b-3) at least one compound selected from compounds that form an ion pair by reacting with the transition metal compound (a), ethylene and the number of carbon atoms The copolymers can be prepared by copolymerizing 4-20 α-olefins with non-conjugated polyenes.

（式［ＶＩＩ］において、
Ｍはチタン原子、ジルコニウム原子またはハフニウム原子であり、
Ｒ⁵およびＲ⁶が、アリール基の水素原子の一つ以上をハメット則の置換基定数σが-0.2以下の電子供与性置換基で置換してなる置換アリール基であって、該電子供与性置換基を複数個有する場合にはそれぞれの該電子供与性置換基は同一でも異なっていてもよく、該電子供与性置換基以外の、炭素数１～２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる置換基を有していてもよく、該置換基を複数個有する場合にはそれぞれの置換基は同一でも異なっていてもよい置換アリール基であり、
Ｑはハロゲン原子、炭素数１～２０の炭化水素基、アニオン配位子および孤立電子対で配位可能な中性配位子から同一のまたは異なる組合せで選ばれ、
ｊは１～４の整数である。）

(In formula [VII],
M is a titanium atom, a zirconium atom or a hafnium atom,
R ⁵ and R ⁶ are substituted aryl groups in which at least one hydrogen atom of the aryl group is substituted with an electron-donating substituent having a Hammett rule substituent constant σ of −0.2 or less, and the electron-donating In the case of having a plurality of substituents, each of the electron-donating substituents may be the same or different, and other than the electron-donating substituents, hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen Substituted aryl which may have a substituent selected from a containing group, an oxygen-containing group, a halogen atom and a halogen-containing group, and in the case of having a plurality of such substituents, each substituent may be the same or different. is the basis,
Q is selected in the same or different combination from a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand and a neutral ligand capable of coordinating with a lone pair;
j is an integer from 1 to 4; )

<Bridged metallocene compound (a)>
As the bridged metallocene compound (a), R ⁵ and R ⁶ are substituted aryl in which one or more hydrogen atoms of an aryl group are substituted with an electron-donating substituent having a Hammett rule substituent constant σ of −0.2 or less. group, and when it has a plurality of said electron-donating substituents, each of said electron-donating substituents may be the same or different, and other than said electron-donating substituents, It may have a substituent selected from a hydrocarbon group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group. Substituted aryl groups, which may be the same or different, can be used.

<Preferred mode for providing a crosslinked metallocene compound to a catalyst for an ethylene/α-olefin/nonconjugated polyene copolymer>
Next, a preferred mode of using the above-mentioned crosslinked metallocene compound as a catalyst for an ethylene/α-olefin/non-conjugated polyene copolymer (olefin polymerization catalyst) will be described.

When a bridged metallocene compound is used as an olefin polymerization catalyst component, the catalyst comprises (a) a bridged metallocene compound represented by the general formula [VII], (b) (b-1) an organometallic compound, and (b-2). at least one compound selected from an organoaluminumoxy compound and (b-3) a compound that forms an ion pair by reacting with the bridged metallocene compound (a), and, if necessary, (c) a particulate carrier Consists of

Each component will be specifically described below.
<(b-1) Organometallic compound>
As (b-1) organometallic compounds, specifically, organometallic compounds of Groups 1 and 2 and Groups 12 and 13 of the periodic table, such as the following general formulas [VIII] to [X], are used.
(b-1a) general formula R ^a _m Al(OR ^b ) _n H _p X _q [VIII]
(In the formula [VIII], R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is 0 < m ≤ 3, n is 0 ≤ n < 3, p is 0 ≤ p < 3, q is a number satisfying 0 ≤ q < 3, and m + n + p + q = 3). .

Such compounds include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, tricycloalkylaluminum, isobutylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methyl Examples include aluminum dichloride, dimethylaluminum chloride, and diisobutylaluminum hydride.

(b-1b) General formula M ² AlR ^a ₄ [IX]
(In the formula [IX], M ² represents Li, Na or K, and R ^a is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.) Complex alkylates of group metals and aluminum.
Examples of such compounds include LiAl(C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ .

(b-1c) general formula R ^a R ^b M ³ [X]
(In the formula [X], R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ³ is Mg, Zn or Cd A dialkyl compound having a Group 2 or Group 12 metal of the periodic table represented by:

Among the above organometallic compounds (b-1), organoaluminum compounds such as triethylaluminum, triisobutylaluminum and tri-n-octylaluminum are preferred. Such organometallic compounds (b-1) may be used singly or in combination of two or more.

<(b-2) Organic aluminum oxy compound>
The (b-2) organoaluminumoxy compound may be a conventionally known aluminoxane, or a benzene-insoluble organoaluminumoxy compound as exemplified in JP-A-2-78687.

Conventionally known aluminoxanes can be produced, for example, by the following method, and are usually obtained as a solution in a hydrocarbon solvent.
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerous chloride hydrate, etc. A method of adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension of (1) and reacting the adsorbed water or water of crystallization with the organoaluminum compound.
(2) A method in which water, ice or steam is directly acted on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may also contain small amounts of organometallic components. Alternatively, the solvent or the unreacted organoaluminum compound may be removed by distillation from the recovered aluminoxane solution, and then redissolved in the solvent or suspended in a poor solvent for the aluminoxane.

Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (b-1a) above.

Among these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum and triisobutylaluminum are particularly preferred.
The organoaluminum compounds as described above may be used singly or in combination of two or more.

(b-2) In the benzene-insoluble organoaluminumoxy compound, which is one embodiment of the organoaluminumoxy compound, the Al component dissolved in benzene at 60° C. is usually 10% by weight or less per 100% by weight of benzene in terms of Al atoms. , preferably 5% by weight or less, particularly preferably 2% by weight or less, that is, those which are insoluble or sparingly soluble in benzene.

As the (b-2) organoaluminum oxy compound, an organoaluminum oxy compound containing boron represented by the following general formula [XI] can also be mentioned.

〔式［ＸＩ］中、Ｒ¹は炭素数が１～１０の炭化水素基を示し、Ｒ²～Ｒ⁵は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素数が１～１０の炭化水素基を示す。〕

[In formula [XI], R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms; R ² to R ⁵ may be the same or different; 10 hydrocarbon groups are shown. ]

The organoaluminumoxy compound containing boron represented by the general formula [XI] is an alkylboronic acid represented by the following general formula [XII],
R ¹ —B(OH) ₂ [XII]
(In formula [XII], R ¹ represents the same group as R ¹ in general formula [XI].)
and an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of −80° C. to room temperature for 1 minute to 24 hours.

Specific examples of alkylboronic acids represented by the general formula [XII] include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid and n-hexylboronic acid. acids, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, 3,5-bis(trifluoromethyl)phenylboronic acid and the like.

Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid and pentafluorophenylboronic acid are preferred. These are used individually by 1 type or in combination of 2 or more types.

Specific examples of the organoaluminum compound to be reacted with such an alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (b-1a) above.

Among these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These are used individually by 1 type or in combination of 2 or more types. The (b-2) organoaluminum oxy compound as described above may be used alone or in combination of two or more.

<(b-3) Compound that forms an ion pair by reacting with transition metal compound (a)>
The compound (b-3) (hereinafter referred to as "ionized ionic compound") that reacts with the transition metal compound (a) to form an ion pair includes JP-A-1-501950 and JP-A-1-502036. Patent Publication, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321106 Lewis acids and ionic compounds described in , borane compounds and carborane compounds. In addition, heteropolycompounds and isopolycompounds may also be mentioned. Such ionized ionic compounds (b-3) may be used singly or in combination of two or more.

Specific examples of Lewis acids include compounds represented by BR ₃ (R is a phenyl group or fluorine optionally having a substituent such as fluorine, a methyl group and a trifluoromethyl group). , for example trifluoroboron, triphenylboron, tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron, tris(pentafluorophenyl)boron, tris( p-tolyl)boron, tris(o-tolyl)boron, tris(3,5-dimethylphenyl)boron and the like.

Examples of the ionic compound include compounds represented by the following general formula [XIII].

（式［ＸＩＩＩ］中、Ｒ¹⁺としては、Ｈ⁺、カルボニウムカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオン、遷移金属を有するフェロセニウムカチオンなどが挙げられる。Ｒ²～Ｒ⁵は、互いに同一でも異なっていてもよく、有機基、好ましくはアリール基または置換アリール基である。）

(In the formula [XIII], R ¹⁺ includes H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, and the like. ² to R ⁵ may be the same or different and are organic groups, preferably aryl groups or substituted aryl groups.)

Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri(n-butyl)ammonium cation;
N,N-dialkylanilinium cations such as N,N-dimethylanilinium cations, N,N-diethylanilinium cations, N,N,2,4,6-pentamethylanilinium cations;
di(isopropyl)ammonium cations, dialkylammonium cations such as dicyclohexylammonium cations, and the like.

Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation.

As R ¹⁺ , carbonium cations, ammonium cations, etc. are preferred, and triphenylcarbonium cations, N,N-dimethylanilinium cations, and N,N-diethylanilinium cations are particularly preferred.

Examples of ionic compounds include trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

Specific examples of trialkyl-substituted ammonium salts include triethylammoniumtetra(phenyl)boron, tripropylammoniumtetra(phenyl)boron, tri(n-butyl)ammoniumtetra(phenyl)boron, trimethylammoniumtetra(p-tolyl) Boron, trimethylammoniumtetra(o-tolyl)boron, tri(n-butyl)ammoniumtetra(pentafluorophenyl)boron, tripropylammoniumtetra(o,p-dimethylphenyl)boron, tri(n-butyl)ammoniumtetra( N,N-dimethylphenyl)boron, tri(n-butyl)ammoniumtetra(p-trifluoromethylphenyl)boron, tri(n-butyl)ammoniumtetra(3,5-ditrifluoromethylphenyl)boron, tri(n -butyl)ammoniumtetra(o-tolyl)boron and the like.

Specific examples of N,N-dialkylanilinium salts include N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)boron, N,N,2,4,6 -pentamethylanilinium tetra(phenyl)boron and the like.

Specific examples of dialkylammonium salts include di(1-propyl)ammoniumtetra(pentafluorophenyl)boron, dicyclohexylammoniumtetra(phenyl)boron and the like.

Furthermore, as ionic compounds, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, ferroceniumtetra(pentafluorophenyl)borate, triphenylcarbeniumpentaphenyl Cyclopentadienyl complexes, N,N-diethylanilinium pentaphenylcyclopentadienyl complexes, boron compounds represented by the following formula [XIV] or [XV], and the like can also be mentioned.

（式［ＸＩＶ］中、Ｅｔはエチル基を示す。）

(In formula [XIV], Et represents an ethyl group.)

（式［ＸＶ］中、Ｅｔはエチル基を示す。）

(In formula [XV], Et represents an ethyl group.)

Specific examples of borane compounds include decaborane; bis[tri(n-butyl)ammonium]nonaborate, bis[tri(n-butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium]undecaborate, salts of anions such as [tri(n-butyl)ammonium] dodecaborate, bis[tri(n-butyl)ammonium]decachlorodecaborate, bis[tri(n-butyl)ammonium]dodecachlorododecaborate; -Butyl) ammonium bis(dodecahydride dodecaborate) cobaltate (III), bis[tri(n-butyl)ammonium] bis(dodecahydride dodecaborate) nickelate (III), and the like salts of metal borane anions, etc. mentioned.

Specific examples of carborane compounds include 4-carbanonabolane, 1,3-dicarbanonabolane, 6,9-dicarbadecaborane, dodecahydride-1-phenyl-1,3-dicarbanonabolane, dodecahydride- 1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarboundecaborane, 2,7-dicarboundecaborane, Undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarbaundecaborate, tri(n-butyl)ammonium 1-carbadecaborate, tri( n-butyl)ammonium-1-carbaundecaborate, tri(n-butyl)ammonium-1-carbadodecaborate, tri(n-butyl)ammonium-1-trimethylsilyl-1-carbadecaborate, tri(n-butyl) ) ammonium bromo-1-carbadodecaborate, tri(n-butyl)ammonium-6-carbadecaborate, tri(n-butyl)ammonium-7-carbaundecaborate, tri(n-butyl)ammonium-7,8 -dicarbaundecaborate, tri(n-butyl)ammonium-2,9-dicarbaundecaborate, tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, tri(n- Butyl)ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri(n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri(n-butyl)ammonium salts of anions such as decahydride-4,6-dibromo-7-carbaundecaborate; tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate) cobaltate (III), (n-butyl) ammonium bis(undecahydride-7,8-dicarboundecaborate) ferrate (III), tri(n-butyl) ammonium bis(undecahydride-7,8-dicarboundecaborate) Cobaltate (III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarboundecaborate)nickelate (III), tri(n-butyl)ammonium bis(undecahydride-7 ,8-dicarbaundecaborate) cuprate (III), tri(n-butyl) ammonium bis(undecahydride-7,8-dicarbaundecaborate) aurate (III), tri(n-butyl) ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) ferrate (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8- dicarboundecaborate) chromate (III), tri(n-butyl) ammonium bis(tribromooctahydride-7,8-dicarboundecaborate) cobaltate (III), tris[tri(n-butyl) ammonium] bis(undecahydride-7-carbaundecaborate) chromate (III), bis[tri(n-butyl)ammonium] bis(undecahydride-7-carbaundecaborate) manganate (IV ), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboundecaborate) cobaltate (III), bis[tri(n-butyl)ammonium]bis(undecahydride-7- salts of metal carborane anions such as carbaundecaborate) nickelate (IV);

The heteropoly compound consists of atoms selected from silicon, phosphorus, titanium, germanium, arsenic and tin and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus tungstic acid, germanotungstic acid, stannotungstic acid, phosphomolybdovanadate, phosphotungstovanadate, germanotungstovanadate, phosphomolybdotungstovanadate, germanomolybdotungstovanadate, phosphomolybdotungstic acid , phosphomolybdoniobic acid, and salts of these acids, such as metals of Groups 1 and 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and organic salts such as triphenylethyl salts can be used, but are not limited to these.

(b-3) Among the ionized ionic compounds, the above-mentioned ionic compounds are preferred, among which triphenylcarbenium tetrakis(pentafluorophenyl)borate and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate. more preferred.

(b-3) Ionization The ionic compounds are used singly or in combination of two or more.
When the transition metal compound (a) represented by the general formula [VII] is used as a catalyst, an organometallic compound (b-1) such as triisobutylaluminum, an organoaluminumoxy compound (b-2) such as methylaluminoxane, or When an ionizing ionic compound (b-3) such as triphenylcarbenium tetrakis(pentafluorophenyl)borate is used together, extremely high polymerization activity is exhibited in the production of an ethylene/α-olefin/nonconjugated polyene copolymer.

The olefin polymerization catalyst is selected from the transition metal compound (a), (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) an ionized ionic compound. A carrier (c) can also be used, if desired, together with at least one compound (b).

<(c) carrier>
In the present invention, the carrier (c), which is optionally used, is an inorganic compound or an organic compound, and is a solid in the form of granules or fine particles.
Among these inorganic compounds, porous oxides, inorganic halides, clays, clay minerals, and ion-exchange layered compounds are preferred.

Specific examples of porous oxides include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , or composites or mixtures containing these. , such as natural or synthetic zeolites, SiO ₂ --MgO, SiO ₂ --Al ₂ O ₃ , SiO ₂ --TiO ₂ , SiO ₂ --V ₂ O ₅ , SiO ₂ --Cr ₂ O ₃ , SiO ₂ --TiO ₂ --MgO, etc. can be used. Among these, those containing SiO ₂ and/or Al ₂ O ₃ as main components are preferred. The properties of such porous oxides vary depending on the type and manufacturing method. 1000 m ² /g, preferably in the range of 100-700 m ² /g, with a pore volume in the range of 0.3-3.0 cm ³ /g. Such a carrier is calcined at 100 to 1000° C., preferably 150 to 700° C., if necessary, before use.

As inorganic halides, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ and the like are used. The inorganic halide may be used as it is, or may be used after pulverizing with a ball mill or vibration mill. Moreover, after dissolving an inorganic halide in a solvent such as alcohol, it is possible to use a product obtained by depositing fine particles using a precipitating agent.

Clay is usually composed mainly of clay minerals. An ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds or the like are stacked in parallel with weak bonding force, and the ions contained therein can be exchanged. Most clay minerals are ion exchange layered compounds. Moreover, as these clays, clay minerals, and ion-exchangeable layered compounds, not only naturally occurring ones but also artificially synthesized ones can be used.

Clays, clay minerals, and ionic crystalline compounds having layered crystal structures such as hexagonal close-packing type, antimony type, _CdCl2 type, and _CdI2 type are used as clays, clay minerals, or ion-exchangeable layered compounds. can be exemplified. Such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudite group, palygorskite, kaolinite, nacrite, and dickite. , halloysite, etc., and the ion-exchangeable layered compounds include α-Zr(HAsO ₄ ) _{2.H 2} O, α-Zr(HPO ₄ ) ₂ , α-Zr(KPO ₄ ) _{2.3H 2} O, α-Ti( _HPO4 ) _{2 ,} α-Ti( _HAsO4 )2.H2O, α-Sn( _HPO4 ) _2.H2O , γ-Zr( _HPO4 ) ₂ , γ _- Ti _{( HPO4} ) ₂ and crystalline acid salts of polyvalent metals such as γ-Ti(NH ₄ PO ₄ ) ₂ ·H ₂ O and the like.

Such a clay, clay mineral or ion-exchange layered compound preferably has a pore volume of 0.1 cc/g or more with a radius of 20 Å or more measured by mercury porosimetry, and preferably 0.3 to 5 cc/g. Especially preferred. Here, the pore volume is measured in the pore radius range of 20 to 30000 Å by mercury porosimetry using a mercury porosimeter.

When a carrier having a pore volume of less than 0.1 cc/g with a radius of 20 Å or more is used, it tends to be difficult to obtain high polymerization activity.
It is also preferable to chemically treat clay and clay minerals. Any chemical treatment can be used, such as a surface treatment for removing impurities adhering to the surface, a treatment for affecting the crystal structure of clay, and the like. Specific examples of chemical treatment include acid treatment, alkali treatment, salt treatment, and organic treatment. The acid treatment removes surface impurities and also elutes cations such as Al, Fe and Mg in the crystal structure to increase the surface area. Alkaline treatment destroys the crystalline structure of the clay, resulting in changes in the clay structure. Also, in salt treatment and organic matter treatment, ionic complexes, molecular complexes, organic derivatives, etc. are formed, and the surface area and interlayer distance can be changed.

The ion-exchangeable layered compound may be a layered compound in which the interlayer spacing is expanded by exchanging the exchangeable ions between the layers with other large bulky ions by utilizing the ion-exchangeability. Such bulky ions play a pillar-like role supporting the layered structure and are usually called pillars. Also, the introduction of another substance between the layers of a layered compound is called intercalation. Guest compounds for intercalation include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti(OR) ₄ , Zr(OR) ₄ , PO(OR) ₃ and B(OR) ₃ ( R is a hydrocarbon group, etc.), metal hydroxide ions such as [ _Al13O4 (OH) ₂₄ ] ⁷⁺ , [ _Zr4 (OH _{) 14} ] ²⁺ , [ _Fe3O ( _OCOCH3 ) ₆ ] ⁺ etc. These compounds are used alone or in combination of two or more. Further, when intercalating these compounds, metal alkoxides (R is a hydrocarbon group, etc.) such as Si(OR) ₄ , Al(OR) ₃ and Ge(OR) ₄ are hydrolyzed. Colloidal inorganic compounds such as polymers and SiO ₂ can also coexist. Examples of pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then dehydrating them by heating.

Clays, clay minerals, and ion-exchangeable layered compounds may be used as they are, or may be used after being subjected to treatments such as ball milling and sieving. Alternatively, water may be newly added and adsorbed, or may be used after heat dehydration treatment. Furthermore, it may be used alone or in combination of two or more.

Among these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, hectorite, taeniolite and synthetic mica.
Examples of organic compounds include granular or particulate solids with particle sizes in the range of 10 to 300 μm. Specifically, (co)polymers produced mainly from α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, and styrene. (Co)polymers produced as the main component and modified products thereof can be exemplified.

The olefin polymerization catalyst is a transition metal compound (a), and at least one compound selected from (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) an ionized ionic compound. It can also contain compound (b) and optionally a carrier (c).

<Method of polymerizing monomers in the presence of catalyst for ethylene/α-olefin/non-conjugated polyene copolymer>
When ethylene, α-olefin, and non-conjugated polyene are copolymerized, the method of use and the order of addition of each component constituting the polymerization catalyst are arbitrarily selected, but the following methods are exemplified.
(1) A method of adding the compound (a) alone to a polymerization vessel.
(2) A method of adding the compound (a) and the compound (b) in any order to the polymerization vessel.
(3) A method in which the catalyst component in which the compound (a) is supported on the carrier (c) and the compound (b) are added in any order to a polymerization vessel.
(4) A method in which the catalyst component in which the compound (b) is supported on the carrier (c) and the compound (a) are added in any order to a polymerization vessel.
(5) A method of adding a catalyst component in which the compound (a) and the compound (b) are supported on the carrier (c) to a polymerization vessel.

In each of the methods (2) to (5) above, at least two of the compound (a), the compound (b) and the carrier (c) may be brought into contact in advance.
In the above methods (4) and (5) in which the compound (b) is supported, the unsupported compound (b) may be added in any order as necessary. In this case, the compound (b) may be the same as or different from the compound (b) supported on the carrier (c).

Further, in the solid catalyst component in which the compound (a) is supported on the carrier (c) and the solid catalyst component in which the compound (a) and the compound (b) are supported on the carrier (c), the olefin is prepolymerized. Alternatively, a catalyst component may be further supported on the prepolymerized solid catalyst component.

In the method for producing an ethylene/α-olefin/non-conjugated polyene copolymer, ethylene, an α-olefin, and a non-conjugated polyene are produced in the presence of the catalyst for the ethylene/α-olefin/non-conjugated polyene copolymer as described above. An ethylene/α-olefin/non-conjugated polyene copolymer can be produced by copolymerizing the above.

The present invention can be carried out by either a liquid phase polymerization method such as solution (dissolution) polymerization or suspension polymerization, or a gas phase polymerization method.
Specific examples of inert hydrocarbon media used in liquid phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, cyclopentane, cyclohexane, and methylcyclopentane. and aromatic hydrocarbons such as benzene, toluene, and xylene, and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, which may be used alone or in combination of two or more. can be done. Also, the olefin itself can be used as a solvent.

When ethylene or the like is polymerized using the copolymer catalyst as described above, the amount of compound (a) is usually 10 ⁻¹² to 10 ⁻² mol, preferably 10 ⁻¹⁰ to 10 mol, per liter of reaction volume. Used in amounts to give ^-8 mol.

In the compound (b-1), the molar ratio [(b-1)/M] of the compound (b-1) to all the transition metal atoms (M) in the compound (a) is usually 0.01 to 50000, It is preferably used in an amount of 0.05 to 10,000. In the compound (b-2), the molar ratio [(b-2)/M] of aluminum atoms in the compound (b-2) and all transition metals (M) in the compound (a) is usually 10 to It is used in an amount of 50,000, preferably 20-10,000. In the compound (b-3), the molar ratio [(b-3)/M] of the compound (b-3) to the transition metal atom (M) in the compound (a) is usually 1 to 20, preferably It is used in an amount such that 1-15.

The polymerization temperature using such a copolymer catalyst is usually -50 to +200°C, preferably 0 to 200°C, more preferably 80 to 200°C. A higher temperature (80° C. or higher) is desirable from the viewpoint of productivity, although it depends on the ultimate molecular weight and polymerization activity of the catalyst system.

The polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous processes. Furthermore, it is also possible to carry out the polymerization in two or more stages with different reaction conditions.

The molecular weight of the resulting copolymer can also be adjusted by allowing hydrogen to exist in the polymerization system or by changing the polymerization temperature. Furthermore, it can also be adjusted by the amount of the compound (b) used. Specific examples include triisobutylaluminum, methylaluminoxane, and diethylzinc. When hydrogen is added, the appropriate amount is about 0.001 to 100 NL per 1 kg of olefin.

《Hydrophobic Silica》
Hydrophobic silica, which is one of the components constituting the copolymer composition of the present invention, is hydrophobic silica surface-treated with a silicon-containing compound, and hydrophobic silica surface-treated with a silicon-containing compound can be used. By this, the adhesion of the copolymer composition can be improved, and the mechanical properties such as tensile strength and elongation of the vibration damping material obtained can be improved.

Examples of silicon-containing compounds for surface treatment of silica include dimethyldichlorosilane, methacryloxysilane, octylsilane, and hexamethyldisilazane. Silazanes are preferred.

The average particle size of the hydrophobic silica (B) is preferably 1 to 50 nm, more preferably 2 to 45 nm, still more preferably 5 to 40 nm. When the average particle size is within the above range, the hydrophobic silica is excellent in dispersibility in the composition. The specific surface area (BED method) of the hydrophobic silica is preferably 50 m ² /g or more, more preferably 100 to 400 m ² /g.

As the silica before the surface treatment, one produced by a known method can be used, but one produced by a dry method or a high-temperature hydrolysis method is preferable. Moreover, the method of surface treatment with hexamethyldisilazane is not particularly limited, and a known method can be applied.

Commercially available products of the hydrophobic silica (B) include, for example, EVONIK Aerosil series R972 and Aerosil RX200, Cabot CAB-O-SIL series TS-610, TS-612, TS-620, TS-622, Tg-709F and the like.

<<Copolymer composition for damping material>>
The copolymer composition for a vibration damping material of the present invention contains 1 to 150 parts by weight, preferably 5 to 140 parts by weight, of the hydrophobic silica per 100 parts by weight of the copolymer. It is preferably in the range of 10 to 120 parts by weight. When the content of hydrophobic silica is within the above range, the effect of improving mechanical strength and workability is excellent.

<Other ingredients>
The copolymer composition of the present invention may contain, in addition to the hydrophobic silica described above, per se known rubber compounding agents, such as non-polar hydrocarbon oils, softeners, and reinforcing agents, as long as the object of the present invention is not compromised. Fillers for fillers, vulcanizing agents (crosslinking agents), metal salts of α,β-unsaturated organic acids, anti-aging agents, cross-linking aids, cross-linking accelerators, fillers, processing aids, activators, antioxidants, Foaming agents, plasticizers, tackifiers and the like can be appropriately added.

<Non-polar hydrocarbon oil>
The non-polar hydrocarbon oil that may be incorporated in the copolymer composition of the present invention preferably has a dynamic viscosity of 1 to 10,000 mm ² /s at 40°C.

An oil having a kinematic viscosity of less than 1 mm ² /s at 40° C. contains a large amount of easily volatilized low-molecular-weight components, and thus may have poor heat resistance. On the other hand, if it exceeds 10,000 mm ² /s, the amount of high molecular weight components increases, the viscosity becomes insufficient, and the effect of improving workability is reduced.

As the non-polar hydrocarbon-based oil according to the present invention, the non-polar hydrocarbon-based oil composed of the ethylene/α-olefin copolymer has compatibility with the ethylene/α-olefin/non-conjugated polyene copolymer according to the present invention. is particularly preferred.

Such a nonpolar hydrocarbon oil composed of an ethylene/α-olefin copolymer is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene linear α-olefins, 4-methyl-pentene, 8-methyl-1-nonene, 7-methyl-1-decene , 6-methyl-1-undecene, 6,8-dimethyl-1-decene and the like, but preferably linear α-olefins, one of these or Two or more types are used as necessary. In addition, such an ethylene/α-olefin copolymer is particularly preferably a random copolymer, and generally contains 5 mol % to 95 mol % of ethylene constitutional units and 95 mol of α-olefin constitutional units. % to 5 mol % (the total of ethylene and α-olefin is 100 mol %).

Further, such an ethylene/α-olefin copolymer generally has a number average molecular weight (Mn) of 100 to 30,000, preferably 100 to 20,000.
If the number-average molecular weight (Mn) is less than 100, the amount of easily volatile low-molecular-weight components increases, possibly deteriorating the heat resistance. On the other hand, if the number average molecular weight (Mn) exceeds 30,000, the amount of high molecular weight components increases, and the effect of improving workability decreases.

Further, its molecular weight distribution (Mw/Mn) is generally from 1.1 to 3, with 1.1 to 2.5 being preferred.
If the molecular weight distribution (Mw/Mn) exceeds 3, the amount of low molecular weight components that are generally easily volatilized increases, and the heat resistance may deteriorate.

Furthermore, the content of unsaturated groups at one end of the molecule in such an ethylene/α-olefin copolymer is 10% or less, preferably 5% or less, more preferably 1% or less.
Methods for producing these ethylene/α-olefin copolymers include JP-A-3-179005, JP-A-3-193796, JP-A-6-122718, JP-A-8-239414 and JP-A-8-239414. There is a method using a catalyst used in producing an α-olefin polymer, as described in JP-A-10-087716 and JP-A-2000-212194.

When the copolymer composition of the present invention contains a non-polar hydrocarbon oil, the content thereof is 1 to 200 parts by mass, preferably 20 to 150 parts by mass, based on 100 parts by mass of the copolymer. It is preferably 20 to 100 parts by mass.
When the copolymer composition of the present invention contains a non-polar hydrocarbon oil, mechanical strength and workability can be balanced.

<Softener>
Examples of softening agents according to the present invention include process oils such as paraffin oil (eg, "Diana Process Oil PS-430" (trade name: manufactured by Idemitsu Kosan Co., Ltd.)), lubricating oils, liquid paraffin, petroleum asphalt, and vaseline. Coal tar softeners such as coal tar and coal tar pitch; Fatty oil softeners such as castor oil, linseed oil, rapeseed oil, soybean oil, and coconut oil; beeswax, carnauba wax, and waxes such as 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 Synthetic polymeric substances such as resins, atactic polypropylene, and coumarone-indene resins; Ester-based softeners such as dioctyl phthalate, dioctyl adipate, and dioctyl sebacate; Others, microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, liquid thiocol , tall oil, and sub (factus). Among these, petroleum-based softening agents are preferred, and process oils, particularly paraffin oil, are preferred. The softening agents may be used alone or in combination of two or more.

When the copolymer composition of the present invention contains a softening agent, its content is 5 to 300 parts by weight, preferably 10 to 250 parts by weight, more preferably 20 to 230 parts by weight, based on 100 parts by weight of the copolymer. part by mass.

<Reinforcing filler>
Specific examples of reinforcing fillers include commercially available “Asahi #55G” and “Asahi #50HG” (trade name: manufactured by Asahi Carbon Co., Ltd.), “Seist (trade name)” series: SRF, GPF , FEF, MAF, HAF, ISAF, SAF, FT, MT and other carbon blacks (manufactured by Tokai Carbon Co., Ltd.), these carbon blacks surface-treated with a silane coupling agent or the like, mica, talc, silica and clay, etc. can be used. Among these, carbon blacks of "Asahi #60G", "Asahi #80" and "Siest HAF" are preferred.

When the copolymer composition of the present invention contains a reinforcing filler, the content thereof is 10 to 300 parts by mass, preferably 20 to 280 parts by mass, more preferably 30 parts by mass with respect to 100 parts by mass of the copolymer. ~260 parts by mass.

<Vulcanizing agent>
As vulcanizing agents (crosslinking agents), sulfur, sulfur compounds, organic peroxides, phenolic resins, oxime compounds, and the like can be used.
Examples of sulfur compounds include sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dithiocarbamate. Among sulfur and sulfur-based compounds, sulfur and tetramethylthiuram disulfide are preferred.

Examples of the organic peroxide include dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2, Examples include 5-diethyl-2,5-di(t-butylperoxy)hexyne-3, di-t-butylperoxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-dibutylhydroperoxide and the like. can. Among these, dicumyl peroxide, di-t-butyl peroxide and di-t-butylperoxy-3,3,5-trimethylcyclohexane are preferred.

When the copolymer composition of the present invention contains a vulcanizing agent, its content is 0.1 to 10 parts by mass, preferably 0.3 to 9.0 parts by mass, per 100 parts by mass of the copolymer. 0 parts by mass, more preferably 0.5 to 8.0 parts by mass.
When the copolymer composition of the present invention contains a sulfur compound as a vulcanizing agent, it is preferable to use a vulcanization accelerator in combination.

<Vulcanization accelerator>
Vulcanization accelerators include N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene-2-benzothiazolesulfenamide, N,N'-diisopropyl-2-benzothiazolesulfenamide, 2-mercapto Benzothiazole (e.g., "Sancellar M" (trade name: manufactured by Sanshin Chemical Industry Co., Ltd.), etc.), 2-(4-morpholinodithio) benzothiazole (e.g., "Noccellar MDB-P" (trade name: Sanshin Chemical Industry Co., Ltd.), 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-diethyl-4-morpholinothio)benzothiazole, thiazoles such as dibenzothiazyl disulfide; Guanidines such as diphenylguanidine, triphenylguanidine and diorthotolylguanidine; acetaldehyde-aniline condensates, butyraldehyde-aniline condensates, aldehyde amines; imidazolines such as 2-mercaptoimidazoline; thioureas such as diethylthiourea and dibutylthiourea Thiuram system such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate (for example, "Sancellar PZ" (product name: manufactured by Sanshin Chemical Industry Co., Ltd.) , "Suncellar BZ" (product name: manufactured by Sanshin Chemical Industry Co., Ltd.), etc.), dithioate salts such as tellurium diethyldithiocarbamate; ), "Suncellar 22-C" (product name: manufactured by Sanshin Chemical Industry Co., Ltd.), etc.), N,N'-diethylthiourea and other thiourea-based products; xanthate-based products such as zinc dibutylxathate; For example, zinc oxide such as “META-Z102” (trade name: manufactured by Inoue Lime Industry Co., Ltd.).
The content of these vulcanization accelerators is 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the copolymer. be.

<Vulcanization aid>
The copolymer composition of the present invention may further contain a vulcanization aid. Specific examples of vulcanization aids include magnesium oxide and zinc white (for example, zinc oxide such as "META-Z102" (trade name: manufactured by Inoue Lime Industry Co., Ltd.)). Examples of vulcanizing aids include quinonedioxime-based agents such as p-quinonedioxime; acrylic-based agents such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; allyl-based agents such as diallyl phthalate and triallyl isocyanurate; divinylbenzene and the like. The vulcanization auxiliaries may be used alone or in combination of two or more. The content of the vulcanization aid is usually 1 to 20 parts by weight per 100 parts by weight of the copolymer.

As fillers other than reinforcing fillers, light calcium carbonate, heavy calcium carbonate, talc, clay and the like can be used. Among these, ground calcium carbonate is preferred. Commercially available “Whiten SB” (trade name: Shiraishi Calcium Co., Ltd.) and the like can be used as heavy calcium carbonate. The content of the filler is usually 30 to 300 parts by mass, preferably 50 to 250 parts by mass, and more preferably 70 to 230 parts by mass with respect to 100 parts by mass of the copolymer.

<Processing aid>
The copolymer composition of the present invention may further contain processing aids.
As the processing aid, a wide range of processing aids generally blended with rubber can be used. Specific examples include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, and esters. Among these, stearic acid is preferred.

When the copolymer composition of the present invention contains a processing aid, the blending amount thereof is 10 parts by mass or less, preferably 8.0 parts by mass or less, more preferably 5.0 parts by mass or less per 100 parts by mass of the copolymer. The amount is 0 parts by mass or less.

<Activator>
The copolymer composition of the present invention may further contain active agents.
Specific examples of active agents include di-n-butylamine, dicyclohexylamine, monoelanolamine, "Acting B" (trade name: manufactured by Yoshitomi Pharmaceutical Co., Ltd.), and "Acting SL" (trade name: Yoshitomi Pharmaceutical Co., Ltd.). ); amines such as diethylene glycol, polyethylene glycol (e.g., "PEG#4000" (manufactured by Lion Corporation)), lecithin, triarylate melitate, zinc compounds of aliphatic and aromatic carboxylic acids (e.g., "Struktol activator 73”, “Struktol IB 531” and “Struktol FA541” (trade name: manufactured by Schill &Seilacher); Zinc peroxide preparations such as “ZEONET ZP” (trade name: manufactured by Nippon Zeon Co., Ltd.) ; Octadecyltrimethylammonium bromide, synthetic hydrotalcite, special quaternary ammonium compounds (for example, "Arkard 2HF" (trade name: manufactured by Lion Akzo Co., Ltd.)) and the like. Among these, polyethylene glycol (for example, "PEG#4000" (manufactured by Lion Corporation) and "Arcade 2HF" are preferred. The active agents can be used alone or in combination of two or more.

When the copolymer composition of the present invention contains an active agent, the amount thereof is 0.2 to 10 parts by weight, preferably 0.3 to 5 parts by weight, more preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the copolymer. is 0.5 to 4 parts by mass.

<Moisture absorbent>
The copolymer composition of the present invention may further contain a moisture absorbent.
Specific examples of moisture absorbents include calcium oxide, silica gel, sodium sulfate, molecular sieves, zeolite, white carbon, and the like. Among these, calcium oxide is preferred. Moisture absorbents can be used alone or in combination of two or more.

When the copolymer composition of the present invention contains a moisture absorbent, its content is 0.5 to 15 parts by mass, preferably 1.0 to 12 parts by mass, more preferably 1.0 to 12 parts by mass, based on 100 parts by mass of the copolymer. is 1.0 to 10 parts by mass.

<Crosslinking method>
The crosslinked product of the present invention is obtained by crosslinking the copolymer composition. For example, the above copolymer, hydrophobic silica, and other components are kneaded to prepare a copolymer composition, this composition is cut into sheets, and then heated at 140 to 230° C. using a hot press. A crosslinked olefin polymer is obtained by heating for 2 to 30 minutes. The lower limit temperature of the temperature range is preferably 150°C, more preferably 160°C, and the upper limit temperature is preferably 220°C, more preferably 200°C.

A raw material composition that is not crosslinked is easily deformed by an external stress and cannot return to its original shape, so it is not practical as a molding material. A crosslinked body obtained by crosslinking the composition has high practicality as a molding material. A criterion for being a crosslinked body is that the tensile stress at break exceeds 5 MPa. If the tensile stress at break exceeds 5 MPa, it is considered that there is no practical problem from the standpoint of removal from the mold, installation of the product, and long-term use.

<Durometer hardness>
The durometer hardness (value immediately after measurement) of the crosslinked product of the present invention is 50-80, preferably 55-78, more preferably 58-75. Since the crosslinked product of the present invention is formed from the composition having the above composition, it has a high durometer hardness (value immediately after measurement) of 50-80. The method for measuring the durometer hardness (value immediately after measurement) was described in detail in Examples. When the durometer hardness (value immediately after measurement) is 50 or more, sticking due to surface tackiness between the crosslinked bodies is reduced, so the handleability is excellent, and it can also be used for high-load applications. On the other hand, when the durometer hardness (value immediately after measurement) exceeds 80, the impact resilience tends to increase and the impact absorption tends to decrease.

Durometer hardness (value 15 seconds after measurement) is not particularly limited, but the crosslinked body of the present invention has a difference of 7 or more between durometer hardness (value immediately after measurement) and durometer hardness (value 15 seconds after measurement). is preferable because it exhibits excellent conformability to irregularities, can be well adhered to the base material, and can exhibit its damping properties, shock absorption, and vibration absorption functions to the maximum extent.

<Dynamic viscoelasticity>
In the crosslinked body of the present invention, the temperature profile of tan δ obtained by measuring the temperature dependence of dynamic viscoelasticity under the conditions of 1 Hz, 0.5%, -70 to 100 ° C. and a heating rate of 4 ° C./min is bimodal, and the tan δ peak preferably satisfies the following requirements (1) and (2), and more preferably satisfies requirement (3).
(1) The peak on the low temperature side exists in the temperature range of -50°C or more and less than -10°C.
(2) A peak on the high temperature side exists in the temperature range of -10 to 40°C.
(3) [The value of tan δ in the peak present in the temperature range of -10°C to 40°C] ≥ [The value of tan δ in the peak present in the temperature range of -50°C or higher and below -10°C]
The temperature profile of tan δ is bimodal, and the peak of tan δ satisfies the requirements (1) and (2), thereby achieving higher hardness and low impact resilience, and requirements (3) and (2). By satisfying the above, even higher hardness and low impact resilience can be achieved.

<Use of crosslinked product>
The crosslinked body of the present invention has high hardness and low impact resilience. That is, both high hardness and low impact resilience are achieved. In particular, both a high durometer hardness of 50 to 80 and a low impact resilience of 20% or less are achieved.

Therefore, various products having both high hardness and low impact resilience can be obtained from the crosslinked product of the present invention. Examples of the products include damping members, shock absorbers, vibration absorbers, resonance suppressors, and the like. The crosslinked body of the present invention can be suitably used in fields where vibration damping is required for automobiles, railroads, aircraft, electrical and electronic equipment, various precision equipment, etc., and in particular, where both high hardness and low impact resilience are required. can.

For molding various products, known molding methods such as injection molding, various extrusion molding, compression molding, calendar molding and vacuum molding can be used.
A foamed molded product can also be obtained by foaming by a known method using a chemical foaming agent or a physical foaming agent at the time of molding. As the foaming agent, a known chemical foaming agent or a known physical foaming agent such as carbon dioxide gas, nitrogen gas, or water can be used.

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. Numerical values relating to components in the table below indicate parts by mass.
The ethylene/α-olefin/non-conjugated polyene copolymers and the like used in Examples and Comparative Examples are shown below.

<Ethylene/α-olefin/non-conjugated polyene copolymer>]
(1) Ethylene/1-butene/ENB copolymer (EBDM-1)
As the ethylene/α-olefin/non-conjugated polyene copolymer, an ethylene/1-butene/ENB copolymer having the following physical properties in the same manner as described in [Synthesis Example C1] of WO 2015/122415 is used. Obtained. Hereinafter, this will be referred to as "EBDM-1".
The structure and physical properties of EBDM-1 are as follows.
Structural unit derived from ethylene: 67.7 mol%
Structural unit derived from 1-butene: 30.0 mol%
Structural unit derived from 5-ethylidene-2-norbornene: 2.3 mol%
Mooney viscosity ML(1+4) 100°C: 30
B value: 1.3

(2) Ethylene/propylene/ENB copolymer (3092M)
Mitsui Chemicals product name Mitsui EPT ^TM 3092M: ML (1+4) 125°C: 61, ethylene content: 65% by weight (75.29 mol%), ethylene/propylene (molar ratio) = 76.2/23.8, ENB : 4.6% by weight (1.24 mol%)
The physical properties of the copolymer compositions for vibration damping materials used in Examples and Comparative Examples were measured by the following methods.

〔hardness〕
Crosslinked sheets having a thickness of 2 mm obtained in Examples and Comparative Examples were punched in the longitudinal direction with a No. 3 dumbbell described in JIS K 6251 (1993) to obtain test pieces. Six flat portions of the test piece were stacked to a thickness of 12 mm, and the hardness (JIS-A) was measured according to JIS K6253.

[Tensile test: tensile stress at break, tensile elongation at break]
A No. 3 dumbbell test piece described in JIS K6251 (1993) was prepared by punching the crosslinked sheets obtained in Examples and Comparative Examples, and using this test piece, JIS K6251 Section 3 According to the method, a tensile test was performed under conditions of a measurement temperature of 25° C. and a tensile speed of 500 mm/min to measure the tensile stress at break (TB) and tensile elongation at break (EB).

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

[Compression set]
A test piece for compression set (CS) measurement was obtained by vulcanizing a right cylindrical test piece having a thickness of 12.7 mm and a diameter of 29 mm at 170° C. for 15 minutes. The obtained test piece was treated for 70 hours at 160° C. according to JIS K6262 (1997), and the compression set was measured.

[Roll workability]
The roll processability of the copolymer composition for vibration damping materials was evaluated by processing Formulation 1 into an 8-inch roll (front roll surface temperature 80 ° C., rear roll surface temperature 80 ° C., front roll rotation speed 16 rpm, rear roll 18 rpm), and the adhesiveness between the roll and compound 1 was evaluated.
Hard and unworkable.
Although it wraps around the roll, it is highly sticky and difficult to process.
It has good winding properties on rolls, and eases stickiness, making it easy to process.

[Example 1]
Using MIXTRON BB MIXER (manufactured by Kobe Steel, Ltd., BB-2 type, volume 1.7 L, rotor 2WH), 100 parts by mass of EBDM-1 was added with active zinc oxide (trade name: meta -Z 102, manufactured by Inoue Lime Co., Ltd.) 5 parts by mass, stearic acid (manufactured by NOF Corporation) as a processing aid 2 parts by mass, polyethylene glycol (trade name: PEG # 4000, manufactured by Lion Corporation) 1 part by mass, 2 parts by mass of a higher fatty acid ester (trade name: Structol WB212, manufactured by S&S Japan Co., Ltd.) as a processing aid, and 2 parts by mass of a pseudo-gelling agent (trade name: NHM-007, manufactured by Mitsui Chemicals, Inc.) as an anti-gelling agent. part, 28 parts by mass of calcium carbonate (trade name: Silver W, manufactured by Shiraishi Calcium Co., Ltd.), 5 parts by mass of carbon black (trade name: Seast G-SO, manufactured by Tokai Carbon Co., Ltd.), and surface-treated with hexamethyldisilazane. 103 parts by mass of hydrophobic silica (trade name: Aerosil RX200, manufactured by Nippon Aerosil Co., Ltd.) and 52 parts by mass of non-polar hydrocarbon oil (trade name: Lucant (registered trademark) HC-2000, manufactured by Mitsui Chemicals). After that, the mixture was kneaded to obtain a compound 1.

The kneading conditions for the preparation of Compound 1 were a rotor speed of 40 rpm, a floating weight pressure of 3 kg/cm ² , a kneading time of 5 minutes, and a kneading discharge temperature of 144°C.
The Mooney viscosity ML(1+4) 125° C. of Formulation 1 was measured using a Mooney viscometer (Model SMV202 manufactured by Shimadzu Corporation) according to JIS K6300 (1994).

Next, after confirming that the temperature of compound 1 has reached 40 ° C., a 6-inch roll is used to add Suncellar CZ (trade name) [Sanshin Chemical Industry Co., Ltd. 1 part by mass of Suncellar BZ (trade name) [Sanshin Chemical Industry Co., Ltd.], 1.5 parts by mass of Suncellar TT (trade name) [Sanshin Chemical Industry Co., Ltd.] , 0.7 parts by mass of Suncellar TRA (trade name) [Sanshin Chemical Industry Co., Ltd.], 0.15 parts by mass of Suncellar TE (trade name) [Sanshin Chemical Industry Co., Ltd.], and Sanfer R (product 1.4 parts by mass of [Sanshin Chemical Industry Co., Ltd.] and 0.27 parts by mass of sulfur as a cross-linking agent were added and kneaded to obtain a compound 2.

The kneading conditions for the preparation of compound 2 were: roll temperature front roll/back roll = 50°C/50°C, roll peripheral speed front roll/back roll = 18 rpm/15 rpm, roll gap 3 mm, kneading time 8 minutes. to obtain Formulation 2.

Formulation 2 was pressed using a press molding machine at 170° C. for 15 minutes to prepare a crosslinked sheet with a thickness of 2 mm. The obtained crosslinked sheet was subjected to a hardness test, a tensile test, a heat aging resistance test and a Gehmann twist test, which will be described later.

Formulation 2 was pressed at 170 ° C. for 20 minutes using a press molding machine equipped with a cylindrical mold to prepare a right cylindrical test piece with a thickness of 12.7 mm and a diameter of 29 mm. Then, a test piece for compression set (CS) measurement was obtained.

[Comparative Example 1]
EBDM-1 used in Example 1 was replaced with 3092M, and the type and amount of the compounding agent were replaced with the compounding agent and compounding amount shown in Table 1 to obtain a copolymer composition for vibration damping materials. was used, the composition was hard and could not be wound around a roll, could not be rolled, and could not be sampled for evaluation of physical properties.

[Comparative Example 2]
A copolymer composition for vibration damping materials was obtained in the same manner as in Example 1 except that the compounding agents listed in Table 1 were used instead of the copolymer composition for vibration damping materials used in Example 1. . The physical properties of the resulting copolymer composition for vibration damping materials were evaluated by the methods described above.
Table 1 shows the results.

Claims (6)

Including a structural unit derived from ethylene [A], a structural unit derived from an α-olefin [B] having 4 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene [C], the following (1) to (4 ), and a copolymer composition for vibration damping materials, comprising 100 parts by mass of said copolymer and 1 to 150 parts by mass of hydrophobic silica. thing.
(1) the molar ratio [[A]/[B]] between structural units derived from ethylene [A] and structural units derived from α-olefin [B] is from 40/60 to 90/10;
(2) The content of the structural units derived from the non-conjugated polyene [C] is 0.1 to 6.0 mol%, with the total of the structural units of [A], [B] and [C] being 100 mol%. and
(3) Mooney viscosity ML at 125°C ₍₁₊₄₎ 125°C is 5 to 100;
(4) The B value represented by the following formula (i) is 1.20 or more.
B value = ([EX] + 2 [Y]) / [2 x [E] x ([X] + [Y])] (i)
[Here, [E], [X] and [Y] respectively represent the mole fractions of ethylene [A], α-olefins having 4 to 20 carbon atoms [B], and non-conjugated polyene [C], [EX] represents ethylene [A]-C4-C20 α-olefin [B] diad chain fraction. ] 2. The copolymer composition for vibration damping material according to claim 1, wherein the α-olefin [B] having 4 to 20 carbon atoms is 1-butene. 3. The copolymer composition for vibration damping materials according to claim 1, further comprising 1 to 200 parts by mass of a non-polar hydrocarbon oil per 100 parts by mass of the copolymer. A crosslinked product comprising the copolymer composition according to any one of claims 1 to 3. A damping material comprising the crosslinked body according to claim 4 . A damping rubber part for automobiles comprising the crosslinked product according to claim 4 .