JP3150181B2 - Damping material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vibration damping material which exhibits excellent vibration damping properties over a wide temperature range and can be effectively used in various fields such as automobiles and home appliances.

[0002]

2. Description of the Related Art In recent years,
Vibration and noise caused by transportation such as automobiles have become a problem. In addition, low vibration and low noise are required in fields such as automobiles, office equipment, and household electric appliances. Conventionally, as a means for reducing such noise and vibration, a method of suppressing the transmission of vibration using a spring, a vibration-proof rubber, or the like has been frequently used, but its effect has not been sufficient.

[0003] On the other hand, a method called vibration suppression for suppressing vibration itself has been conventionally used. In this method, by attaching a damping material made of a viscoelastic body to a vibrating material,
This is a method of suppressing the occurrence of vibration. Examples of such a vibration damping material include polyester-based (JP-A-62-295949), polyamide-based (JP-A-56-159160), and epoxy resin-based (Japanese Patent Publication No. 58-23426). Stuff has been proposed. However, these damping materials are difficult to form, process,
It did not sufficiently meet various requirements such as vibration damping performance.

On the other hand, in order to solve the above-mentioned problem of the vibration damping material, it has been proposed to use a specific block copolymer as a material of the vibration damping material (Japanese Patent Laid-Open No. 63-254657). However, although this vibration damping material has a relatively wide temperature range showing the vibration damping performance, there is a problem that it does not function sufficiently as a vibration damping material depending on the operating temperature.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a vibration damping material exhibiting excellent vibration damping performance in a wide temperature range.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that a specific cyclic olefin having a glass transition temperature (Tg) of 25 ° C. or less and a melting point of 90 ° C. or less is used. When a copolymer is used as the material of the damping material, the glass transition temperature (Tg) can be arbitrarily controlled in accordance with the operating temperature of the damping material, and the vibration absorbing effect at the operating temperature can be maximized. The present inventors have found that it is possible to increase the elastic modulus and lower the elastic modulus, thereby obtaining a vibration damping material exhibiting excellent vibration damping performance in a wide temperature range, and have accomplished the present invention.

Accordingly, the present invention is a copolymer obtained by copolymerizing a cyclic olefin and an α-olefin, having a glass transition temperature (Tg) of 25 ° C. or less and a melting point of 90 ° C.
Provided is a vibration damping material comprising a cyclic olefin-based copolymer having a temperature of not more than ° C. In this case, it is more preferable that the cyclic olefin-based copolymer has a tensile modulus of 2000 kg / cm ² or less.

[0008] It is a random copolymer of a specific cyclic olefin and ethylene, and has a glass transition temperature (Tg).
Are known in the range of 20 to 80 ° C or 10 to 130 ° C (JP-A-61-211315, JP-A-62-252406).
No.). However, this copolymer is different from the cyclic olefin-based copolymer used in the present invention in that the one having a low glass transition temperature (Tg) has a high melting point, and has a high elastic modulus. Improper.

Hereinafter, the present invention will be described in more detail.
The vibration damping material of the present invention comprises a cyclic olefin-based copolymer obtained by copolymerizing a cyclic olefin and an α-olefin. Here, the α-olefin is not necessarily limited, but for example, the following general formula [X]

Embedded image (In the formula [X], Ra represents ^a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms). In the repeating unit represented by the general formula [X], ^Ra represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

Here, as the hydrocarbon group having 1 to 20 carbon atoms, specifically, for example, methyl group, ethyl group, isopropyl group, n-propyl group, isobutyl group, n-butyl group, n-hexyl group, Examples include an octyl group and an octadecyl group. Specific examples of the α-olefin that provides a repeating unit represented by the general formula [X] include:
For example, ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, decene, eicosene and the like can be mentioned.

The cyclic olefin is not particularly limited, but may be, for example, a compound represented by the following general formula [Y]:

Embedded image (In the formula [Y], R ^{b to} R ^m each represent a hydrogen atom and a carbon atom of 1;
Represents a hydrocarbon group or a substituent containing a halogen atom, an oxygen atom or a nitrogen atom, and n represents an integer of 0 or more. R ^j or R ^k and R ^l or R ^m may form a ring with each other. R ^{b to} R ^m may be the same or different from each other. )). In the repeating unit represented by the general formula [Y], R ^{b to} R ^m each represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a substituent containing a halogen atom, an oxygen atom or a nitrogen atom. .

Here, specific examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and the like. An alkyl group having 1 to 20 carbon atoms such as a hexyl group, an aryl group having 6 to 20 carbon atoms such as a phenyl group, a tolyl group, a benzyl group, an alkylaryl group or an arylalkyl group, a methylidene group, an ethylidene group, a propylidene group; Examples thereof include an alkenyl group having 2 to 20 carbon atoms such as an alkylidene group having 1 to 20 carbon atoms, a vinyl group and an allyl group. ^{However, R b, R c, R} f, R g excluding an alkylidene group. When any one of R ^d , R ^e , and R ^{h to} R ^m is an alkylidene group, the carbon atom to which it is bonded has no other substituent.

Specific examples of the substituent containing a halogen atom include halogen groups having 1 to 20 carbon atoms such as halogen groups such as fluorine, chlorine, bromine and iodine, and chloromethyl, bromomethyl and chloroethyl groups. Examples include an alkyl group. Specific examples of the substituent containing an oxygen atom include, for example, an alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a phenoxy group, and a carbon atom having 1 to 20 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group. And the like. Specifically as a substituent containing a nitrogen atom,
Examples thereof include an alkylamino group having 1 to 20 carbon atoms such as a dimethylamino group and a diethylamino group, and a cyano group.

Specific examples of the cyclic olefin giving the repeating unit represented by the general formula [Y] include, for example, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, -Methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene, 5-
Phenylnorbornene, 5-benzylnorbornene, 5
-Ethylidene norbornene, 5-vinyl norbornene,
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-methyl-
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-ethyl-
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4
4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4
4a, 5,8,8a-octahydronaphthalene, 1,5
-Dimethyl-1,4,5,8-dimetano-1,2,3
4,4a, 5,8,8a-octahydronaphthalene, 2
-Cyclohexyl-1,4,5,8-dimetano-1,
2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Octahydronaphthalene, 1,2-dihydrodicyclopentadiene,
5-chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene,
5,6-dicarboxyl norbornene anhydrate, 5-dimethylamino norbornene, 5-cyano norbornene and the like can be mentioned.

The cyclic olefin copolymer used in the present invention is basically obtained by copolymerizing an α-olefin and a cyclic olefin as described above. In addition to these two essential components,
If necessary, another copolymerizable unsaturated monomer component may be used. As such an unsaturated monomer which may be optionally copolymerized, specifically, among the above-mentioned α-olefin components, those not previously used, among the above-mentioned cyclic olefin components, Examples thereof include those not used, cyclic dienes such as dicyclopentadiene and norbornadiene, chain dienes such as butadiene, isoprene, and 1,5-hexadiene, and monocyclic olefins such as cyclopentene and cycloheptene.

The glass transition temperature (Tg) of the cyclic olefin copolymer must be 25 ° C. or less. When such a copolymer is used, the ratio of the loss modulus (E ″) to the storage modulus (E ′), that is, the loss tangent (tan)
δ = E ″ / E ′) exists in a daily use temperature range, so that vibration energy can be converted into heat energy with high efficiency.More preferable glass transition temperature (Tg)
Is -20 to 20C, particularly -10 to 15C. In this case, the cyclic olefin-based copolymer used in the present invention can control the glass transition temperature (Tg) arbitrarily by changing the type and composition of the monomer, and is used for the intended application and use. Glass transition temperature (Tg) depending on temperature, etc.
Can be changed arbitrarily.

Further, the cyclic olefin-based copolymer is D
The melting point by SC is preferably 90 ° C. or lower, particularly preferably 10 to 85 ° C., particularly preferably 20 to 80 ° C. In this case, the cyclic olefin-based copolymer preferably has a broad melting peak of less than 90 ° C. by DSC. Copolymers whose DSC has a sharp melting peak at 90 ° C. or higher have insufficient uniformity of copolymerization of cyclic olefin and α-olefin, and have poor vibration absorption when molded into a vibration damping material. May be enough. In the DSC measurement, the melting point (melting peak) of the cyclic olefin-based copolymer used in the present invention is not sharply observed. No peak.

In the cyclic olefin-based copolymer used in the present invention, the ratio of the content [x] of the repeating unit derived from α-olefin and the content [y] of the repeating unit derived from cyclic olefin ([x]: [Y]) differs depending on the type and combination of the α-olefin and the cyclic olefin, and cannot be generally specified, but is usually 70 to 99.8 mol%: 30 to 0.2 mol%, preferably 80 to 99 mol%: 20 to 1 mol%. When the content [y] of the cyclic olefin repeating unit is more than 30 mol% or less than 0.2 mol%, the vibration damping material may have insufficient vibration absorption.

The cyclic olefin copolymer is a substantially linear copolymer in which repeating units derived from an α-olefin and repeating units derived from a cyclic olefin are randomly arranged, and has a gel-like crosslinked structure. It is preferable that it does not have. The absence of a gel-like crosslinked structure can be confirmed by the fact that the copolymer is completely dissolved in decalin at 135 ° C.

The cyclic olefin copolymer has an intrinsic viscosity [η] of 0.005 to 2 as measured in decalin at 135 ° C.
It is preferably 0 dl / g. If the intrinsic viscosity [η] is less than 0.005 dl / g, the strength of the vibration damping material may decrease, and if it exceeds 20 dl / g, the formability of the vibration damping material may deteriorate. More preferred intrinsic viscosity [η]
Is 0.05 to 10 dl / g.

The molecular weight of the cyclic olefin copolymer is not particularly limited, but the weight average molecular weight Mw measured by gel permeation chromatography (GPC) is 1,000 to 2,000,000, Especially 5,000 to 1,000,000, number average molecular weight Mn
Is 500 to 1,000,000, especially 2,000 to 80
000, and a molecular weight distribution (Mw / Mn) of 1.3.
To 4, particularly preferably 1.4 to 3. When the molecular weight distribution (Mw / Mn) is more than 4, the content of the low molecular weight substance increases, which may cause the surface to become sticky when molded into a vibration damping material.

Further, the cyclic olefin copolymer preferably has a crystallinity of 0 to 40% as measured by an X-ray diffraction method. If the crystallinity exceeds 40%, the vibration absorption of the vibration damping material may decrease. A more preferred crystallinity is 0 to 30%, particularly 0 to 25%.

The cyclic olefin copolymer used in the present invention preferably has a tensile modulus of 2000 kg / cm ² or less. The tensile modulus is 2000Kg / cm ²
If it exceeds 3, when used as a damping material, the flexibility may be insufficient. More preferred tensile modulus is 50 to 1,
500 kg / cm ² , especially 100-1300 kg / c
m ² .

The cyclic olefin-based copolymer used in the present invention may be a copolymer consisting of only those having the physical properties in the above-mentioned range. In this case, the glass transition temperature (Tg) is 25 ° C. or less. It may be a mixture of copolymers having certain different Tg. Further, the copolymer may partially contain a copolymer having physical properties outside the above range. In the latter case, it is sufficient that the entire physical property value is included in the above range.

The method for producing the cyclic olefin copolymer used in the present invention is not limited, but a catalyst containing the following compounds (A) and (B) as main components or the following compound (A):
By efficiently copolymerizing an α-olefin and a cyclic olefin using a catalyst containing (B) and (C) as main components, it is possible to efficiently produce the copolymer. (A) a transition metal compound (B) a compound which reacts with a transition metal compound to form an ionic complex (C) an organoaluminum compound

In this case, the transition metal compound (A) may be selected from the groups IVB, VB, VIB, VIIB, VIB of the periodic table.
Transition metal compounds containing transition metals belonging to Group II can be used. As the transition metal, specifically, titanium, zirconium, hafnium, chromium, manganese, nickel, palladium, platinum and the like are preferable, and among them, zirconium, hafnium, titanium, nickel and palladium are preferable.

As such a transition metal compound (A), various compounds can be mentioned. In particular, compounds containing a transition metal of Group IVB and Group VIII, especially a transition metal selected from Group IVB of the periodic table, ie, Compounds containing titanium (Ti), zirconium (Zr) or hafnium (Hf) can be suitably used. Particularly, compounds represented by the following general formula (I),
A cyclopentadienyl compound represented by (II) or (III) or a derivative thereof, or a compound represented by the following general formula (IV) or a derivative thereof is preferable. ^{_{CpM 1 R 1 a R 2 b}} R 3 c ... (I) Cp 2 M 1 R 1 a R 2 b ... (II) (Cp-A e -Cp) M 1 R 1 a R 2 b ... (III) M ¹ R ¹ _a R ² _b R ³ _c R ⁴ _d ... (IV)

[In the formulas (I) to (IV), M ¹ is Ti, Zr
Or Hf atom, Cp is a cyclopentadienyl group,
It represents a cyclic unsaturated hydrocarbon group or a chain unsaturated hydrocarbon group such as a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group. R ¹ , R ² , R ³ and R ⁴ are each σ
Ligands such as binding ligands, chelating ligands, and Lewis bases are shown. Specific examples of the σ binding ligand include a hydrogen atom, an oxygen atom, a halogen atom, and a carbon atom having 1 to 1 carbon atoms. 20 alkyl groups, C1-C20 alkoxy groups, C6-C6
Examples of the aryl group include an aryl group, an alkylaryl group or an arylalkyl group having 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an allyl group, a substituted allyl group, a substituent containing a silicon atom, and the like. Examples include an acetylacetonate group and a substituted acetylacetonate group. A represents a covalent crosslink. a, b, c and d
Is an integer of 0 to 4, and e is an integer of 0 to 6. R
Two or more of ¹ , R ² , R ³ and R ⁴ may combine with each other to form a ring. When Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms. In the formulas (II) and (III), the two Cp's may be the same or different from each other. ]

The substituted cyclopentadienyl groups in the above formulas (I) to (III) include, for example, methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2-dimethyl Cyclopentadienyl group, tetramethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,
2,3-trimethylcyclopentadienyl group, 1,2,2
4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group and the like. In addition, the above (I) to (I
Specific examples of R ^{1 to} R ^{4 in} the formula V) include, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom as a halogen atom; a methyl group, an ethyl group, and an n-propyl group as an alkyl group having 1 to 20 carbon atoms. Group, iso-propyl group,
n-butyl group, octyl group, 2-ethylhexyl group; methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group as C1-C20 alkoxy group; C6-C20 aryl group, alkylaryl group or A phenyl group, a tolyl group, a xylyl group, or a benzyl group as an arylalkyl group; a heptadecylcarbonyloxy group as an acyloxy group having 1 to 20 carbon atoms; a trimethylsilyl group or a (trimethylsilyl) methyl group as a substituent containing a silicon atom: Lewis base As dimethyl ether,
Ethers such as diethyl ether and tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as acetonitrile and benzonitrile, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 2, Amines such as 2'-bipyridine and phenanthroline; phosphines such as triethylphosphine and triphenylphosphine; linear unsaturated hydrocarbons such as ethylene, butadiene, 1-pentene, isoprene, pentadiene, 1-hexene and derivatives thereof;
Examples of the cyclic unsaturated hydrocarbon include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene, and derivatives thereof. Examples of the crosslink by a covalent bond of A in the above formula (III) include a methylene bridge, a dimethylmethylene bridge, an ethylene bridge,
Examples include a cyclohexylene cross-link, a dimethylsilylene cross-link, a dimethylgermylene cross-link, and a dimethylstannylene cross-link.

Examples of such compounds include the following and compounds obtained by substituting zirconium of these compounds with titanium or hafnium. Compounds of formula (I) (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl) tribenzylzirconium, (pentamethylcyclopentadienyl) trichloro Zirconium, (pentamethylcyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium, (cyclopentadienyl) tribenzylzirconium, (cyclopentadienyl) trichloro Zirconium, (cyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) dimethyl (methoxy) zirconium, (methylcyclopentadienyl) trimethyldi Ruconium, (methylcyclopentadienyl) triphenylzirconium, (methylcyclopentadienyl) tribenzylzirconium, (methylcyclopentadienyl) trichlorozirconium, (methylcyclopentadienyl) dimethyl (methoxy) zirconium,
(Dimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium, (trimethylsilylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium,

A compound of formula (II) bis (cyclopentadienyl) dimethylzirconium,
Bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) diethyl zirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium , Bis (cyclopentadienyl) dihydridozirconium, bis (cyclopentadienyl) monochloromonohydridozirconium, bis (methylcyclopentadienyl) dimethylzirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclo Pentadienyl) dibenzyl zirconium, bis (pentamethylcyclopentadienyl) dimethyl zirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, Scan (pentamethylcyclopentadienyl) dibenzyl zirconium, bis (pentamethylcyclopentadienyl) chloromethyl zirconium,
Bis (pentamethylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl) (pentamethylcyclopentadienyl) dichlorozirconium,

Compound of the formula (III) : ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) dichlorozirconium, ethylenebis (tetrahydroindenyl) dimethylzirconium, ethylenebis (tetrahydroindenyl) dichlorozirconium, dimethylsilylenebis (cyclo) (Pentadienyl) dimethylzirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dichlorozirconium , [Phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, diphenylmethylene Tadienyl)
(9-fluorenyl) dimethyl zirconium, ethylene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclohexylidene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium,
Cyclopentylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclobutylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium,
Dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dimethylzirconium, dimethylsilylenebis (indenyl) dichlorozirconium

Examples of compounds other than the cyclopentadienyl compounds represented by the above general formulas (I), (II) and (III) include the compounds of the above formula (IV). Examples include zirconium compounds, hafnium compounds, and titanium compounds having one or more alkyl groups, alkoxy groups, and halogen atoms, such as compounds in which zirconium is replaced with hafnium or titanium. Tetramethyl zirconium, tetrabenzyl zirconium, tetramethoxy zirconium, tetraethoxy zirconium, tetrabutoxy zirconium, tetrachloro zirconium, tetrabromo zirconium,
Butoxytrichlorozirconium, dibutoxydichlorozirconium, bis (2,5-di-t-butylphenoxy) dimethylzirconium, bis (2,5-di-t-butylphenoxy) dichlorozirconium, zirconium bis (acetylacetonate),

The transition metal compound containing a VB-VIII group transition metal is not particularly limited. Specific examples of the chromium compound include, for example, tetramethylchromium, tetra (t
-Butoxy) chromium, bis (cyclopentadienyl) chromium, hydridetricarbonyl (cyclopentadienyl) chromium, hexacarbonyl (cyclopentadienyl) chromium, bis (benzene) chromium, tricarbonyltris (triphenylphosphonate) Chromium, tris (allyl) chromium, triphenyltris (tetrahydrofuran) chromium, chromium tris (acetylacetonate) and the like can be mentioned.

Specific examples of the manganese compound include, for example, tricarbonyl (cyclopentadienyl) manganese, pentacarbonylmethylmanganese, bis (cyclopentadienyl) manganese, manganese bis (acetylacetonate) and the like.

Specific examples of the nickel compound include, for example, dicarbonylbis (triphenylphosphine) nickel, dibromobis (triphenylphosphine) nickel, dinitrogenbis (bis (tricyclohexylphosphine) nickel), chlorohydridobis (tricyclohexyl) Phosphine) nickel, chloro (phenyl) bis (triphenylphosphine) nickel, dimethylbis (trimethylphosphine) nickel, diethyl (2,
2'-bipyridyl) nickel, bis (allyl) nickel, bis (cyclopentadienyl) nickel, bis (methylcyclopentadienyl) nickel, bis (pentamethylcyclopentadienyl) nickel, allyl (cyclopentadienyl) Nickel, (cyclopentadienyl)
(Cyclooctadiene) nickel tetrafluoroborate, bis (cyclooctadiene) nickel, nickel bisacetylacetonate, allylnickel chloride,
Tetrakis (triphenylphosphine) nickel, nickel _{chloride, (C 6 H 5) Ni} {OC (C 6 H 5) CH = P (C 6 H 5) 2} {P (C 6 H 5) 3}, ( _{C 6 H 5) Ni {OC} (C 6 H 5) C (SO 3 Na) = P (C 6 H 5) 2} {P (C 6 H 5) 3} and the like.

Specific examples of the palladium compound include, for example, dichlorobis (benzonitrile) palladium, carbonyltris (triphenylphosphine) palladium,
Dichlorobis (triethylphosphine) palladium, bis (t-butyl isocyanate) palladium, palladium bis (acetylacetonate), dichloro (tetraphenylcyclobutadiene) palladium, dichloro (1,5
-Cyclooctadiene) palladium, allyl (cyclopentadienyl) palladium, bis (allyl) palladium, allyl (1,5-cyclooctadiene) palladium tetrafluoroborate, (acetylacetonate)
(1,5-cyclooctadiene) palladium tetrafluoroborate, tetrakis (acetonitrile) palladium ditetrafluoroborate and the like can be mentioned.

Next, as the compound (B), any compound can be used as long as it reacts with the transition metal compound (A) to form an ionic complex. A compound comprising a bound anion, particularly a coordination complex compound comprising a cation and an anion having a plurality of groups bound to an element, can be suitably used. As a compound comprising such a cation and an anion in which a plurality of groups are bonded to an element, the following formula (V) or (VI)
The compound shown by can be used suitably. ^{([L 1 -R 7] k} +) p ([M 3 Z 1 Z 2 ... Z n] (nm) -) q ... (V) ([L 2] k +) p ([M 4 Z 1 Z 2 ... ^{Z n] (nm) -)} q ... (VI) ( where, L ² is ^{M 5, R 8 R 9 M} 6, R 10 is ₃ C or R ¹¹ M ⁶⁾

In the formulas (V) and (VI), L ¹ is a Lewis base, and M ³ and M ⁴ are VB group, VIB group and V
IIB, VIII, IB, IIB, IIIA, IVA and
Element selected from Group VA, preferably, a Group IIIA, elements selected from Group IVA, and group VA, IIIB group of M ⁵ and M ^6, respectively Periodic Table, IVB group, VB group, VIB group, VIIB group, V
Group III, IA Group, IB, Group IIA, element selected from Group IIB and VIIA group, Z ¹ to Z ⁿ are each a hydrogen atom, a dialkylamino group, an alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms Aryloxy group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group, arylalkyl group, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, acyloxy having 1 to 20 carbon atoms group, an organometalloid group or a halogen atom, Z ¹ to Z ⁿ may form a ring of two or more thereof with each other. R ⁷
Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
20 aryl group, an alkyl group, or an arylalkyl group, each R ⁸ and R ⁹ are a cyclopentadienyl group, substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, R ¹⁰ is 1 to 20 carbon atoms It represents an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group. R ¹¹ is tetraphenylporphyrin,
It shows a macrocyclic ligand such as phthalocyanine. m is M ³ , M
A valence of ⁴ and an integer of 1 to 7, n is an integer of 2 to 8 and k is an integer of 1 to 7 of an ionic valence of [L ¹ -R ⁷ ] and [L ² ];
p is an integer of 1 or more, and q = (p × k) / (nm). ]

Specific examples of the above Lewis base include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as trimethylamine, triethylamine, tri-n-butylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p-promo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline; Phosphines such as fin, triphenylphosphine and diphenylphosphine;
Ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane; thioethers such as diethylthioether and tetrahydrothiophene; and esters such as ethylbenzoate. Specific examples of M ³ and M ⁴ include B, Al, Si, P, As, Sb
Preferred examples of B or P, M ⁵ are Li,
Na, Ag, Cu, Br, I, I 3 , etc., specific examples of ^{M 6 Mn, Fe, Co,} Ni, Zn and the like.

Specific examples of Z ^{1 to} Z ⁿ include, for example, a dimethylamino group and a diethylamino group as a dialkylamino group; a methoxy group, an ethoxy group and an n-butoxy group as an alkoxy group having 1 to 20 carbon atoms; A phenoxy group, a 2,6-dimethylphenoxy group, a naphthyloxy group as an aryloxy group having from 20 to 20; a methyl group, an ethyl group, an n-propyl group as an alkyl group having from 1 to 20 carbon atoms;
iso-propyl group, n-butyl group, n-octyl group,
2-ethylhexyl group; an aryl group having 6 to 20 carbon atoms,
A phenyl group, p-tolyl group, benzyl group, 4-tert-butylphenyl group, 2,6-dimethylphenyl group,
3,5-dimethylphenyl group, 2,4-dimethylphenyl group, 2,3-dimethylphenyl group; p-fluorophenyl group, 3,5-difluorophenyl group as a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, Pentachlorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-di (trifluoromethyl) phenyl group; F, Cl, Br,
I; Examples of the organic metalloid group include a pentamethylantimony group, a trimethylsilyl group, a trimethylgermyl group, a diphenylarsine group, a dicyclohexylantimony group, and a diphenylboron group. Specific examples of R ⁷ and R ¹⁰ include:
The same ones as mentioned above can be mentioned. R ⁸ and R ⁹
Specific examples of the substituted cyclopentadienyl group include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Here, the alkyl group usually has 1 to 6 carbon atoms, and the number of substituted alkyl groups can be selected as an integer of 1 to 5. (V), (V
Among the compounds of the formula (I), those in which M ³ and M ⁴ are boron are preferred.

Among the compounds of the formulas (V) and (VI), the following compounds can be particularly preferably used. Compound of formula (V) Triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyltri (n-butyl) ammonium tetraphenylborate, benzyltriphenyltetraborate (N-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyltetraphenylborate (2-cyanopyridinium ), Trimethylsulfonium tetraphenylborate, benzyldimethylsulfonium tetraphenylborate ,

Triethylammonium tetra (pentafluorophenyl) borate, tri (n-butyl) ammonium tetra (pentafluorophenyl) borate, triphenylammonium tetra (pentafluorophenyl) borate, tetrabutylammonium tetra (pentafluorophenyl) borate, Tetra (pentafluorophenyl) borate (tetraethylammonium), tetra (pentafluorophenyl) borate (methyltri (n-butyl) ammonium), tetra (pentafluorophenyl) borate (benzyltri (n-butyl) ammonium), tetra (pentafluoroammonium) Methyldiphenylammonium phenyl) borate, methyltriphenylammonium tetra (pentafluorophenyl) borate Dimethyldiphenyltetra (pentafluorophenyl) borate Phenyl ammonium, anilinium tetra (pentafluorophenyl) borate, methylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, trimethylanilinium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) ) Dimethyl borate (m-nitroanilinium), dimethyl tetra (pentafluorophenyl) borate (p-bromoanilinium),

Pyridinium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) borate (p-cyanopyridinium), tetra (pentafluorophenyl) borate (N-methylpyridinium), tetra (pentafluorophenyl) borate (N- Benzylpyridinium), tetra (pentafluorophenyl) borate (O
-Cyano-N-methylpyridinium), tetra (pentafluorophenyl) borate (p-cyano-N-methylpyridinium), tetra (pentafluorophenyl) borate (p-cyano-N-benzylpyridinium), tetra (pentafluorophenyl) ) Trimethylsulfonium borate, benzyldimethylsulfonium tetra (pentafluorophenyl) borate, tetraphenylphosphonium tetra (pentafluorophenyl) borate, triphenylphosphonium tetra (pentafluorophenyl) borate, tetra (3,5-ditrifluoromethylphenyl) borate Dimethylanilinium, triethylammonium hexafluoroarsenate,

Compound of formula (VI) Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, manganese tetraphenylborate, ferrocenium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) borate (1,1′-dimethylferrocenium), decamethylferrocenium tetra (pentafluorophenyl) borate, acetylferrocenium tetra (pentafluorophenyl) borate, formylferrocenium tetra (pentafluorophenyl) borate, tetra (Pentafluorophenyl) cyanoferrocenium borate, silver tetra (pentafluorophenyl) borate, trityl tetra (pentafluorophenyl) borate,
Lithium tetra (pentafluorophenyl) borate, sodium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) borate (tetraphenylporphyrin manganese), tetra (pentafluorophenyl) borate (tetraphenylporphyrin iron chloride), tetra (penta Fluorophenyl) borate (zinc tetraphenylporphyrin), silver tetrafluoroborate,
Silver hexafluoroarsenate, silver hexafluoroantimonate,

Compounds other than formulas (V) and (VI), for example, tri (pentafluorophenyl) boron, tri (3,3)
5-Di (trifluoromethyl) phenyl) boron, triphenylboron and the like can also be used.

Examples of the organoaluminum compound as the component (C) include compounds represented by the following formulas (VII), (VIII) or (IX). R ¹² _r AlQ _3-r (VII) (R ¹² is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to ¹² carbon atoms such as an alkyl group, an alkenyl group, an aryl group and an arylalkyl group; Q is a hydrogen atom; Represents an alkoxy group or a halogen atom having 1 to 20 carbon atoms, and r is in the range of 1 ≦ r ≦ 3.) As the compound of the formula (VII), specifically, trimethylaluminum, triethylaluminum, triisopropyl Examples include aluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, and ethylaluminum sesquichloride.

[0048]

Embedded image (R ¹² is the same as in formula (VII). S indicates the degree of polymerization, and is usually 3 to 50, preferably 7 to 40.)

[0049]

Embedded image (R ¹² is the same as in formula (VII). S represents the degree of polymerization, and the number of repeating units is preferably from 3 to 50, and preferably from 7 to 40.) Aluminoxane. Among the compounds of the formulas (VII) to (IX), preferred are an alkyl group having 3 or more carbon atoms, especially an alkyl group-containing aluminum compound having at least one or more branched alkyl group or an aluminoxane. Particularly preferred is triisobutylaluminum or an aluminoxane having a degree of polymerization of 7 or more. When this triisobutylaluminum, aluminoxane having a polymerization degree of 7 or more, or a mixture thereof, high activity can be obtained.

Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water. The method is not particularly limited, and the reaction may be carried out according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, a method in which an organoaluminum compound is added at the beginning of polymerization and water is added later, a crystal water contained in a metal salt or the like, A method of reacting water adsorbed on inorganic or organic substances with an organoaluminum compound, a method of reacting a trialkylaluminum with a tetraalkyldialuminoxane, and further reacting water.

The catalyst used in the production of the cyclic olefin-based copolymer has the above components (A) and (B) or the above components (A), (B) and (C) as main components. is there. In this case, the use conditions of the component (A) and the component (B) are not limited, but the ratio (molar ratio) of the component (A) to the component (B) is 1: 0.01 to 1: 100, particularly 1: 1: 0.
5 to 1:10, preferably 1: 1 to 1: 5. The working temperature is preferably in the range of -100 to 250 ° C, and the pressure and time can be set arbitrarily.

The amount of component (C) used is generally 0 to 2,000 mol, preferably 5 to 2000 mol per mol of component (A).
It is 1,000 mol, particularly preferably 10 to 500 mol. When the component (C) is used, the polymerization activity can be improved. However, when the content is too large, a large amount of the organic aluminum compound remains in the polymer, which is not preferable. The use form of the catalyst is not limited. For example, the components (A) and (B) may be brought into contact with each other in advance, or the contact product may be separated and washed before use. May be used.
Further, the component (C) may be used in contact with the component (A), the component (B) or a contact product of the component (A) and the component (B) in advance. The contact may be made in advance, or may be brought into contact in the polymerization system. Further, the catalyst component can be added in advance to the monomer and the polymerization solvent, or can be added to the polymerization system.

The polymerization methods include bulk polymerization, solution polymerization,
Any method such as suspension polymerization and gas phase polymerization may be used.
Further, a batch method or a continuous method may be used. Regarding the polymerization conditions,
Polymerization temperature is -100 to 250C, especially -50 to 200C
It is preferable that The ratio of the catalyst used to the reaction raw material is expressed by: raw material monomer / component (A) (molar ratio)
Alternatively, the raw material monomer / the component (B) (molar ratio) is 1
It is preferably from 10 to 10 ⁹ , particularly preferably from 100 to 10 ⁷ . Further, the polymerization time is usually 1 minute to 10 hours, and the reaction pressure is normal pressure to 100 kg / cm ² G, preferably normal pressure to 50 kg / cm ^2.
cm ² G. As a method of adjusting the molecular weight of the polymer,
The amount of each catalyst component, the selection of the polymerization temperature, and the polymerization reaction in the presence of hydrogen can be used.

When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, pentane, hexane,
Aliphatic hydrocarbons such as heptane and octane, and halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. Further, a monomer such as an α-olefin may be used as the solvent.

The method for producing the vibration damping material of the present invention is not limited, and it can be produced by a conventional method using the above-mentioned cyclic olefin copolymer. For example, single-screw extruder, vented extruder, twin-screw extruder, conical twin-screw extruder, co-kneader, plasticizer, mixed extruder, twin-screw conical screw extruder, planetary screw extruder, gear type extruder Extrusion molding, injection molding, compression molding, blow molding, rotational molding or thermoforming from a sheet is performed using a screwless extruder or the like. Among these, injection molding can be particularly preferably employed.

The cyclic olefin-based copolymer may contain other elastomers, if necessary, and various additives such as stabilizers such as antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, etc. Agents, anti-blocking agents, lubricants, slip agents, anti-fog agents, foaming agents, flame retardants, inorganic fillers, organic fillers, dyes, pigments and the like can be added.

The vibration damping material of the present invention can be formed into an arbitrary shape depending on the purpose and application, for example, a sheet shape, a block shape and the like. The vibration damping material of the present invention thus formed can be used for various applications, for example, various machines and devices that generate vibration and noise due to rotational motion and reciprocating motion, housings thereof, structures such as bridge floors, water supply, gas and the like. It is used as a vibration damping material for conduits, air conditioning ducts, and various vehicles. In this case, the damping material of the present invention exhibits particularly excellent characteristics as a damping material for a panel for a vehicle such as a building or an automobile.

[0058]

EXAMPLES Next, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to the following examples. First, prior to the production of the damping material, the following Reference Examples 1 to 4
Was produced.

Reference Example 1 (1) Preparation of ferrocenium tetra (pentafluorophenyl) borate 20 mmol of ferrocene (Cp ₂ Fe) and 40 sulfuric acid
The reaction with milliliters was carried out at room temperature for 1 hour to obtain a dark blue solution. This solution was poured into 1 liter of water and stirred, and the resulting deep blue aqueous solution was added to 500 ml of an aqueous solution of 20 mmol of lithium tetra (pentafluorophenyl) borate. The light blue solid that had precipitated was collected by filtration and washed with water 5
After washing five times with 00 ml, the product was dried under reduced pressure and the desired product ferrocenium tetra (pentafluorophenyl) borate ([Cp ₂ Fe] [B (C
₆ F ₅ ) ₄ ]), 17 mmol.

(2) Copolymerization of ethylene and 2-norbornene In a 30 liter autoclave at room temperature under a nitrogen atmosphere, 15 liter of toluene, 23 mmol of triisobutylaluminum (TIBA), 0.11 mmol of biscyclopentadienyl zirconium dichloride were added. 0.15 mmol of ferrocenium tetra (pentafluorophenyl) borate prepared in (1) above was added in this order,
Subsequently, 2.25 liter of a toluene solution containing 70% by weight of 2-norbornene (15.
(0 mol), and the mixture was heated to 90 ° C. and reacted for 110 minutes while continuously introducing ethylene so that the ethylene partial pressure became 7 kg / cm ² . After completion of the reaction, the polymer solution was poured into 15 liters of methanol to precipitate a polymer, and the polymer was collected by filtration and dried to obtain a cyclic olefin-based copolymer (a1). The yield of the cyclic olefin copolymer (a1) was 3.48 kg. The polymerization activity was 347 Kg / gZr.

The obtained cyclic olefin copolymer (a)
Physical properties of 1) were as described below. 30 of ¹³ C-NMR
The sum of the peak based on ethylene and the peak based on methylene at the 5- and 6-positions of norbornene, which appears around ppm, and 3
The norbornene content determined from the ratio to the peak based on a methylene group at the 7-position of norbornene appearing at around 2.5 ppm was 9.2 mol%. The intrinsic viscosity [η] measured in decalin at 135 ° C. was 0.99 dl / g, and the crystallinity determined by X-ray diffraction was 1.0%. Using a piperon 11-EA type manufactured by Toyo Boulding Co., Ltd., a measuring piece having a width of 4 mm, a length of 40 mm, and a thickness of 0.1 mm was measured at a heating rate of 3 ° C./min and a frequency of 3.5 Hz. The glass transition temperature (Tg) was determined from the peak of the loss modulus of elasticity (E ″) of the sample, and the Tg was 3 ° C. ALC / OPC150C manufactured by Waters, Inc. was used as a measuring device, and 1,2,4-trichlorobenzene solvent was used. 135 ° C
The weight average molecular weight Mw, number average molecular weight Mn, and molecular weight distribution (Mw / Mn) were calculated in terms of polyethylene.
Mw is 54,200, Mn is 28,500, Mw / Mn
= 1.91. Using a Perkin-Elmer 7 series DSC at a rate of 10 ° C./min, -50 ° C.
When the melting point (Tm) was measured in the range of 150 ° C., the Tm
Was 73 ° C (broad peak) ° C.

Reference Example 2 Reference Example 1 was repeated except that the amount of biscyclopentadienyl zirconium dichloride was changed to 0.075 mmol and the amount of 2-norbornene was changed to 7.5 mol in (2) of Reference Example 1. In the same manner as in the above, a cyclic olefin-based copolymer (a2) was obtained. The yield of the cyclic olefin copolymer (a2) was 2.93 kg, and the polymerization activity was 428 kg / gZr. The norbornene content obtained in the same manner as in Reference Example 1 was 4.9 mol%, and the intrinsic viscosity [η] was 1.22 dl.
/ G, glass transition temperature (Tg) is -7 ° C, Mw is 72,
400, Mn is 36,400, Mw / Mn is 1.99,
Melting point (Tm) was 84 ° C. (broad peak).

Reference Example 3 In (2) of Reference Example 1, the amount of biscyclopentadienyl zirconium dichloride was 0.064 mmol, the amount of ferrocenium tetra (pentafluorophenyl) borate was 0.11 mmol, A cyclic olefin copolymer (a3) was obtained in the same manner as in Reference Example 1, except that the amount of norbornene used was 7.5 mol, the polymerization temperature was 70 ° C., and the ethylene partial pressure was 9 kg / cm ² . The yield of the cyclic olefin copolymer (a3) was 2.36 kg, and the polymerization activity was 460 kg / gZr. The norbornene content determined in the same manner as in Reference Example 1 was 4.5 mol%, the intrinsic viscosity [η] was 3.07 dl / g, and the glass transition temperature (T
g) is −8 ° C., Mw is 213,000, Mn is 114,
000, Mw / Mn 1.87, melting point (Tm) 81 ° C
(Broad peak).

Reference Example 4 In (2) of Reference Example 1, 30 parts of ethyl aluminum sesquichloride were used instead of triisobutyl aluminum.
0 mmol, 30 mmol of VO (OC ₂ H ₅ ) Cl ₂ was used in place of biscyclopentadienyl zirconium dichloride, ferrocenium tetra (pentafluorophenyl) borate was not used, and the amount of 2-norbornene was 4 mmol. A cyclic olefin-based copolymer (a4) was obtained in the same manner as in Reference Example 1 except that 9.9 mol, the polymerization temperature was 40 ° C., the ethylene partial pressure was 3 kg / cm ² , and the polymerization time was 180 minutes. The yield of the cyclic olefin copolymer (a4) was 550 g. The norbornene content determined in the same manner as in Reference Example 1 was 9.4 mol%, the intrinsic viscosity [η] was 1.18 dl / g, and the melting point (Tm) was 100 ° C.
(Sharp peak), glass transition temperature (Tg) is 1
° C and Mw / Mn were 3.20.

Next, using the cyclic olefin copolymers a1 to a4 obtained in the above Reference Examples 1 to 4 and a commercially available thermoplastic resin, the vibration damping materials of the following Examples 1 to 3 and Comparative Examples 1 to 4 were used. Was manufactured. Examples 1 to 3 and Comparative Examples 1 to 4 Using resin pellets shown in Table 1, using an injection molding machine (IS25EP manufactured by Toshiba Corporation), set temperature 150 ° C., mold temperature 30 ° C., injection pressure (primary / Secondary) 80 / 40Kg
Injection molding was performed under the condition of / cm ² to obtain a test piece. Table 1 shows the results of measuring the tensile properties and the rebound resilience of the obtained test pieces.

Here, the measurement of each item was performed as follows. Tensile modulus: JIS-K7113 using autograph
Was performed according to Tensile breaking strength: JIS-K711 using an autograph
3 was performed. Tensile elongation at break: JIS-K711 using autograph
3 was performed. Rebound resilience: Performed according to JIS-K6301.

[0067]

[Table 1]

[0068]

As described above, the vibration damping material of the present invention exhibits excellent vibration damping performance over a wide temperature range.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 10/00-10/14 C08F 32/00-32/08 C08F 210/00-210/18 C08F 232 / 00-232/08 F16F 15/02

Claims (2)

(57) [Claims] 1. A copolymer obtained by copolymerizing a cyclic olefin and an α-olefin, wherein the copolymer has a glass transition temperature (Tg) of 25 ° C. or lower and a melting point of 90 ° C. or lower. A vibration damping material formed by: 2. The vibration damping material according to claim 1, wherein the cyclic olefin-based copolymer has a tensile modulus of 2000 kg / cm ² or less.