JP3255537B2 - Cyclic olefin polymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cyclic olefin polymer composition. More specifically, the present invention relates to a cyclic olefin polymer composition containing a cyclic olefin polymer and having excellent impact resistance.

[0002]

BACKGROUND OF THE INVENTION Applicants have previously disclosed a cyclic olefin-based random copolymer obtained by copolymerizing ethylene with a cyclic olefin such as tetracyclododecene or norbornene, which has excellent transparency and heat resistance. It is a synthetic resin with a good balance of heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and rigidity, and exhibits excellent performance in the field of optical materials such as optical memory disks and optical fibers. Heading, JP-A-60-168708, JP-A-61-98780, JP-A-61-11
5912, JP-A-61-115916, JP-A-61-120816, JP-A-62-2524
No. 07 publication. The cyclic olefin random copolymers described in these publications are known to exhibit excellent performance also in the field of structural materials.

[0003] However, although these cyclic olefin copolymers are excellent in heat resistance and rigidity, there is room for improvement of impact resistance, and the transparency of these cyclic olefin copolymers is maintained. In addition, further improvement in impact resistance is required.

[0004] The present applicant also discloses a specific softening temperature (TM).
A composition comprising a cyclic olefin-based random copolymer having A) and a specific α-olefin-based elastic copolymer,
It has been found that a resin having improved impact resistance can be obtained without impairing excellent properties such as heat resistance, heat aging resistance, and chemical resistance, and has already been proposed in JP-A-1-163241.

Further, the applicant of the present invention discloses a cyclic olefin polymer composition having improved impact resistance, comprising a specific cyclic olefin random copolymer and a specific soft copolymer, an organic peroxide. JP-A-167318 has already proposed a cyclic olefin-based copolymer composition comprising a product obtained by reacting in the presence of.

[0006] However, the cyclic olefin polymer compositions proposed in JP-A-1-163241 and JP-A-2-167318 have improved impact resistance, but are not always sufficiently transparent. Nevertheless, there was room for improvement.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a cyclic olefin polymer composition. Another object of the present invention is to provide a cyclic olefin polymer composition having improved impact resistance without impairing the original transparency of the cyclic olefin copolymer. Still other objects and advantages of the present invention will become apparent from the following description.

[0008]

According to the present invention, the above objects and advantages of the present invention are as follows: [A]. [A-1] (i) At least one of α-olefins having 2 or more carbon atoms. One kind, and (ii) the following formula [I] or [II]

[0009]

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(In the formula [I], u is 0 or 1, and v
Is 0 or a positive integer, w is 0 or 1, R
^{61 to} R ⁷⁸ and R ^a1 and R ^b1 are each independently:
Hydrogen atom, a halogen atom or a hydrocarbon group, R ⁷⁵
To R ⁷⁸ may also form a monocyclic or polycyclic bonded to each other, and may have monocyclic or polycyclic a double bond, also in the R ⁷⁵ and R ^76, Or R ⁷⁷ and R ⁷⁸ may form an alkylidene group),

[0011]

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(In the formula [II], x and d are 0 or 1
And y and z are 0, 1 or 2
R⁸¹~ R⁹⁹Are each independently a hydrogen atom or a halogen atom
, Aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon
A hydrogen group or an alkoxy group,⁸⁹Or R⁹⁰Tied
Combined carbon atom and R⁹³To the carbon atom to which
Or R⁹¹Is directly or carbon
Even when bonded via an alkylene group having 1 to 3 atoms.
Well, and when y = z = 0, R⁹⁵And R⁹²Or R ⁹⁵When
R⁹⁹Is linked to each other to form a monocyclic or polycyclic aromatic ring
At least one kind represented by
Cyclic olefin obtained by copolymerization with cyclic olefin
[A-2] the above-mentioned formula [I] or
At least one cyclic olefin represented by [II]
A ring-opened polymer of the formula [I-3] or [I-3]
I] of at least one cyclic olefin represented by
Cyclic olefins selected from the group consisting of hydrogenated ring-opened polymers
A fin-based polymer, which is
The intrinsic viscosity [η] is 0.05 to 5.0 dl / g, and the DSC
The glass transition temperature (Tg) measured by
And a refractive index nD measured at 25 ° C. of 1.500 to 1.6
A cyclic olefin polymer which is 50,

[B]. [B-1] 40 to 85 parts by weight of a core component comprising a styrene-butadiene rubber having a styrene unit of 50% by weight or less, and [B-2] (b-1) a monovinyl aromatic unit. (B-2) 20 to 80% by weight of an alkyl (meth) acrylate monomer copolymerizable therewith and (b-3) 0 to 3% by weight of a polyfunctional monomer. It comprises 15 to 60 parts by weight of a shell component composed of a copolymer containing a monomer mixture as a constituent component, provided that the total of the core component [B-1] and the shell component [B-2] is 10%.
0 parts by weight, and the average diameter of the primary particles is 100 to
A core-shell elastomer characterized by being in the range of 300 nm; and [C] a fluid lubricant, and wherein the weight ratio of the component [A] to the component [B] is in the range of 40/60 to 95/5. And the amount of the component [C] is in the range of 1 to 20 parts by weight per 100 parts by weight of the total of the components [A] and [B]. .

The cyclic olefin random copolymer [A-
[1] as α-olefin having 2 or more carbon atoms used when copolymerizing [1], specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene,
-Methyl-1-pentene, 1-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecene,
2 to 2 carbon atoms such as 1-octadecene and 1-eicosene
Α-olefin of 0. These may be used in combination of two or more. Of these, ethylene is particularly preferably used.

The compounds represented by the formulas [I] and [II] used for copolymerizing the cycloolefin random copolymer [A-1] will be described below.

In the formula [I], u is 0 or 1, v is 0 or a positive integer, and w is 0 or 1. When w is 1, the ring represented by w is a 6-membered ring, and when w is 0, the ring is a 5-membered ring.

R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 are each independently a hydrogen atom, a halogen atom or a hydrocarbon group. Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The hydrocarbon group is usually an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group. Is mentioned. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. These alkyl groups may be substituted with a halogen atom.

Examples of the cycloalkyl group include a cyclohexyl group, and examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. Further, the above formula [I]
In the above, R ⁷⁵ and R ⁷⁶ are, R ⁷⁷ and R ⁷⁸ are, R ⁷⁵ and R
⁷⁷ , R ⁷⁶ and R ⁷⁸ , R ⁷⁵ and R ⁷⁸ , or R
⁷⁶ and R ⁷⁷ may be bonded together (in cooperation with each other) to form a monocyclic or polycyclic group, and the monocyclic or polycyclic ring thus formed forms a double bond. You may have. Specific examples of the monocyclic or polycyclic ring formed here include the following.

[0020]

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In the above examples, the carbon atoms numbered 1 or 2 represent R in formula [I], respectively.
^Represents a carbon atom to which ⁷⁵ (R ⁷⁶ ) or R ⁷⁷ (R ⁷⁸ ) is bonded. Further, R ⁷⁵ and R ⁷⁶ or R ⁷⁷ and R ⁷⁸ may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include an ethylidene group, a propylidene group and an isopropylidene group.

In the formula [II], x and d are 0 or a positive integer, and y and z are 0, 1 or 2. R ^{81 to} R ⁹⁹ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group.

Examples of the halogen atom include the same as the halogen atom in the above formula [I]. Examples of the aliphatic hydrocarbon group usually include an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. These alkyl groups may be substituted with a halogen atom.

Examples of the cycloalkyl group include a cyclohexyl group. Examples of the aromatic hydrocarbon group include an aryl group, an aralkyl group, and the like, and specific examples include a phenyl group, a tolyl group, a funtyl group, a benzyl group, and a phenylethyl group.

Examples of the alkoxy group include a methoxy group and an ethoxy group.
Examples include a xy group and a propoxy group. Where R⁸⁹
And R⁹⁰And a carbon atom to which R⁹³Are combined
Carbon atom or R⁹¹Is bonded to the carbon atom
Directly or through an alkylene group having 1 to 3 carbon atoms
They may be combined. That is, the two carbon atoms are
When linked via an alkylene group, R⁸⁹And R
⁹³And or R⁹⁰And R ⁹¹And cooperate with each other,
Len group (-CH_Two-), Ethylene group (-CH_TwoCH_Two−)
Or a propylene group (-CH_TwoCH_TwoCH_TwoInside of-)
Some alkylene groups are formed.

Further, when y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. Specifically, y = z = 0
In this case, the following aromatic rings formed by R ⁹⁵ and R ⁹² can be mentioned.

[0027]

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Here, 1 is the same as d in the formula [II].

Specific examples of the cyclic olefin represented by the above formula [I] or [II] include bicyclo-2-heptene derivatives (bicyclohept-2-ene derivatives), tricyclo-3-decene derivatives, Tricyclo-
3-undecene derivative, tetracyclo-3-dodecene derivative, pentacyclo-4-pentadecene derivative, pentacyclopentadecadiene derivative, pentacyclo-3-pentadecene derivative, pentacyclo-4-hexadecene derivative, pentacyclo-3-hexadecene derivative, hexacyclo-4 -Heptadecene derivative, heptacyclo-5-
Eicosene derivatives, heptacyclo-4-eicosene derivatives, heptacyclo-5-heneicosene derivatives, octacyclo-5-docosene derivatives, nonacyclo-5-pentacosene derivatives, nonacyclo-6-hexacocene derivatives,
Cyclopentadiene-acenaphthylene adduct, 1,4-
And methano-1,4,4a, 9a-tetrahydrofluorene derivatives, 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene derivatives.

In the following, formula [I] or [I
Specific examples of the cyclic olefin represented by I] are shown below.

[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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The above general formula [I] or [II]
Can be produced by subjecting cyclopentadiene and an olefin having a corresponding structure to a Diels-Alder reaction.

The structural unit derived from the cyclic olefin represented by the formula [I] or [II] is a cyclic olefin-based random copolymer having a repeating structure represented by the following formula [I '] or [II'] It is considered to form a unit.

[0054]

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(In the formula [I '], u, v, w and R ⁶¹
R ⁷⁸ and R ^a1 and R ^b1 are the same as defined in the above formula [I]. )

[0056]

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(In the formula [II ′], y, z, x, d and R ^{81 to} R ⁹⁹ are the same as defined in the formula [II].) These cyclic olefins may be used alone or in combination of two or more. They can be used in combination.

The cyclic olefin random copolymer [A-1] used in the present invention comprises (i) at least one kind of α-olefin having 2 or more carbon atoms as described above and (i)
i) a catalyst (a) formed from a soluble vanadium compound and an organoaluminum compound (A), as described below, with at least one cyclic olefin represented by the above formula [I] or [II], or Periodic Table IVB
And a metallocene compound of a transition metal selected from the group consisting of lanthanides and lanthanides, and an organic aluminum oxy compound, and if necessary, copolymerization in the presence of a catalyst (b) formed from an organic aluminum compound (B). Can be.

The soluble vanadium compound forming such a catalyst (a) is specifically represented by the following general formula. VO (OR) _{a Xb} or V (OR) _c X _d wherein R is a hydrocarbon group, and a, b, c, and d are respectively 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3,0
≤ c ≤ 4, 0 ≤ d ≤ 4, and 3 ≤ c + d ≤ 4. More specifically, VOCl ₃ , VO (OC ₂ H ₅ ) Cl ₂ , VO (OC ₂ H ₅ ) ₂ Cl, VO (O-iso-C ₃ H ₇ ) Cl ₂ , VO (On-C _{4 H 9) Cl 2, VO} (OC 2 H 5) 3, VOBr 2, VCl 4, VOCl 2, VO (O-n-C 4 H 9) 3, VOCl 3 · 2OC 8 H 17 7OH vanadium compound such as Is used. These compounds can be used alone or in combination of two or more.

The above-mentioned soluble vanadium compound can also be used as an electron donor adduct obtained by contacting an electron donor as shown below. Examples of such electron donors include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, esters of organic or inorganic acids, ethers, diethers, acid amides, and acid anhydrides. Substances, oxygen-containing electron donors such as alkoxysilanes, and nitrogen-containing electron donors such as ammonias, amines, nitriles, pyridines, and isocyanates.

More specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol,
C1-C18 alcohols such as cumyl alcohol, isopropyl alcohol, and isopropylbenzyl alcohol; and C1-C18 halogen-containing alcohols such as trichloromethanol, trichloroethanol, and trichlorohexanol; phenol, cresol, xylenol, and ethylphenol , Propylphenol,
C6-20 phenols which may have a lower alkyl group such as nonylphenol, cumylphenol and naphthol; C3-15 ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone , Acetaldehyde, propionaldehyde, octylaldehyde,
Aldehydes having 2 to 15 carbon atoms, such as benzaldehyde, tolualdehyde, and naphthaldehyde;

Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, crotonic acid Ethyl, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate , Ethyl ethyl benzoate, methyl anisate,
Ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide,
Organic acid esters having 2 to 18 carbon atoms such as ethyl carbonate;
Acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride; having 2 to 2 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, and diphenyl ether 20 ethers; acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride; alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane; acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluyl Acid amides such as acid N, N-dimethylamide; amines such as trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylethylenediamine; acetonitrile, benzonitrile, trinitrile Nitriles; pyridine, and the like can be exemplified pyridines such as methylpyridine, ethylpyridine, dimethylpyridine.

When preparing an electron donor adduct of a soluble vanadium compound, these electron donors can be used alone or in combination of two or more. The organoaluminum compound (A) which forms the catalyst (a) together with the soluble vanadium compound as described above has at least one Al-C bond in the molecule. For example, the following formulas (a) and (b) Is represented by

[0064] (a) the general formula _{^{R 1 m Al (OR 2)}} n H p X q ( wherein, R ¹ and R ^2, typically 1 to 15 carbon atoms, preferably 1-4 hydrocarbon group And these may be the same or different, X is 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
(B) a complex alkylated product of a Group 1 metal and aluminum represented by the general formula M ¹ AlR ¹ (wherein M ¹ is Li, Na, K, and R ¹ is the same as described above) Specific examples of the organoaluminum compound represented by (a) include the following compounds.

(1) General formula R ¹ _m Al (OR ² ) _{3 -m} (wherein R ¹ and R ² are the same as above, and m is preferably a number satisfying 1.5 ≦ m <3) (2) General Formula R ¹ _m AlX _3-m (wherein R ¹ is the same as above, X is halogen, and m is preferably a number of 0 <m <3). Formula R ¹ _m AlH _3-m (wherein R ¹ is the same as above, and m is preferably 2 ≦
(4) General formula R ¹ _m Al (OR ² ) _n X _q (wherein R ¹ and R ² are the same as above, X is halogen, and 0 <m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, m
+ N + q = 3) As the organoaluminum compound (A) represented by (a), more specifically, the following compounds can be exemplified.

Examples of the organoaluminum compound represented by (1) include trialkylaluminums such as triethylaluminum and tributylaluminum; trialkenylaluminums such as triisopropenylaluminum; dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; ethylaluminum sesquichloride ethoxide, and butyl aluminum sesqui butoxide, R ¹ _2.5 Al (O
R ² ) A partially alkoxylated alkyl aluminum having an average composition represented by _0.5 or the like can be mentioned.

Examples of the organoaluminum compound represented by (2) include dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride and diethylaluminum bromide; alkyls such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide Aluminum sesquihalide; alkyl aluminum partially halogenated such as ethyl aluminum dichloride, propyl aluminum dichloride, and butyl aluminum dibromide;

Examples of the organoaluminum compound represented by (3) include dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; and partially hydrogenated alkylaluminums such as ethylaluminum dihydride and propylaluminum dihydride. Can be mentioned.

Examples of the organoaluminum compound represented by (4) include partially aluminum-alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, and ethylaluminum ethoxybromide.

Further, a compound similar to the compound represented by the above general formula (a), for example, an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom may be used. As such a compound, specifically, (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ AlOAl (C ₄ H ₉ ) ₂ , (C ₂ H ₅ ) ₂ AlN (C ₆ H ₅ ) Al (C ₂ H ₅ ) _{2 and the} like can be exemplified.

The compounds belonging to the above (b) include:
LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ can be exemplified. Of these, alkyl aluminum halides, alkyl aluminum dihalides or mixtures thereof are particularly preferred.

Next, a catalyst (b) formed from a metallocene compound of a transition metal selected from Group IVB or a lanthanide of the periodic table and an organoaluminum oxy compound and, if necessary, an organoaluminum compound (B) will be described. I do.

Examples of the transition metal compound of Group IVB of the periodic table or a lanthanide containing such a ligand having a cyclopentadienyl skeleton include compounds represented by the following general formula [X]. .

ML _X ... [X] In the above general formula [X], M is a transition metal selected from the group IVB of the periodic table and lanthanides. Specifically, zirconium, titanium, hafnium, neodymium and samarium Or ytterbium, L is a ligand that coordinates to the transition metal, and at least one L is
L is a ligand having a cyclopentadienyl skeleton, and L other than the ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl. Group, SO ₃ R
(Where R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen) or a hydrogen atom, and x is a valence of a transition metal.

The ligand having a cyclopentadienyl skeleton includes, for example, cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl Group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclo Examples thereof include an alkyl-substituted cyclopentadienyl group such as a pentadienyl group and a hexylcyclopentadienyl group, an indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

Among the ligands which coordinate to these transition metals, an alkyl-substituted cyclopentadienyl group is particularly preferred. When the compound represented by the general formula [X] contains two or more groups having a cyclopentadienyl skeleton, two of the groups having the cyclopentadienyl skeleton are alkylene groups such as ethylene and propylene, and isopropyl The bond may be formed through a substituted alkylene group such as lidene or diphenylmethylene, a substituted silylene group such as a silylene group or a dimethylsilylene group, a diphenylsilylene group, or a methylphenylsilylene group.

The ligands other than those having a cyclopentadienyl skeleton include the following. Specifically as a hydrocarbon group having 1 to 12 carbon atoms,
Alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and neophyl group. Is exemplified. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a butoxy group.
Examples of the aryloxy group include a phenoxy group. Examples of the halogen include fluorine, chlorine, bromine, and iodine. The ligand represented by SO ₃ R includes a p-toluenesulfonato group, a methanesulfonato group,
Examples thereof include a trifluoromethanesulfonato group.

The compound represented by the general formula [X] is
For example, when the valence of the transition metal is 4, it is more specifically represented by the following general formula [X ′]. R ¹ _a R ² _b R ³ _c R ⁴ _d M ... [X ′] (In the formula [X ′], M is zirconium, titanium, hafnium, neodymium, samarium or yttrium, and R ¹ is a cyclopentadienyl skeleton R ² , R ³ and R ⁴ are a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group , SO ₃ R or a hydrogen atom, a is an integer of 1 or more, and a + b + c +
d = 4. )

In the present invention, a transition metal compound in which one of R ² , R ³ and R ^{4 in} the general formula [X ′] is a group having a cyclopentadienyl skeleton, for example, when R ¹ and R ² are cyclopentane A transition metal compound which is a group having a dienyl skeleton is preferably used. These groups having a cyclopentadienyl skeleton are substituted with alkylene groups such as ethylene and propylene, alkylidene groups such as isopropylidene, substituted alkylene groups such as diphenylmethylene, silylene groups or substituted dimethylsilylene, diphenylsilylene, and methylphenylsilylene groups. They may be bonded via a silylene group or the like. Also, R ³ and R ⁴
Is a group having a cyclopentadienyl skeleton, an alkyl group,
It is a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, SO ₃ R or a hydrogen atom.

Specific examples of the transition metal compound in which M is zirconium are shown below. Bis (indenyl) zirconium dichloride, bis (indenyl)
Zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonate), bis (4,5,
6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride,

Ethylene bis (indenyl) zirconium dichloride, ethylene bis (indenyl) zirconium dibromide, ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) diphenyl zirconium, ethylene bis (indenyl) methyl zirconium monochloride, ethylene bis (indenyl) ) Zirconium bis (methanesulfonato), ethylenebis (indenyl) zirconiumbis (p-toluenesulfonato), ethylenebis (indenyl) zirconiumbis (trifluoromethanesulfonato), ethylenebis (4,5,6,7-tetrahydro) Indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (methylcyclopentadi (Enyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl)
Dimethyl zirconium,

Dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) ) Zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (indenyl)
Zirconium bis (trifluoromethanesulfonate),
Dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, methylphenylsilylenebis (indenyl) zirconium dichloride ,

Bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride, bis ( Cyclopentadienyl) cyclohexylzirconium monochloride, bis (cyclopentadienyl) phenylzirconium monochloride, bis (cyclopentadienyl) benzylzirconium monochloride, bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclo Pentadienyl) methyl zirconium monohydride, bis (cyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) diphenyl zirconium, (Cyclopentadienyl) dibenzyl zirconium, bis (cyclopentadienyl) zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methane sulfonato),
Bis (cyclopentadienyl) zirconium bis (p-
Toluenesulfonato), bis (cyclopentadienyl)
Zirconium bis (trifluoromethanesulfonate),

Bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxycyclolide, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethane Sulfonato), bis (dimethylcyclopentadienyl) dimethylzirconium, bis (ethylcyclopentadienyl) zirconium dichloride,
Bis (methylethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl)
Zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis ( (Methanesulfonato), bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride , Bis (trimethylsilylcyclopentadienyl) zirconium dichloride.

In the above examples of the transition metal compound, the disubstituted cyclopentadienyl ring includes 1,2- and 1,3-substituted, and the tri-substituted cyclopentadienyl ring includes 1,2,3- and 1,1,3-substituted. Includes 2,4-substituted products. Alkyl groups such as propyl and butyl include isomers such as n-, i-, sec- and tert-.

In the present invention, a transition metal compound in which the zirconium metal is replaced with a titanium metal, a hafnium metal, a neodymium metal, a samarium metal, or a yttrium metal in the zirconium compound as described above can also be used.

Organic aluminum oxy compounds which form a catalyst (b) together with a transition metal compound of Group IVB of the periodic table or a lanthanide containing a ligand having a cyclopentadienyl skeleton as described above are known aluminum oxide compounds. It may be a nooxane or a benzene-insoluble organic aluminum oxy compound. Such conventionally known aluminoxane is specifically represented by the following general formula.

[0088]

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(Wherein R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group, preferably a methyl group, an ethyl group, particularly preferably a methyl group,
Is an integer of 2 or more, preferably 5 to 40. Here, this aluminoxane has the formula (OAl (R ¹ ))
In alkyloxyaluminum unit [where represented by alkyloxy aluminum units and formula represented ^{(OAl (R 2)),} R 1 and R ² can be exemplified the same hydrocarbon groups and R, R ¹ and R ² represents a different group].

A conventionally known aluminoxane is prepared, for example, by the following method, and is usually recovered as a solution of an aromatic hydrocarbon solvent. (1) Compounds containing water of adsorption or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate,
Addition of an organoaluminum compound such as trialkylaluminum to an aromatic hydrocarbon solvent in which aluminum sulfate hydrate, nickel sulfate hydrate, cerous chloride hydrate and the like are suspended and reacted with the aromatic hydrocarbon A method of recovering as a solvent solution.

(2) Water (water, ice or steam) is allowed to act directly on an organoaluminum compound such as a trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran to recover as a solution of an aromatic hydrocarbon solvent. how to.

(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.

Among these methods, it is preferable to employ the method (1). As the organoaluminum compound used when preparing the solution of aluminoxane, specifically, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trisec- Butyl aluminum,
Trialkyl aluminum such as tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; tricyclohexylaluminum, tricycloalkylaluminum such as tricyclooctylaluminum; dimethylaluminum chloride, diethylaluminumchloride, Dialkylaluminum halides such as diethylaluminum bromide and diisobutylaluminum chloride; dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide; diethylaluminum phenoxy And dialkyl aluminum aryloxides such as

Among these, trialkylaluminum is particularly preferred. Further, isoprenyl aluminum represented by the following general formula can also be used as the organic aluminum compound.

(I-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (where x, y, and z are positive numbers and z ≧ 2x). The compounds are used alone or in combination.

The benzene-insoluble organoaluminum oxy compound used in the present invention can be prepared, for example, by contacting a solution of aluminoxane with water or an active hydrogen-containing compound, or by contacting the above-mentioned organoaluminum compound with water. And the like.

[0097] In benzene-insoluble organoaluminum oxy-compound used in the present invention, the compound was analyzed by infrared spectroscopy (IR), the absorbance at around 1220 cm ^-1 and (D _1220), the absorbance at around 1260 cm ^-1 (D ₁₂₆₀₎ and the ratio of (D _{12 60} / D ₁₂₂₀₎ is 0.09
Or less, preferably 0.08 or less, particularly preferably 0.4 to
It is desirable to be in the range of 0.07.

The above-mentioned benzene-insoluble organoaluminum oxy compound is presumed to have an alkyloxyaluminum unit represented by the following formula.

[0099]

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In the formula, R ³ is a hydrocarbon group having 1 to 12 carbon atoms. Specific examples of such hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, and n.
-Butyl group, isobutyl group, pentyl group, hexyl group,
Examples include an octyl group, a decyl group, a cyclohexyl group, a cyclooctyl group, and the like. Of these, a methyl group and an ethyl group are preferred, and a methyl group is particularly preferred.

The benzene-insoluble organoaluminum oxy compound may contain an oxyaluminum unit represented by the following formula in addition to the alkyloxyaluminum unit represented by the above formula.

[0102]

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In the formula, R ⁴ is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a hydroxyl group, a halogen or a hydrogen atom. R ⁴ and R ³ in the above formula represent different groups.

When the benzene-insoluble organoaluminum oxy compound contains an oxyaluminum unit,
An organic aluminum oxy compound having an alkyloxyaluminum unit containing an alkyloxyaluminum unit in an amount of 30 mol% or more, preferably 50 mol% or more, particularly preferably 70 mol% or more is desirable.

Such a benzene-insoluble organoaluminum oxy compound is obtained by dissolving Al in the benzene at 60 ° C.
The component is 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, and is insoluble or hardly soluble in benzene. The organic aluminum oxy compound used in the present invention may contain a small amount of an organic compound component of a metal other than aluminum. As the organoaluminum compound (B) optionally used in the catalyst (b), for example, the following general formula [XI]
The organic aluminum compound represented by these can be illustrated.

R ⁵ _n AlX _3-n ... [XI] (In the formula [XI], R 5 is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1
~ 3. )

In the general formula [XI], R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group. Propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl, tolyl and the like.

As such an organoaluminum compound, specifically, the following compounds are used. Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum; alkenylaluminum such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutyl Dialkylaluminum halides such as aluminum chloride and dimethylaluminum bromide; alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; Aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide; diethylaluminum hydride, and alkyl aluminum hydride such as diisobutyl aluminum hydride.

As the organoaluminum compound (B), a compound represented by the following general formula [XII] can also be used. R ⁵ _n AlY _3-n ... [XII] (in the formula [XII], R ⁵ is the same as above, and Y is -O
R ⁶ groups, -OSiR ⁷ ₃ group, -OAlR ⁸ ₂ group, -NR ⁹ ₂ group,
-SiR ¹⁰ ₃ group or -N (R ¹¹⁾ is AlR ¹² ₂ group, n
Is 1-2, R ⁶ , R ⁷ , R ⁸ and R ¹² are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., and R ⁹ is a hydrogen atom,
Examples thereof include a methyl group, an ethyl group, an isopropyl group, a phenyl group, and a trimethylsilyl group. R ¹⁰ and R ¹¹ are a methyl group, an ethyl group, and the like. As the organoaluminum compound, specifically, the following compounds are used. _{^{(I) R 5 n Al (}} OR 6) compounds represented by _3-n, e.g., dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum _{^{methoxide, (ii) R 5 n Al}} (OSiR 7 3) 3- _n , for example, Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂
Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OSiE
t _{3), ^{etc., (iii) R 5 n Al}} (OAlR 8 2) a compound represented by _3-n, e.g., _{Et 2 AlOAlEt 2, (iso-} Bu) 2 Al
OAl (iso-Bu) ₂ etc.

[0110] _{^{(iv) R 5 n Al (}} NR 9 2) compounds represented by _3-n, e.g., Me ₂ AlNEt _2, Et ₂ AlNHM
e, Me ₂ AlNHEt, Et ₂ AlN (SiMe ₃ ) ₂ ,
(Iso-Bu) such as _{2 AlN (SiMe 3) 2,} (v) R 5 n Al (SiR 10 3) compounds represented by _3-n,
For example (iso-Bu) such as _{2 AlSiMe 3, (vi) R} 5 n Al (N (R 11) AlR 12 2) compounds represented by _3-n, e.g., _{Et 2 AlN (Me) AlEt 2} , (is
such as _{o-Bu) 2 AlN (Et} ) Al (iso-Bu) 2.

[0111] Among the above general formula [XI] and an organoaluminum compound represented by [XII], the general formula R ⁵ _{3
^{Al, R 5 n Al (OR}} 6) 3-n, R 5 n Al (OAlR 8 2)
Preferred examples include an organoaluminum compound represented by _3-n , wherein R ⁵ is an isoalkyl group,
Those having n = 2 are particularly preferred. These organoaluminum compounds can be used as a mixture of two or more kinds.

The ring-opening polymer of cyclic olefin [A-2] used in the present invention is a ring-opening polymer of at least one type of cyclic olefin represented by the above formula [I] or [II].

The ring-opened polymer of such a cyclic olefin can be prepared by ring-opening polymerization of the cyclic olefin represented by the above formula [I] or [II] alone or in combination. That is, a ring-opened polymer is prepared by subjecting at least one type of cyclic olefin represented by the above formula [I] or [II] to ring-opening polymerization in the presence of a ring-opening polymerization catalyst.

Examples of the ring-opening polymerization catalyst used herein include:
For example, ruthenium, rhodium, osmium, indium, platinum, metal halides such as molybdenum and tungsten, nitrates of these metals and acetylacetone compounds of these metals, and a catalyst comprising a reducing agent such as alcohols or tin compounds, and Examples include a halogen compound of a metal such as titanium, vanadium, zirconium, tungsten, and molbden, and a catalyst comprising an acetylacetone compound of these metals and a metal aluminum compound.

In preparing the above ring-opened polymer, other cyclic olefins other than at least one cyclic olefin represented by the above formula [I] or [II] may be used. As the cyclic olefin of
Cyclobutene, cyclopentene, cyclooctene, cyclononene, methylcyclopentene, methylcycloheptene, methylcyclooctene, methylcyclononene, methylcyclodecene, ethylcyclopentene, ethylcycloheptene, ethylcyclooctene, ethylcyclononene, dimethylcycloheptene, 4 carbon atoms such as dimethylcyclooctene, dimethylcyclononene, dimethylcyclodecene, cyclooctadiene and cyclodecadiene
The above monocyclic olefins and 2,3,3a, 7a-tetrahydro-4,7-methano-1H-indene, 3a,
5,6,7a-tetrahydro-4,7-methano-1H-indene and the like.

Also, propylene,
Alkenes such as 1-butene, 1-pentene and 1-hexene can be used as copolymerization components. In such a ring-opened polymer, it is considered that at least a part of the cyclic olefin represented by the formula [I] has a structure represented by the following formula [I] -a,
At least a part of the cyclic olefin represented by I]
It is considered to have a structure represented by the following formula [II] -a.

[0117]

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(In the formula [I] -a, u, v, w, R ^{61 to} R
⁷⁸ and R ^a1 and R ^b1 have the same meanings as in formula [I])

[0119]

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(In the formula [II] -a, x, y, z, d, R
^{81 to} R ⁹⁹ have the same meaning as in the formula [II]. The hydrogenated product [A-3] of the ring-opened polymer of a cyclic olefin used in the present invention is any of the above formulas [I] or [II].
Is a hydrogenated product of a ring-opening polymer of at least one cyclic olefin represented by the formula:

The hydrogenated cyclic olefin ring-opening polymer can be obtained by hydrogenating the cyclic olefin ring-opening polymer prepared as described above. For the addition, an ordinary hydrogenation method performed in the presence of a hydrogenation catalyst can be employed.

The hydrogenation catalyst used here includes:
A hydrogenation catalyst such as a heterogeneous catalyst generally used for hydrogenation of an olefinic compound or a homogeneous catalyst can be used. Specific examples of heterogeneous catalysts include metals such as nickel, palladium and platinum,
And a solid catalyst (eg, nickel / silica, nickel / diatomaceous earth, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / diatomaceous earth) in which these metals are supported on a carrier such as carbon, silica, diatomaceous earth, alumina and titanium oxide. / Alumina). Examples of homogeneous catalysts are catalysts based on metals of Group VIII of the Periodic Table. Examples of such catalysts are cobalt naphthenate, triethylaluminum, cobalt octenoate / n-butyllithium, An organic metal compound formed from a nickel compound such as nickel acetylacetonate / triethylaluminum or a cobalt compound and a metal of Groups I to III of the periodic table can be used, and a Rh compound can also be used.

The hydrogenation reaction using the hydrogenation catalyst as described above can be carried out in any of a heterogeneous system and a homogeneous system depending on the type of the catalyst. The reaction conditions in such a system are usually under a hydrogen atmosphere of 1 to 150 atm, usually 0 to 180 ° C, preferably 20 to 100 ° C.
Set to a temperature of ° C. The hydrogenation rate under such conditions can be adjusted by appropriately setting conditions such as hydrogen pressure, reaction temperature, reaction time, and catalyst concentration, but the double bond existing in the main chain of the polymer can be adjusted. Of these,
50% or more, preferably 80% or more, more preferably 90% or more is hydrogenated.

In such a hydrogenated cyclic polymer,
It is considered that at least a part of the cyclic olefin represented by the above formula [I] has a structure represented by the following formula [I] -b, and at least a part of the cyclic olefin represented by the above formula [II] Is considered to have a structure represented by the following formula [II] -b.

[0125]

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(In the formula [I] -b, u, v, w, R ^{61 to} R
⁷⁸ and R ^a1 and R ^b1 have the same meanings as in formula [I])

[0127]

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(In the formula [II-b], x, y, z, d, R
^{81 to} R ⁹⁹ have the same meaning as in formula [II])

Next, the cyclic olefin polymer will be described more specifically. [A-1] The cyclic olefin-based random copolymer is α-
The repeating unit derived from the olefin component is usually 35 to
Desirably, it is present in an amount in the range of 90 mol%, preferably 40-85 mol%, of the above formula [I] or [II]
The repeating unit derived from the cyclic olefin represented by the formula (1) is usually present in an amount of 10 to 65 mol%, preferably 15 to 60 mol%.

The intrinsic viscosity [η] at 135 ° C. in decalin is 0.05 to 5.0 dl / g, preferably 0.15 to 4.5 d.
1 / g is desirable. It is desirable that the glass transition temperature (Tg) measured by DSC is 70 ° C. or higher, preferably in the range of 70 to 250 ° C.

The refractive index n _D measured at 25 ° C. is usually 1.5
It is desirably in the range of 0.001 to 1.650, preferably 1.510 to 1.600. In the present invention, the refractive index is measured at 25 ° C. using an Abbe refractometer (D line, 589 nm). The iodine value is 3
It is desirably 0 or less.

[A-2] Ring-opened polymer of cyclic olefin,
And the intrinsic viscosity [η] of the hydrogenated product of the ring-opening polymer of [A-3] cyclic olefin in decalin at 135 ° C. is 0.05.
５5.0 dl / g, preferably 0.15 to 4.5 dl / g
Is desirably within the range.

The glass transition temperature (T
g) is 70 ° C. or more, preferably 70 to 250 ° C.
Is desirably within the range. The refractive index n _D measured at 25 ° C. is usually from 1.500 to 1.650, preferably 1.510.
It is desirably in the range of ~ 1.600.

The iodine value is desirably 30 or less.

Hereinafter, the core / shell elastomer which is the component [B] will be described. [B] component is [B-1]
40 to 85 parts by weight of a core component comprising a styrene-butadiene rubber having a styrene unit of 50% by weight or less;
-2] (b-1) 20 to 80% by weight of a monovinyl aromatic monomer, (b-2) 20 to 80% by weight of an alkyl (meth) acrylate monomer copolymerizable therewith, and (b)
-3) 15 to 60 parts by weight of a diene component comprising a copolymer comprising a monomer mixture comprising 0 to 3% by weight of a polyfunctional monomer. The core-shell elastomer is produced by seeding latex particles of a styrene-butadiene rubber as the component [B-1] as a seed, and subjecting the monomer mixture of the component [B-2] to seed polymerization according to a method known per se. can do.

A styrene-butadiene rubber latex having a styrene unit of 50% by weight or less is usually obtained by emulsion polymerization. The content of styrene units is 50% by weight or less, preferably 30% by weight or less. When producing a rubber latex, a known molecular weight regulator and a known crosslinking agent can be added. As a crosslinking agent, a crosslinking monomer,
Polyvinyl esters of polybasic acids such as divinyl adipate; di and trimethacrylates of polyhydric alcohols such as mono or polyethylene glycol dimethacrylate (or di and triacrylates of polyhydric alcohols); ethylene glycol divinyl ether Di- or triallyl esters of polybasic acids such as divinyl ether, diallyl phthalate, diallyl maleate, diallyl fumarate, diallyl sebacate, etc .; triallyl such as diallyl ether, triallyl cyanurate, triallyl isocyanurate Compounds: Allyl esters of polymerizable carboxylic acids such as allyl methacrylate, allyl acrylate, allyl itaconate, monoallyl fumarate, and monoallyl allate It can gel. The crosslinkable polymer is preferably used in a proportion of 3% by weight or less.

It is also possible to use other vinyl monomers copolymerizable with styrene and butadiene, for example, vinyl cyanide compounds such as acrylonitrile, and alkyl esters of acrylic acid and methacrylic acid at a ratio of 3% by weight or less. it can. Rubber latex used in the present invention,
Preferably in the range 50-250 nm, more preferably 6
It has an average primary particle diameter in the range of 0 to 200 nm.

As the monovinyl aromatic monomer (b-1) constituting the component (B-2), a compound represented by the following formula is preferably used.

[0139]

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(In the above formula, R ⁵² , R ⁵³ and R ⁵⁴ may be the same or different and each is a hydrogen atom or a lower alkyl group.) Specifically, styrene, α- Methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, m-ethyl styrene, p-ethyl styrene, o-isopropyl styrene, m-isopropyl styrene, p-
Isopropylstyrene and the like can be mentioned.

The above compounds may be used alone or
Used in combination of more than one species. Examples of the copolymerizable alkyl (meth) acrylate (b-2) include monomers represented by the following general formula.

[0142]

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In the above formula, R ⁵⁵ represents a hydrogen atom or a methyl group, R ⁵⁶ is an alkyl group having 1 to 10 carbon atoms, and these may have a substituent. Examples of the substituent include a hydroxyl group (-OH), an epoxy group, a halogen, an oxymethylene group, and an oxyethylene group.

Specific examples of such a (meth) acrylate include, for example, (meth) acrylic esters shown below. Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth)
Acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth)
Acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetramethylolethane mono (meth) acrylate, butenediol Mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2- (6
-Hydroxyhexanoyloxy) ethyl acrylate, glycidyl (meth) acrylate and the like. The above compounds are used alone or in combination of two or more.

Further, as the polyfunctional monomer (b-3), the same compounds as those exemplified as the crosslinkable monomer with respect to the rubber latex can be exemplified. In the monomer mixture, a monovinyl aromatic monomer (b-1)
Is 20 to 80% by weight, preferably 30 to 70% by weight, and the alkyl (meth) acrylate monomer (b-2) copolymerizable therewith is 20 to 80% by weight, preferably 30 to 7% by weight.
0% by weight, and the polyfunctional monomer (b-3) can account for 0-3% by weight, preferably 0-2% by weight.

The core / shell elastomer has an average primary particle diameter in the range of 100 to 300 nm, preferably in the range of 150 to 250 nm. The core-shell elastomer preferably has a refractive index n _D of 1.52 to 1.56, more preferably 1.525 to 1.555.

Next, the fluid lubricant as the component [C] will be described. Examples of the fluid lubricant used as the component [C] include petroleum resins, low molecular weight polyolefin waxes, and silicone oils.

Specific examples of the petroleum resin include aliphatic, alicyclic, aliphatic-alicyclic, aliphatic alicyclic-aromatic, aliphatic-aromatic, and aliphatic-aromatic compounds. Polar group-based, synthetic terpene-based, aliphatic-terpene-based, terpene-phenol-based, aromatic-terpene-based, styrene-based, aromatic olefin resin, aliphatic-aromatic-based, alicyclic saturated hydrocarbon resin, and the like. be able to.

Specific examples of the low molecular weight polyolefin wax include general polymerization type polyethylene wax (high density, low density), modified polyethylene wax (acid value type, acid modified type, styrene modified type), and pyrolysis type polyolefin wax. Can be mentioned.

Specific examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil,
Polyether-modified silicone oil, alcohol-modified silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, epoxy / polyether-modified silicone oil, phenol-modified silicone oil,
Examples thereof include a carboxyl-modified silicone oil and a mercapto-modified silicone oil.

The components [A], [B] and [C] can be blended, for example, by the following method. (1) A method in which these components are melt-blended using an extruder, a kneader or the like. (2) A method in which these components are dissolved or dispersed in an appropriate solvent (for example, a saturated hydrocarbon such as heptane, hexane, decane, or cyclohexane; an aromatic hydrocarbon such as toluene, benzene, or xylene) and blended.

The cyclic olefin polymer composition of the present invention comprises the above component [A] and component [B] in combination with the component [A] /
Component (B) is contained in a weight ratio of component 40/60 to 95/5, preferably in a range of 60/40 to 90/10. The component [C] is a total of 10 [A] and [B] components.
It is contained in an amount of 1 to 20 parts by weight, preferably 3 to 10 parts by weight per 0 parts by weight. The cyclic olefin polymer composition of the present invention improves the compatibility between the component [A] and the component [B] due to the presence of the component [C], and improves the compatibility of the component [A] /
It has improved fluidity, superior transparency and impact resistance, and a good balance of transparency, heat resistance and impact strength as compared to the composition comprising only the component [B].

Further, the components [A], [B] and [C] are subjected to a radical reaction in the presence of an organic peroxide and, if necessary, a radically polymerizable polyfunctional monomer to obtain a composition. You may.

In such a radical reaction, the cyclic olefin polymer and the core / shell elastomer powder of the present invention are subjected to a radical reaction in the presence of an organic peroxide and, if necessary, a radically polymerizable polyfunctional monomer. This is done by:

The organic peroxide used here includes ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; 1,1-
Bis (tert-butylperoxy) cyclohexane, 2,
Peroxy ketals such as 2-bis (tert-butylperoxy) octane; tert-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroxy peroxide, 1,1,3 ,
Hydroperoxides such as 3-tetramethylbutyl hydroperoxide; di-tert-butyl peroxide;
Dialkyl peroxides such as 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-diethyl-2,5-di (tert-butylperoxy) hexyne-3, lauroylperoxide Oxides, diacyl peroxides such as benzoyl peroxide; peroxyesters such as tert-butylperoxyacetate, tert-butylperoxybenzoate, and 2,5-dimethyl-2,5-di (benzoylperoxy) hexane Can be mentioned.

Examples of the radical polymerizable polyfunctional monomer used as required include divinylbenzene, vinyl acrylate, vinyl methacrylate, triaryl isocyanurate, diaryl phthalate, ethylene dimethacrylate trimethylolpropane trimeta. Acrylate and the like can be mentioned.

When the above components are subjected to a radical reaction in the presence of an organic peroxide and, if necessary, a radically polymerizable polyfunctional monomer to prepare a composition, the composition is prepared using one reactor. May be prepared, and using a plurality of reactors, reacting the above components in one reactor, reacting the three components in the other reactor in the same manner, and then blending both. It may be a final composition.

In such a radical reaction, the amount of the organic peroxide is usually 0.1 to 100 parts by weight of each component in total.
The radical-polymerizable polyfunctional monomer is used in an amount of from 0.01 to 10 parts by weight, preferably from 0.05 to 5 parts by weight, and is optionally used. 0.01 to 15 parts by weight, preferably 0.1 to 10 parts by weight
Used in parts by weight.

When the components are subjected to a radical reaction, it is desirable to react at a temperature at which the organic peroxide decomposes.
At the time of the reaction, each raw material can be mixed and reacted at the same time, but after mixing both, a method of mixing and reacting an organic peroxide and, if necessary, a radical polymerizable polyfunctional monomer is preferable. . The organic peroxide is desirably added in a state where the respective components are sufficiently mixed.

The components can be mixed by melt blending the components separately produced by an extruder or the like, or by mixing the components with a suitable solvent (for example, heptane, hexane, decane,
For example, a method of sufficiently dissolving or dispersing in a saturated hydrocarbon such as cyclohexane; an aromatic hydrocarbon such as toluene, benzene, or xylene and blending them can be employed.

An organic peroxide and, if necessary, a radical polymerizable polyfunctional monomer are added to the thus obtained mixture of the components and blended, and the mixture is reacted at a temperature at which the organic peroxide is decomposed.

Such a radical reaction can be carried out in a state where the mixture of the raw materials is molten, or in a solution state in which the mixture of the raw materials is dissolved or dispersed in a solvent. When a radical reaction is performed in a molten state, the raw material mixture is melted and mixed using a kneading device such as a mixing roll, a Banbury mixer, an extruder, a kneader, or a continuous mixer. The radical reaction is performed at a temperature equal to or higher than the one-minute half-life of the organic peroxide, usually 150 to 300
C., preferably at 170 to 270.degree. C., usually for 10 seconds to 30 minutes, preferably 3 to 10 minutes.

As the solvent used when the radical reaction is carried out in the state of being dissolved or dispersed in a solvent, the same solvents as those used in the solution blending method can be used. The radical reaction is desirably carried out at a temperature of not less than the half-life of 10 minutes of the organic peroxide, usually at a temperature of 50 to 300 ° C., usually for 10 seconds to 2 hours.

The composition can be used alone, or can be blended with another transparent resin. The cyclic olefin polymer composition provided in this manner is molded and processed by a known method. For example, single-screw extruder, vented extruder, twin-screw extruder, conical twin-screw extruder, co-kneader, plasticizer, mixtruder, twin-screw conical screw extruder, planetary screw extruder, gear-type extruder Extrusion molding, injection molding, blow molding and rotational molding are performed by a screwless extruder or the like.

A rubber component may be added to such a cyclic olefin polymer composition in order to further improve the impact strength of the composition, and heat-resistant stabilizers, weather-resistant stabilizers, antistatic agents, slip agents , An antiblocking agent, an antifogging agent, a lubricant, a dye, a pigment, a natural oil, a synthetic oil, a wax and the like can be appropriately compounded.

For example, phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, fatty acid metal salts and fatty acid esters of polyhydric alcohols are preferably used as stabilizers to be added as optional components. Can be As the phenolic antioxidant, for example, the following formula A
n-1

[0167]

Embedded image

(Where R ₁ and R ₂ each have 1 to 1 carbon atoms)
An alkyl group having a linear or side chain of 4, R ₃ is an alkyl group having a linear or side chain having 8 to 20 carbon atoms, or —CH ₂ —CH ₂ —COOX, and X is an alkyl group having 8 to 20 carbon atoms. A linear or branched alkyl group), a compound represented by the following formula An-2

[0169]

Embedded image

(Where R ₁ and R ₂ are defined by the above formula A
n-1), and R ₄ and R ₅ are independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or the following formula:

[0171]

Embedded image

Compounds represented by the following formulas can be mentioned. As the compound represented by the above formula An-1, 2,
6-di-tert-butyl-4-nonylphenol, 2,6-di-tert-butyl-4-dodecylphenol, 2,6-di-t-
Butyl-4-hexadecylphenol, 2,6-di-t-
Butyl-4-octadecylphenol, 2-t-butyl-6-isopropyl-4-octadecylphenol,
2,6-diisopropyl-4-octadecylphenol, 3- (4'hydroxy-3 ', 5'-di-tert-butylphenyl) -n-dodecylpropionate, 3- (4'-hydroxy-3', 5 ' -Di-tert-butylphenyl) propionic acid-hexadecyl, 3- (4'-hydroxy-3 ', 5'-
Di-tert-butylphenyl) -n-octadecylpropionate, 3- (4'-hydroxy-3'-tert-butyl-5'-
N-octadecyl isopropylphenyl) propionate, 3- (4'-hydroxy-3'-t-butyl-3'-
Methylphenyl) -n-octadecyl propionate.

Examples of the compound represented by the above formula An-2 include 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane (registered trademark “Topanol CA”). And 4,4′-butylidenebis (6-tert-butyl-m-cresol) (registered trademark “Sant
owhite Powder ”).
anol CA "is preferred. Other phenolic antioxidants include tetrakis [methylene-3 (3,5-di-t).
-Butyl-4-hydroxyphenyl) propionate]
Methane, β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2′-
Oxamidobis [ethyl-3 (3,5-di-t-butyl-4-hydroxyphenyl)] propionate and the like can be mentioned.

As the sulfur-based antioxidant, the following formula An
-3

[0175]

Embedded image

[0176] (wherein, m, n is an integer of from 1 to 4, R ₆
And R ₇ is an alkyl group having 8 to 20 carbon atoms and having a straight or side chain). Examples of the compound represented by the formula An-3 include dicapryl thiodipropionate, dilauryl thiodipropionate, dipalmityl thiodipropionate, and distearyl thiodipropionate. Other sulfur-based antioxidants include 4,4'-thiobis (6-t-butyl) -3-methylphenol, 2,4-
Bis (n-octylthio) -6- (4-hydroxy-
(3,5-di-t-butylanilino) -1,3,5-triazine and the like.

Further, as the phosphorus-based antioxidant, the following formula A
n-4

[0178]

Embedded image

(Where X is an oxygen atom or a lone electron pair, and R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a mono- or di- Which is an alkyl) -substituted phenyl having 1 to 20). Phosphorus compounds represented by the formula An-4 include phosphoric acid and tris (nonylphenyl) phosphite.

Examples of the fatty acid metal salt include zinc stearate, calcium stearate, calcium 12-hydroxystearate and the like. Examples of the fatty acid ester of the polyhydric alcohol include, for example, glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. . These may be used alone or in combination. For example, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, zinc stearate and glycerin A combination with monostearate and the like can be exemplified.

Particularly, it is preferable to use a combination of a phenolic antioxidant and a fatty acid ester of a polyhydric alcohol.
It is preferable that the polyhydric alcohol is a polyhydric alcohol fatty acid in which a part of the alcoholic hydroxyl group of the polyhydric alcohol having a valency or higher is esterified. As the fatty acid ester of such a polyhydric alcohol, specifically, glycerin monostearate, glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin distearate, glycerin fatty acid esters such as glycerin dilaurate, Pentaerythritol monostearate,
Fatty acid esters of pentaerythritol such as pentaerythritol monolaurate, pentaerythritol dilaurate, pentaerythritol distearate and pentaerythritol tristearate are used. Such a phenolic antioxidant is used in an amount of 0 to 5 parts by weight, preferably 0 to 2 parts by weight, more preferably 0 to 1 part by weight based on 100 parts by weight of the cyclic olefin polymer composition. . The sulfur-based antioxidant is used in an amount of 0 to 5 parts by weight, preferably 0 to 2 parts by weight, more preferably 0 to 1 part by weight, based on 100 parts by weight of the cyclic olefin polymer composition. The phosphorus antioxidant is used in an amount of 0 to 5 parts by weight, preferably 0.01 to 2 parts by weight, more preferably 0.01 to 1 part by weight, per 100 parts by weight of the cyclic olefin polymer composition.
Used in parts by weight.

The fatty acid metal salt is used in an amount of 0 to 5 parts by weight, preferably 0 to 5 parts by weight, based on 100 parts by weight of the cyclic olefin polymer composition.
To 2 parts by weight, more preferably 0 to 1 part by weight. The fatty acid ester of the polyhydric alcohol is used in an amount of 0 to 5 parts by weight, preferably 0 to 2 parts by weight, based on 100 parts by weight of the cyclic olefin polymer composition.

If necessary, the cyclic olefin-based copolymer composition may contain silica, diatomaceous earth, alumina, titanium oxide,
Magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate,
Barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, polycarbon number 2 Fillers such as the above-mentioned α-olefin fibers, polypropylene fibers, polyester fibers, polyamide fibers and the like can also be blended.

[0184]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In the present invention, measurement and evaluation of various physical property values were performed as follows.

Various Physical Properties of Core / Shell Elastomer (1) Amount of Copolymer Component Constituting Core / Shell Elastomer Calculated from the charged amount and yield. (2) Refractive index 25 ° C. using Abbe's refractometer (D line, 589 nm)
Was measured. (3) Average particle size of primary particles of core / shell elastomat Laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, SA
LD-200).

Various Physical Properties of Cyclic Olefin Copolymer (1) Intrinsic Viscosity ([η]) Measured at 135 ° C. in a decalin solution using an Ubbelohde viscometer. (2) Glass transition point (Tg) The glass transition point (Tg) was measured at a heating rate of 10 ° C./min in a N ₂ atmosphere using DSC-220C manufactured by Seiko Instruments Inc. (3) Monomer composition ratio in polymer Measured by ¹³ C-NMR. (4) Iodine value It was measured by the iodine monochloride method according to JIS K3331.

Method for Measuring and Evaluating Various Physical Properties of Core / Shell Elastomer / Cyclic Olefin Copolymer Composition (1) Method for Preparing Composition A predetermined amount of the core / shell elastomer and the cyclic olefin copolymer were prepared by mixing polyolefin under nitrogen atmosphere. The mixture was mixed well in a bag and replaced with nitrogen for 2 hours. The mixture was heated at a cylinder maximum temperature of 230 ° C. using a twin screw extruder (Model TW100 manufactured by Haake)
The mixture was melt-blended at a residence time of 1 minute and pelletized with a pelletizer. (2) Preparation of test piece The test piece was molded under the following molding conditions using an injection molding machine IS50EPN manufactured by Toshiba Machine Co., Ltd. and a predetermined test piece mold. The test pieces were left for 48 hours at room temperature after molding and then subjected to measurement. Molding conditions: Cylinder temperature: 230 ° C., mold temperature: 30 ° C., injection pressure: primary / secondary = 1000/800 kg / cm ² (3) Haze value manufactured by Nippon Denshoku Industries Co., Ltd. according to ASTM D-1003 Using a digital turbidity (cloudiness) meter NDH-20D, a 2 mm-thick press sheet was measured as a sample. (4) Izod impact strength Measured according to ASTM D256. Test specimen shape: 5/2 x 1/8 x 1/2 ^t inch (with notch) Test temperature: 23 ° C

[Synthesis Example of Cyclic Olefin Copolymer I (hereinafter referred to as Copolymer I)] Using a vanadium catalyst,
Ethylene, tetracyclo [4.4.0.1 ^2,5 .1 ^{7, 10]}
Copolymerization with -3-dodecene (hereinafter sometimes abbreviated as "TCD" S) was continuously performed by the following method.

A cyclohexane solution of TCD was continuously supplied from the top of a 1-liter glass polymerization vessel equipped with a stirring blade so that the supply concentration of TCD in the polymerization vessel was 40 g / liter. A cyclohexane solution of VO (O.ethyl) Cl ₂ is used as a catalyst from the upper part of the polymerization vessel so that the vanadium concentration in the polymerization vessel becomes 0.5 mmol / L, and ethyl aluminum sesquichloride (Al (C ₂ H) is used. ₅ ) A cyclohexane solution of _1.5 Cl _1.5 ) was continuously supplied into the polymerization vessel so that the aluminum concentration in the polymerization vessel was 4.0 mmol / L. In addition, ethylene was added to the polymerization system using a bubbling tube.
6.0 liters / hour, nitrogen 35.0 liters / hour,
Hydrogen was supplied at a rate of 1.0 liter / hour.

A copolymerization reaction was carried out while maintaining the polymerization system in which a heating medium was circulated in a jacket attached to the outside of the polymerization vessel at 10 ° C. The polymerization solution of the copolymer produced by the above-mentioned copolymerization reaction is continuously fed from the top of the polymerization vessel so that the polymerization liquid in the polymerization vessel always becomes 1 liter (that is, so that the average residence time is 0.5 hour). Extracted. To the extracted polymerization solution, a cyclohexane / isopropyl alcohol (1: 1) mixed solution was added to stop the polymerization reaction. Thereafter, an aqueous solution in which 5 ml of concentrated hydrochloric acid was added to 1 liter of water and the polymerization solution were mixed in a ratio of 1: Using a homomixer at a ratio of 1 under strong stirring, the catalyst residue was transferred to the aqueous phase.
After allowing this contact mixture to stand, separating and removing the aqueous phase,
Further, washing with distilled water was performed twice, and the polymerization liquid phase was purified and separated. Next, the polymer solution purified and separated was brought into contact with a three-fold amount of acetone under vigorous stirring to precipitate a copolymer, and then the solid portion was collected by filtration and sufficiently washed with acetone. Further, in order to extract unreacted TCD present in the copolymer, this solid portion was poured into acetone so as to have a concentration of 40 g / liter, and an extraction operation was performed at 60 ° C. for 2 hours. After the extraction treatment, the solid portion was collected by filtration and dried at 130 ° C. and 350 mmHg for 12 hours under a nitrogen flow.

As described above, the obtained ethylene / T
The CD copolymer (hereinafter referred to as copolymer I) has an intrinsic viscosity [η] of 0.65 dl / g, a Tg of 82 ° C., and a TC
The D content was 28.1 mol%, and the iodine value was 0.1 g iodine / 100 g. The refractive index (nD) of the copolymer I was 1.538.

[Synthesis Example of Core / Shell Elastomer [B] Component] (1) Into an autoclave equipped with a stirrer sufficiently substituted with nitrogen so as to have the following composition, and reacted at 50 ° C. with stirring for 15 hours. I let it. Butadiene 75 parts Styrene 25 parts Polyethylene glycol dimethacrylate 1.0 parts Diisopropylbenzene hydroperoxide 0.2 parts Sodium formaldehyde sulfoxylate 0.2 parts Ethylenediaminetetraacetic acid (EDTA) disodium salt 0.0006 parts Ferrous sulfate heptahydrate 0.002 parts Sodium pyrophosphate 0.3 parts Sodium oleate 2.0 parts Ion exchange water 200 parts )was gotten.

(2) The obtained latex was charged into an autoclave equipped with a stirrer, which had been sufficiently substituted with nitrogen in the same manner as described above, to have the following composition, and was polymerized at 50 ° C. for 50 hours. Latex A (as solid content) 8 parts Styrene 23 parts Butadiene 69 parts Diisopropylbenzene hydroperoxide 0.1 parts Sodium formaldehyde sulfoxylate 0.1 parts EDTA / 2 sodium salt 0.004 parts Ferrous sulfate / 7 water Salt 0.001 part Sodium pyrophosphate 0.3 part Sodium oleate 0.5 part Deionized water 150 parts

Every 10 hours after the start of the reaction, 0.1 part of diisopropylbenzene hydroperoxide and 0.1 part of sodium formaldehyde sulfoxylate were added. On the other hand, 1.5 parts of sodium oleate was made into a 1% aqueous solution and continuously added over 40 hours. The final conversion was about 95%, and the average particle size of the obtained rubber latex (hereinafter, referred to as latex B) was 170 nm. When latex B was observed with an electron microscope,
There were no latex particles having a particle size of 100 nm or less and a particle size of 300 nm or more. As described above, a styrene-butadiene rubber latex containing 25% by weight of styrene and 75% by weight of butadiene (=
The core component) was synthesized (latex B).

(3) Using latex B, a core / shell elastomer was synthesized by the following method. While performing nitrogen substitution, the raw materials were charged into a glass container so as to have the following composition, and the mixture was stirred at 70 ° C. Latex B (as solid content) 70 parts EDTA disodium salt 0.008 part Ferrous sulfate heptahydrate 0.002 part Sodium formaldehyde sulfoxylate 0.2 part Ion-exchanged water 250 parts The composition was added continuously over 2 hours. Methyl methacrylate (MMA) 17 parts Polyethylene glycol dimethacrylate 1.0 part Diisopropylbenzene hydroperoxide 0.1 part

When stirring was further continued for 1 hour after the completion of the addition, the conversion was 98%. Further, the following composition was continuously added over 2 hours. Styrene 13 parts Diisopropylbenzene hydroperoxide 0.2 part After the addition was completed, diisopropylbenzene hydroperoxide 0.1 part was added, and the mixture was further stirred for 3 hours. As a result, the conversion was 98%, and the obtained latex , Latex D) had an average particle size of 180 nm. Observation of latex C with an electron microscope showed that
There were no latex particles having a particle size of 00 nm or less and 300 nm or more. Latex D obtained
Then, 1 part of 2,6-ditert-butyl-p-cresol (BHT) and 0.5 part of dilaurylthiodipropionate are added as stabilizers, and after sufficient stirring, an aqueous hydrochloric acid solution is added, followed by coagulation, dehydration and drying. Was.

Example 1 80 parts by weight of the cyclic olefin copolymer (copolymer I) shown in the above Preparation Example, 20 parts by weight of the core / shell elastomer shown in the preparation example of Component B, and Escolets 5320 as Component C A mixture consisting of 3 parts by weight (manufactured by Tonex) was thoroughly mixed in a plastic bag under a nitrogen atmosphere, and the atmosphere was replaced with nitrogen for 2 hours. The mixture is supplied to a twin-screw extruder (Haake, T
(W100 type), melt-blended at a cylinder maximum temperature of 200 ° C. and a residence time of 1 minute, and pelletized with a pelletizer. Table 1 shows the obtained results.

Example 2 Example 1 was repeated except that FTR6100 (manufactured by Mitsui Petrochemical Co., Ltd.) was used as the C component.
A composition was prepared in the same manner as described above. The results are shown in Table 1.

Example 3 In Example 1, Mitsui High Wax 11 was used as the C component.
A composition was prepared in the same manner as in Example 1 except that 1.5 parts by weight of 0P and 1.5 parts by weight of 1120H were used (manufactured by Mitsui Petrochemical Co., Ltd.). The results are shown in Table 1.

Example 4 In Example 1, the silicone oil SH was used as the C component.
A composition was prepared in the same manner as in Example 1 except that 710 (manufactured by Toray Silicone Co., Ltd.) was used. The results are shown in Table 1.

Comparative Example 1 A composition was prepared in the same manner as in Example 1, except that nothing was added as the component C. The results are shown in Table 1.

[0202]

[Table 1]

[0203]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08L 91/06 C08L 91/06 (72) Inventor Masayuki Okabe 1-2 1-2 Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Within Kogyo Kogyo Co., Ltd. (72) Inventor Masahiro Kishine 6-1-2, Waki, Waki-cho, Kuga-gun, Yamaguchi Pref. Mitsui Petrochemical Industry Co., Ltd. JP-A-7-233302 (JP, A) JP-A-7-233301 (JP, A) JP-A-4-266950 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 1 / 00-101/16

Claims (4)

(57) [Claims] 1. [A]. [A-1] (i) at least one α-olefin having 2 or more carbon atoms
And (ii) the following formula [I] or [II]:(In the formula [I], u is 0 or 1, and v is 0 or positive.
And w is 0 or 1, and R⁶¹~ R⁷⁸If
R^a1And R^b1Are each independently a hydrogen atom,
A hydrogen atom or a hydrocarbon group;⁷⁵~ R⁷⁸Is
May combine to form a monocyclic or polycyclic ring,
The monocyclic or polycyclic ring may have a double bond;
R⁷⁵And R⁷⁶With or R⁷⁷And R⁷⁸And alkylidene
May form a group),(In the formula [II], x and d are 0 or an integer of 1 or more.
And y and z are 0, 1 or 2;⁸¹~ R⁹⁹
Are each independently a hydrogen atom, a halogen atom, an aliphatic carbon
Hydrogen group, alicyclic hydrocarbon group, aromatic hydrocarbon group or
A alkoxy group;⁸⁹Or R⁹⁰To which the carbon is attached
Atom and R⁹³Is bonded to a carbon atom or R⁹¹Is combined
The carbon atom being used is directly or has 1 to 3 carbon atoms.
May be bonded via an alkylene group of
When z = 0, R⁹⁵And R⁹²Or R ⁹⁵And R⁹⁹And each other
May combine to form a monocyclic or polycyclic aromatic ring.
At least one cyclic olefin represented by
Cyclic olefin copolymer obtained by copolymerization of
[A-2] represented by the above formula [I] or [II]
A ring-opening polymer of at least one cyclic olefin,
[A-3] represented by the above formula [I] or [II],
Hydrogenation of ring-opening polymer of at least one cyclic olefin
A cyclic olefin polymer selected from the group consisting of
The intrinsic viscosity [η] in decalin at 135 ° C. is
0.05-5.0 dl / g, measured by DSC
Glass transition temperature (Tg) is 70 ° C or higher, and at 25 ° C
A ring having a measured refractive index nD of 1.500 to 1.650
[B]. [B-1] Styrene unit having a styrene unit of 50% by weight or less.
Core component 40 to 85 made of tylene-butadiene rubber
By weight and [B-2] (b-1) 20 to 80% by weight of a monovinyl aromatic monomer (b-2) 20 to 80% by weight of an alkyl (meth) acrylate monomer copolymerizable therewith and (B-3) a copolymer comprising a monomer mixture consisting of 0 to 3% by weight of a polyfunctional monomer as a constituent component
Shell component consisting of 15 to 60 parts by weight,
The total of the component [B-1] and the shell component [B-2] is 10
0 parts by weight, and the average diameter of the primary particles is 100 to
In the range of 300 nm
A core / shell elastomer and [C] a fluid lubricant, and the component [A]
[B] The weight ratio of the component is in the range of 40/60 to 95/5.
In addition, a total of 100% by weight of the components [A] and [B]
[C] component per part is in the range of 1 to 20 parts by weight.
A cyclic olefin polymer composition characterized by the following. 2. The cyclic olefin polymer composition according to claim 1, wherein the component [C] is a petroleum resin. 3. The cyclic olefin polymer composition according to claim 1, wherein the component [C] is a low molecular weight polyolefin wax. 4. The cyclic olefin polymer composition according to claim 1, wherein the component [C] is a silicone oil.