JPH07247386A - Cycloolefin polymer composition - Google Patents

Abstract

PURPOSE: To obtain a cycloolefin polymer compsn. which has an improved impact strength without losing its clarity by incorporating, a cycloolefin polymer, a core-shell elastomer, and a specific compd. into an α-olefin.

CONSTITUTION: This compsn. comprises at least one 2C or higher α-olefin, a cycloolefin polymer (A) selected from among cycloolefin random copolymers of formula I or II, at least one cycloolefin ring-opening polymer of formula I or II, and a hydrogenation product of at least one cycloolefin ring-opening polymer of formula I or II, a core-shell elastomer (B) comprising cores formed from a styrene-butadiene rubber having a styrene unit content of 50 wt.% or lower and shells formed from a copolymer of a monovinylarom. monomer, an alkyl (meth)acrylate monomer copolymerizable therewith, and a polyfunctinal monomer, and a (co)polymer (C) of an acrylate or methacrylate monomer having an aliph. backbone of formula I or IV or a mixture of such monomers.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a cycloolefin polymer composition. More specifically, it relates to a cycloolefin polymer composition containing a cycloolefin polymer and having excellent impact resistance.

[0002]

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

However, although these cyclic olefin-based copolymers have excellent heat resistance and rigidity, there is room for improvement in impact resistance, and the transparency possessed by these cyclic olefin-based copolymers is maintained. At the same time, further improvement in impact resistance is required.

Further, the applicant of the present invention has found that 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 it has already been proposed in JP-A-1-163241.

Further, the present applicant has proposed, as a cycloolefin polymer composition having improved impact resistance, a specific cyclic olefin random copolymer and a specific soft copolymer as an organic peroxide. A cyclic olefin-based copolymer composition comprising a product obtained by the reaction in the presence of the above has been already proposed in JP-A-2-167318.

However, the cycloolefin polymer compositions proposed in JP-A-1-163241 and JP-A-2-167318 have improved impact resistance, but are not sufficiently transparent. No, 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 cycloolefin polymer composition having improved impact resistance without impairing the original transparency of the cycloolefin copolymer. Further objects and advantages of the present invention will be 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 an α-olefin having 2 or more carbon atoms. 1 type, and (ii) the following formula [I] or [II]

[0009]

[Chemical 7]

(In the formula [I], u is 0 or 1, and v
Is 0 or a positive integer, w is 0 or 1, and R
^{61 to} R ⁷⁸ and R ^a1 and R ^b1 are each independently
A hydrogen atom, a halogen atom or a hydrocarbon group, R ⁷⁵
To R ⁷⁸ may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and R ⁷⁵ and R ⁷⁶ are each represented by Or R ⁷⁷ and R ⁷⁸ may form an alkylidene group),

[0011]

[Chemical 8]

(In the formula [II], x and d are 0 or 1
Is an integer greater than or equal to y and z is 0, 1 or 2.
R⁸¹~ R⁹⁹Are independently hydrogen atom and halogen atom
Child, aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic carbonization
A hydrogen group or an alkoxy group, R⁸⁹Or R⁹⁰Concludes
A carbon atom and a R⁸³The carbon atom to which
Or R⁹¹The carbon atom to which is bound is directly or
Even if it is bonded through an alkylene group having 1 to 3 elementary atoms
Well, when y = z = 0, R⁸⁵And R⁸²Or R ⁸⁵When
R⁹⁹And are bonded to each other to form a monocyclic or polycyclic aromatic ring.
At least one of
Cyclic olefin obtained by copolymerizing with cyclic olefin
-Based random copolymer, [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
So, the intrinsic viscosity [η] in decalin at 135 ℃ is
0.05-5.0 dl / g, measured by DSC
Glass transition temperature (Tg) is 70 ℃ or more, at 25 ℃
Measured refractive index n_DWith 1.500 to 1.650
Olefin polymer,

[B]. [B-1] 40 to 85 parts by weight of a core component consisting of styrene-butadiene rubber having a styrene unit content of 50% by weight or less and [B-2] (b-1) monovinyl aromatic Monomer 20 to 80% by weight (b-2) 20 to 80% by weight of an alkyl (meth) acrylate monomer copolymerizable therewith and (b-3) a polyfunctional monomer 0 to 3% by weight 15 to 60 parts by weight of a shell component made of a copolymer having a monomer mixture of as a constituent, 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]. [C-1] the following general formula [III]

[0014]

[Chemical 9]

(In the formula [III], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸ and R ^a and R ^b are respectively Independently a hydrogen atom, a halogen atom or a hydrocarbon group,
R ¹⁵ to R ¹⁸ may form a monocyclic or polycyclic bonded to each other, and may be monocyclic or polycyclic have a double bond, also R ¹⁵ and R ¹⁶ Or R ¹⁷ and R ¹⁸ may form an alkylidene group, and X ¹ and X ²
One of the groups is an acryloyloxy group or a methacryloyloxy group represented by the following formula [X],
The other is a hydrogen atom or an alkyl group),

[0016]

[Chemical 10]

## STR1 ## wherein R is a hydrogen atom or a methyl group, a compound of the following general formula [IV]

[0018]

[Chemical 11]

(In the formula [IV], p and l are 0 or an integer of 1 or more, and r and s are 0, 1 or 2
And R ^{21 to} R ³⁹ each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, and R ²⁹ and R ³⁰ are The carbon atom bonded to R ³³ and the carbon atom bonded to R ³³ or the carbon atom bonded to R ³¹ may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and , R = s = 0,
R ³⁵ and R ³² or R ³⁵ and R ³⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring, and one of X ³ and X ⁴ is represented by the above formula [X]. An acryloyloxy group or a methacryloyloxy group, the other of which is a hydrogen atom or an alkyl group), and a compound represented by the following formula [V]

[0020]

[Chemical 12]

(In the formula [V], t is 4 or 5, and R is
^{41 to} R ⁴³ each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group, and X ⁵ represents an acryloyloxy group or a methacryloyloxy group represented by the following formula [X]). An acrylate or methacrylate monomer having an alicyclic skeleton selected from the group consisting of a (co) polymer having as a constituent a monomer or monomer mixture containing at least 20 to 100% by weight, The weight ratio of the component [A] to the component [B] is in the range of 40/60 to 95/5, and [C] per 100 parts by weight of the total of the components [A] and [B].
This is achieved by a cycloolefin polymer composition characterized in that the components are in the range of 3 to 40 parts by weight.

Cycloolefin random copolymer [A-
Examples of the (i) α-olefin having 2 or more carbon atoms used in the copolymerization of 1] include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 4
-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
0 α-olefins. You may use these in combination of 2 or more types. Of these, ethylene is particularly preferably used.

The compounds represented by the formulas [I] and [II] used for copolymerizing the cyclic olefin 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, this 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.

The cycloalkyl group includes a cyclohexyl group, and the aromatic hydrocarbon group includes a phenyl group and a naphthyl group. Furthermore, the above formula [I]
, R ⁷⁵ and R ⁷⁶ , R ⁷⁷ and R ⁷⁸ , R ⁷⁵ and R
⁷⁷ and R ⁷⁶ and R ⁷⁸ , R ⁷⁵ and R ⁷⁸ , or R
⁷⁶ and R ⁷⁷ may be bonded to each other (cooperatively 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 monocycle or polycycle formed here include the following.

[0028]

[Chemical 13]

In the above examples, the carbon atoms numbered 1 or 2 are each R in the formula [I].
^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. Further, 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 are the same as the halogen atom in the above formula [I]. The aliphatic hydrocarbon group usually includes 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 and an aralkyl group, and specific examples thereof include a phenyl group, a tolyl group, a funatyl group, a benzyl group and a phenylethyl group.

Examples of the alkoxy group include methoxy group and eth
Examples thereof include a xy group and a propoxy group. Where R⁸⁹
And R⁹⁰The carbon atom to which R is attached, and R⁹³Combined with
Carbon atom or R⁹¹The carbon atom to which is bound is
Directly or through an alkylene group having 1 to 3 carbon atoms
May be combined. That is, the above two carbon atoms are
When linked via an alkylene group, R⁸⁹And R
⁹³Or or R⁹⁰And R ⁹¹Together with each other,
Ren group (-CH₂-), Ethylene group (-CH₂CH₂−)
Or propylene group (-CH₂CH₂CH₂-)
It forms some alkylene group.

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 ring formed by R ⁹⁵ and R ⁹² can be mentioned.

[0035]

[Chemical 14]

Here, l 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 derivative (bicyclohept-2-ene derivative), tricyclo-3-decene derivative, 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 derivative, heptacyclo-4-eicosene derivative, heptacyclo-5-heneicosene derivative, octacyclo-5-docosene derivative, nonacyclo-5-pentacosene derivative, nonacyclo-6-hexacosene derivative,
Cyclopentadiene-acenaphthylene adduct, 1,4-
Examples thereof include methano-1,4,4a, 9a-tetrahydrofluorene derivative and 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene derivative.

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

[0039]

[Chemical 15]

[0040]

[Chemical 16]

[0041]

[Chemical 17]

[0042]

[Chemical 18]

[0043]

[Chemical 19]

[0044]

[Chemical 20]

[0045]

[Chemical 21]

[0046]

[Chemical formula 22]

[0047]

[Chemical formula 23]

[0048]

[Chemical formula 24]

[0049]

[Chemical 25]

[0050]

[Chemical formula 26]

[0051]

[Chemical 27]

[0052]

[Chemical 28]

[0053]

[Chemical 29]

[0054]

[Chemical 30]

[0055]

[Chemical 31]

[0056]

[Chemical 32]

[0057]

[Chemical 33]

[0058]

[Chemical 34]

[0059]

[Chemical 35]

General formula [I] or [II] as described above
The cyclic olefin represented by can be produced by subjecting cyclopentadiene and olefins having a corresponding structure to a Diels-Alder reaction.

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

[0062]

[Chemical 36] (In the formula [I ′], u, v, w and R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 are the same as defined in the above formula [I].)

[0063]

[Chemical 37]

(In the formula [II '], y, z, x, d and R ^{81 to} R ⁹⁹ are the same as defined in the above formula [II].) These cyclic olefins may be used alone or in combination of two or more. It 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 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
Produced by copolymerizing in the presence of a metallocene compound of a transition metal selected from the group or lanthanides and an organoaluminum oxy compound, and optionally a catalyst (b) formed from an organoaluminum compound (B). You can

The soluble vanadium compound which forms such a catalyst (a) is specifically represented by the following general formula. VO (OR) _a X _b or V (OR) _c X _d where R is a hydrocarbon group, and a, b, c, d are 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦, respectively. a + b ≦ 3,0
≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ c + d ≦ 4 are satisfied. 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 (O-n-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 kinds.

The soluble vanadium compound can also be used as an electron-donor adduct obtained by contacting an electron donor as shown below. Such electron donors include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, organic acid or inorganic acid esters, ethers, diethers, acid amides, acid anhydrides. Examples thereof include oxygen-containing electron donors such as substances and 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,
Alcohols having 1 to 18 carbon atoms such as cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol, and halogen-containing alcohols having 1 to 18 carbon atoms such as trichloromethanol, trichloroethanol and trichlorohexanol; phenol, cresol, xylenol, ethylphenol , Propylphenol,
C6 to C20 phenols which may have a lower alkyl group such as nonylphenol, cumylphenol and naphthol; C3 to C15 ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone , Acetaldehyde, propionaldehyde, octyl aldehyde,
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 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;
C2 to C15 acid halides such as acetyl chloride, benzoyl chloride, toluic acid chloride and anisic acid chloride; C2 to C2 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, benzoic anhydride; alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane; acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluyl Acid N, N-dimethylamide and other acid amides; trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylethylenediamine and other amines; acetonitrile, benzonitrile, trinitrile, etc. 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 kinds. The organoaluminum compound (A) that forms the catalyst (a) with the above-mentioned soluble vanadium compound has at least one Al-C bond in the molecule, and for example, the following formulas (a) and (b) are used. It is represented by.

(A) General formula R ¹ _m Al (OR ² ) _n H _p X _q (wherein R ¹ and R ² are usually a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms). 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 0 ≦ q <3, and m + n + p + q = 3
(B) General formula M ¹ AlR ¹ (in the formula, M ¹ is Li, Na, K, and R ¹ is the same as the above), and a complex alkyl compound of a Group 1 metal and aluminum. Specific examples of the organic aluminum 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 of 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) (3) General Formula R ¹ _m AlH _3-m (wherein R ¹ is the same as above, and m is preferably 2 ≦
m <3 is a number) (4) General formula R ¹ _m Al (OR ² ) _n X _q (wherein R ¹ and R ² are the same as defined above, X is a halogen, and 0 <m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, m
+ N + q = 3) More specifically, as the organoaluminum compound (A) represented by (a), 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; Ethyl aluminum sesquiethoxide, butyl aluminum sesquibutoxide and R ¹ _2.5 Al (O
Partially alkoxylated alkylaluminum having an average composition represented by R ² ) _{0.5 and the} like can be mentioned.

Examples of the organoaluminum compound represented by (2) include dialkyl aluminum halides such as diethyl aluminum chloride, dibutyl aluminum chloride and diethyl aluminum bromide; alkyl aluminum such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide. Aluminum sesquihalide; partially halogenated alkyl aluminum such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide and the like can be mentioned.

Examples of the organoaluminum compound represented by (3) include dialkyl aluminum hydrides such as diethyl aluminum hydride and dibutyl aluminum hydride; partially hydrogenated alkyl aluminums such as ethyl aluminum dihydride and propyl aluminum dihydride. Can be mentioned.

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

Further, it may be a compound similar to the compound represented by the above general formula (a), for example, an organoaluminum compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom. Such compounds _{include, (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.

Further, as the compound belonging to (b) above,
_{LiAl (C 2 H 5) 4} , LiAl (C 7 H 15) 4 and the like can be exemplified. Of these, alkylaluminum halides, alkylaluminum dihalides, and mixtures thereof are particularly preferable.

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

Examples of the transition metal compound of Group IVB or lanthanide of the periodic table 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 Group IVB and lanthanides of the periodic table, and specifically, zirconium, titanium, hafnium, neodymium, samarium. Or yttrium, L is a ligand that coordinates to a 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. Group, SO ₃ R
(However, 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 the valence of the transition metal.

Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group. 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.

Of these ligands which coordinate to the transition metal, an alkyl-substituted cyclopentadienyl group is particularly preferable. When the compound represented by the above general formula [X] contains two or more groups having a cyclopentadienyl skeleton, two of the groups having a cyclopentadienyl skeleton are alkylene groups such as ethylene and propylene, and isopropyl group. They may be bonded via a substituted alkylene group such as lidene or diphenylmethylene, a silylene group or a dimethylsilylene group, a substituted silylene group such as a diphenylsilylene group or a methylphenylsilylene group.

Examples of the ligand other than the ligand 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 neophyll group It is illustrated. Examples of the alkoxy group include methoxy group, ethoxy group, butoxy group and the like.
A phenoxy group etc. are illustrated as an aryloxy group. Examples of halogen include fluorine, chlorine, bromine, iodine and the like. 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 above 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 ytterbium, and R ¹ is a cyclopentadienyl skeleton. R ² , R ³ and R ⁴ are groups having a cyclopentadienyl skeleton, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, halogen atoms, trialkylsilyl groups. , 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 above general formula [X ′] is a group having a cyclopentadienyl skeleton, for example, R ¹ and R ² are cyclopenta A transition metal compound which is a group having a dienyl skeleton is preferably used. Groups having these cyclopentadienyl skeletons include alkylene groups such as ethylene and propylene, alkylidene groups such as isopropylidene, substituted alkylene groups such as diphenylmethylene, silylene groups or dimethylsilylene, diphenylsilylene, substituted methylphenylsilylene groups and the like. It may be bound 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-toluenesulfonato), bis (4,5,
6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride,

Ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) ) Zirconium bis (methane sulfonate), ethylene bis (indenyl) zirconium bis (p-toluene sulfonate), ethylene bis (indenyl) zirconium bis (trifluoromethane sulfonate), ethylene bis (4,5,6,7-tetrahydro) Indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (methylcyclopentadiene (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, dimethylsilylene bis (indenyl) zirconium dichloride, dimethylsilylene bis (indenyl)
Zirconium bis (trifluoromethane sulfonate),
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) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride, bis (cyclopentadienyl) benzyl zirconium monochloride, bis (cyclopentadienyl) zirconium monochloride, bis (cyclo Pentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bi (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 (trifluoromethane sulfonate),

Bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethane) Sulfonato), bis (dimethylcyclopentadienyl) dimethyl zirconium, 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 compounds, the disubstituted products of the cyclopentadienyl ring include 1,2- and 1,3-substituted products, and the trisubstituted products are 1,2,3- and 1,3. Including 2,4-substituted compounds. Further, alkyl groups such as propyl and butyl include isomers such as n-, i-, sec- and tert-.

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

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

[0095]

[Chemical 38]

(Wherein R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group or a butyl group, preferably a methyl group or an ethyl group, particularly preferably a methyl group, m
Is an integer of 2 or more, preferably 5 to 40. ) Where this aluminoxane is of 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 different groups] and may be formed from a mixed alkyloxyaluminum unit.

The 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 adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate,
Aromatic hydrocarbons obtained by adding an organic aluminum compound such as trialkylaluminum to an aromatic hydrocarbon solvent in which aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. are suspended and reacting A method of collecting as a solution of a solvent.

(2) Water (ice, ice or steam) is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran to recover it 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.

Of these methods, the method (1) is preferably adopted. Specific examples of the organoaluminum compound used when preparing the solution of aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-aluminum. Butyl aluminum,
Tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and other trialkylaluminums; tricyclohexylaluminum, tricyclooctylaluminum and other tricycloalkylaluminums; dimethylaluminum chloride, diethylaluminum chloride, Dialkyl aluminum halides such as diethyl aluminum bromide and diisobutyl aluminum chloride; Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; Dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide; Diethyl aluminum phenoxy Examples thereof include dialkylaluminum aryloxides and the like.

Of these, trialkylaluminum is particularly preferable. Further, as the organoaluminum compound, isoprenylaluminum represented by the following general formula can also be used.

[0102] _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≧ 2x.) The organic aluminum such as The compounds may be used alone or in combination.

The benzene-insoluble organoaluminum oxy compound used in the present invention can be obtained, for example, by contacting a solution of aluminoxane with water or a compound containing active hydrogen, or by contacting the organoaluminum compound with water as described above. Can be obtained.

[0104] 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 that the range is 0.07.

The benzene-insoluble organoaluminum oxy compound as described above is presumed to have an alkyloxy aluminum unit represented by the following formula.

[0106]

[Chemical Formula 39]

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

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.

[0109]

[Chemical 40]

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. Further, R ⁴ and R ³ in the above formula represent different groups.

When the benzene-insoluble organoaluminum oxy compound contains an oxyaluminum unit,
An organoaluminumoxy compound having an alkyloxyaluminum unit containing an alkyloxyaluminum unit in a proportion 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 an Al that dissolves in 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 organoaluminum oxy compound used in the present invention may contain a small amount of an organic compound component of a metal other than aluminum. Examples of the organoaluminum compound (B) used as necessary in the catalyst (b) include an organoaluminum compound represented by the following general formula [XI].

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 above 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, and specifically, a methyl group, an ethyl group, n- Examples include propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

As such an organoaluminum compound, the following compounds are specifically used. Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutyl. Dialkyl aluminum halides such as aluminum chloride and dimethyl aluminum bromide; alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; methyl 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. During ^{_{R 5 n AlY 3-n ...}} [XII] ( wherein [XII], R ⁵ are as defined above, Y is -O
R ⁶ groups, -OSiR ⁷ ₃ group, -OAlR ⁸ ₂ group, -NR ⁹ ₂ group,
A —SiR ¹⁰ ₃ group or a —N (R ¹¹ ) AlR ¹² ₂ group, and n
Is 1 to 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 and the like, R ⁹ is a hydrogen atom,
It is a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group or the like, and R ¹⁰ and R ¹¹ are a methyl group, an ethyl group or the like. As such an organoaluminum compound, the following compounds are specifically used. (I) a compound represented by R ⁵ _n Al (OR ⁶ ) _3-n , such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide; and (ii) R ⁵ _n Al (OSiR ⁷ ₃ ) _3- a compound represented by _n , such as Et ₂ Al (OSiMe ₃ ), (iso-B
u) ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OS
iEt ₃ ), such as (iii) a compound represented by R ⁵ _n Al (OAlR ⁸ ₂ ) _3-n , such as Et ₂ AlOAlEt ₂ , (is
o-Bu) ₂ AlOAl (iso-Bu) _2, etc., (iv) R ⁵ _n
A compound represented by Al (NR ⁹ ₂ ) _3-n , such as Me ₂ A
1NEt ₂ , Et ₂ AlNHMe, Me ₂ AlNHEt,
Et ₂ AlN (SiMe ₃ ) ₂ , (iso-Bu) ₂ AlN (S
iMe ₃ ) _{2 and} other compounds represented by (v) R ⁵ _n Al (SiR ¹⁰ ₃ ) _3-n , such as (iso-Bu) ₂ AlSiMe _{3 and} others (vi) R ⁵ _n Al (N (R 11) AlR A compound represented by ¹² ₂ ) _3-n , for example, Et ₂ AlN (Me) AlEt ₂ ,
(Iso-Bu) ₂ AlN (Et) Al (iso-Bu) _{2 and the} like.

Among the organoaluminum compounds represented by the above general formulas [XI] and [XII], the general formula R ⁵ _{3
^{Al, R 5 n Al (OR}} 6) 3-n, R 5 n Al (OAlR 8 2)
_A preferred example is an organoaluminum compound represented by _3-n , wherein R ⁵ is an isoalkyl group,
Particularly preferably, n = 2. Two or more kinds of these organoaluminum compounds can be mixed and used.

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

Such a ring-opening polymer of 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-opening polymer is prepared by subjecting at least one cyclic olefin represented by the above formula [I] or [II] to ring-opening polymerization in the presence of a ring-opening polymerization catalyst.

As the ring-opening polymerization catalyst used here,
For example, a catalyst comprising a halide of a metal such as ruthenium, rhodium, osmium, indium, platinum, molybdenum and tungsten, a nitrate of these metals and an acetylacetone compound of these metals, and a reducing agent such as an alcohol or a tin compound, and Mention may be made of halogen compounds of metals such as titanium, vanadium, zirconium, tungsten and morphudene, catalysts composed of acetylacetone compounds of these metals and metal aluminum compounds.

When preparing the above ring-opening polymer, a cyclic olefin 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, 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 can be mentioned.

As the molecular weight regulator, propylene,
Alkenes such as 1-butene, 1-pentene and 1-hexene can be used as a copolymerization component. In such a ring-opening polymer, at least a part of the cyclic olefin represented by the above formula [I] is considered to have a structure represented by the following formula [I] -a.
I] at least part of the cyclic olefin is
It is considered to have a structure represented by the following formula [II] -a.

[0123]

[Chemical 41]

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

[0125]

[Chemical 42]

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

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

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

The hydrogenation reaction using the hydrogenation catalyst as described above can be carried out in either a heterogeneous system or a homogeneous system depending on the kind of the catalyst. The reaction conditions in such a system are usually 0 to 180 ° C., preferably 20 to 100 ° C. under a hydrogen atmosphere at 1 to 150 atm.
Set to a temperature of ℃. 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 present in the main chain of the polymer Of these,
50% or more, preferably 80% or more, more preferably 90% or more is hydrogenated.

In such a hydrogenated cyclic polymer,
At least a part of the cyclic olefin represented by the above formula [I] is considered to have 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.

[0131]

[Chemical 43]

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

[0133]

[Chemical 44]

(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. The [A-1] cyclic olefin-based random copolymer is α-
The repeating unit derived from the olefin component is usually 35 to
It is desirable to be present in an amount in the range of 90 mol%, preferably 40 to 85 mol%, and the formula [I] or [II]
The repeating unit derived from the cyclic olefin represented by is usually present in an amount in the range of 10 to 65 mol%, preferably 15 to 60 mol%.

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

The refractive index n _D measured at 25 ° C. is usually 1.5.
It is desirable that the range is from 00 to 1.650, preferably from 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 preferably 0 or less.

[A-2] Ring-opening 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
~ 5.0 dl / g, preferably 0.15 to 4.5 dl / g
It is desirable that the range is.

Glass transition temperature (T
g) is 70 ° C. or higher, preferably 70 to 250 ° C.
It is desirable that the range is. The refractive index n _D measured at 25 ° C. is usually 1.500 to 1.650, preferably 1.510.
It is preferably in the range of 1.600.

The iodine value is preferably 30 or less.

The core / shell elastomer which is the component [B] will be described below. The component [B] is [B-1]
40 to 85 parts by weight of a core component composed of a styrene-butadiene rubber having a styrene unit of 50% by weight or less 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) 15 to 60 parts by weight of a diene component composed of a copolymer composed of 0 to 3% by weight of a polyfunctional monomer as a constituent. The core-shell elastomer is produced by using latex particles of styrene-butadiene rubber as a component [B-1] as a seed and subjecting a monomer mixture of the component [B-2] to seed polymerization according to a method known per se. can do.

The latex of styrene-butadiene rubber having a styrene unit content 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. Further, known molecular weight modifiers and cross-linking agents can be added when producing the rubber latex. As the crosslinking agent, a crosslinking monomer,
For example, divinylbenzene; 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. Dibasic or triallyl esters of polybasic acids such as divinyl ethers of polyhydric alcohols, diallyl phthalate, diallyl maleate, diallyl fumarate, diallyl sebacate; triallyls 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 type monomers copolymerizable with styrene and butadiene, for example, vinyl cyan compounds such as acrylonitrile, alkyl esters of acrylic acid or methacrylic acid in a proportion of 3% by weight or less. it can. The rubber latex used in the present invention is
It is preferably in the range of 50 to 250 nm, more preferably 6
It has a primary particle average particle diameter in the range of 0 to 200 nm.

A compound represented by the following formula is preferably used as the monovinyl aromatic monomer (b-1) which constitutes the component (B-2).

[0145]

[Chemical formula 45]

(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 and α- Methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, m-ethylstyrene, p-ethylstyrene, o-isopropylstyrene, m-isopropylstyrene, p-
Examples thereof include isopropyl styrene.

The above compounds may be used alone or in combination with 2
Used in combination of two or more species. Further, as the copolymerizable alkyl (meth) acrylate (b-2), a monomer represented by the following general formula can be given.

[0148]

[Chemical formula 46]

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 this substituent include a hydroxyl group (—OH), an epoxy group, a halogen, an oxymethylene group, and an oxyethylene group.

Specific examples of such (meth) acrylates include (meth) acrylic acid esters as 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 may be 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 for the rubber latex can be exemplified. Monovinyl aromatic monomer (b-1) in the monomer mixture
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 occupy 0 to 3% by weight, preferably 0 to 2% by weight.

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

Next, the (co) polymer as the component [C] will be described. The component [C] is (C-1) the following general formula [III]

[0154]

[Chemical 47]

(In the formula [III], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸ and R ^a and R ^b are respectively Independently a hydrogen atom, a halogen atom or a hydrocarbon group,
R ^{15 to} R ¹⁸ may combine with each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may form a double bond, and R ¹⁵ and R ¹⁶ or R ^{15 17} and R ¹⁸ may form an alkylidene group, ^one of X ¹ and X ² is an acryloyloxy group or a methacryloyloxy group represented by the following formula [X], and the other is a hydrogen atom. Alternatively, it is an alkyl group. );

[0156]

[Chemical 48]

(Wherein R is a hydrogen atom or a methyl group), a compound represented by the following general formula [IV]

[0158]

[Chemical 49]

(In the formula [IV], p and l are 0 or an integer of 1 or more, and r and s are 0, 1 or 2
And R ^{21 to} R ³⁹ each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group and an alkoxy group, and R ²⁹ and R ³⁰ are The carbon atom bonded to R ³³ and the carbon atom bonded to R ³³ or the carbon atom bonded to R ³¹ may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and When r = s = 0, R
³⁵ and R ³² or R ³⁵ and R ³⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring, and X ³ and X ⁴
One of the groups is an acryloyloxy group or a methacryloyloxy group represented by the above formula [X],
The other is a hydrogen atom or an alkyl group. ); And a compound represented by the following formula [V]

[0160]

[Chemical 50]

(In the formula [V], t is 4 or 5, and R is
^{41 to} R ⁴³ each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group, and X ⁵ represents an acryloyloxy group or a methacryloyloxy group represented by the following formula [X]. ) A monomer or monomer mixture containing 20 to 100% by weight of at least one acrylate or methacrylate monomer having an alicyclic skeleton selected from the group consisting of compounds represented by (Co) polymer.

In the above formula [III], X ¹ and X ²
One of the groups is an acryloyloxy group or a methacryloyloxy group represented by the above formula [X],
The other is a hydrogen atom or an alkyl group.

In the above formula [IV], one of X ³ and X ⁴ is an acryloyloxy group or a methacryloyloxy group represented by the above formula [X], and the other is a hydrogen atom or an alkyl group. is there. Formula [I
The definitions of other symbols in [II] and [IV] will be clear from the definitions of the symbols in the above formulas [I] and [II]. Further, in the formula [V], t is 4 or 5.
When t is 4, the compound of formula [V] is a compound having a 5-membered ring, and when t is 5, the compound of formula [V] is a compound having a 6-membered ring. R ⁴¹ , R ⁴² and R ⁴³ are each independently a hydrogen atom, a halogen atom or a hydrocarbon group. Examples of the halogen atom are the same as those exemplified for the formula [I]. Examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group. Specific examples of these groups are the same as those exemplified for R ^{81 to} R ^{99 in} the formula [II]. X ⁵ is an acryloyloxy group or a methacryloyloxy group represented by the above formula [X]. The following compounds may be mentioned as specific examples of the compound represented by the above formula [III].

[0164]

[Chemical 51]

[0165]

[Chemical 52]

[0166]

[Chemical 53]

[0167]

[Chemical 54]

[0168]

[Chemical 55]

[0169]

[Chemical 56]

[0170]

[Chemical 57]

[0171]

[Chemical 58]

[0172]

[Chemical 59]

[0173]

[Chemical 60]

[0174]

[Chemical formula 61]

[0175]

[Chemical formula 62]

[0176]

[Chemical formula 63]

[0177]

[Chemical 64]

[0178]

[Chemical 65]

The compound represented by the above formula [III] is known and is disclosed in, for example, JP-A-3-79611. The following compounds may be mentioned as specific examples of the compound represented by the above formula [IV].

[0180]

[Chemical formula 66]

[0181]

[Chemical formula 67]

[0182]

[Chemical 68]

[0183]

[Chemical 69]

[0184]

[Chemical 70]

[0185]

[Chemical 71]

The polycyclic acrylate compound having an aromatic group represented by the above general formula [IV] is IR (infrared)
It can be identified by spectroscopic analysis and NMR (nuclear magnetic resonance) analysis. For example, in formula [IV], p, l,
r and s are 0, R ^{21 to} R ³⁹ and X ⁴ are each a hydrogen atom, and X ³ is a methacryloyloxy group, 5-phenyl-bicyclo [2.2.1] heptyl-2- Regarding the methacrylate, in the IR spectrum, peaks derived from the C = O bond and C = C bond of the methacryloyl group at 1725 cm ^-1 and 1635 cm ^-1 , respectively, and a peak derived from the phenyl group at 700 cm ^-1 were obtained. Is recognized. In addition, in the NMR spectrum,
The peak derived from the phenyl group at 7.1 to 7.3 ppm,
A peak derived from a norbornene ring is observed at 4.7 to 5.1 ppm, and a peak derived from a methacrylic acid ester is observed at 5.5 to 6.5 ppm.

The monocyclic acrylate compound having an aromatic group represented by the above general formula [IV] is known and is exemplified in, for example, JP-A-5-140231.
The polycyclic acrylate compound having an aromatic group represented by the general formula [IV] is produced, for example, as follows. In the first production method, acrylic acid, methacrylic acid or their ester-forming derivatives and the following general formula [I] having a structure corresponding to a polycyclic acrylate compound
V] -a is reacted with a polycyclic alcohol or an ester-forming derivative thereof.

[0188]

[Chemical 72]

In the above formula [IV] -a, the meanings of the respective symbols other than Y ¹ and Y ² are the same as in the formula [IV]. Y ¹
One of Y ² and Y ² is a hydroxyl group, and the other is a hydrogen atom or an alkyl group.

Such a polycyclic alcohol represented by the general formula [IV] -a or an ester-forming derivative thereof has the following general formula having a structure corresponding to the alcohol compound represented by the above general formula [IV] -a. A formic acid is added to an unsaturated bond of a polycyclic olefin represented by [IV] -b to form a formic acid ester of the polycyclic olefin, and then the formic acid ester is hydrolyzed. You can

[0191]

[Chemical formula 73]

The definition of each symbol in the above formula [IV] -a is the same as that in the above formula [IV]. The method for preparing such a cyclic olefin will be described in detail later. General formula [I
The reaction of the polycyclic olefin represented by V] -b with formic acid is carried out in a molar ratio of the polycyclic olefin to the polycyclic olefin of usually 1 to 10 times, preferably 2 to 6 times. The mixture with formic acid is usually 50 to 200 ° C., preferably 70
It is carried out at ˜150 ° C., particularly preferably under the condition that formic acid is refluxed. In this reaction, formic acid is added to the double bond site of the cyclic olefin represented by the general formula [IV] -b to form a formic acid ester of polycyclic olefin. Then, the formic acid ester of the polycyclic olefin is hydrolyzed in a mixed solvent of water and ethanol using a caustic alkali such as caustic soda at room temperature to 100 ° C. to give a compound represented by the general formula [IV] -a. A polycyclic alcohol is obtained. At this time, the caustic alkali is usually used in a molar ratio of 0.7 to 2 with respect to the formic acid ester of the polycyclic olefin,
It is desirable to use it in an amount of preferably 1.0 to 1.5.

Then, the above-mentioned general formula [IV] -a
When a polycyclic alcohol represented by the following is reacted with (i) acrylic acid or methacrylic acid, or (ii) an ester-forming derivative of acrylic acid or methacrylic acid to form an ester, the compound of the general formula [IV] A polycyclic acrylate compound represented by is obtained.

This esterification reaction is carried out under the following conditions. When a polycyclic alcohol represented by the general formula [IV] -a is directly esterified with (i) (meth) acrylic acid, the alcohol and (meth) acrylic acid are reacted in the presence of an acidic catalyst. , Normal pressure, 60 ℃ ~ 150
It is preferable to carry out the esterification reaction under the condition of ° C while removing the produced water. Specific examples of the acidic catalyst include sulfuric acid, p-toluenesulfonic acid, sulfonic acid type ion exchange resin, hydrochloric acid and the like.

Further, polycyclic alcohols [IV] -a and (i
i) When the esterification reaction is carried out using the ester-forming derivative of (meth) acrylic acid, the alcohol and the ester-forming derivative of (meth) acrylic acid are mixed at −10 ° C. to 30 ° C. under normal pressure. It is preferable to carry out the esterification reaction at 0 ° C. for several hours. At this time, an alkali such as triethylamine or sodium hydroxide may be added as a receptor for the generated hydrochloric acid. Specific examples of the ester-forming derivative of (meth) acrylic acid include acrylic acid halides such as acrylic acid chloride and methacrylic acid chloride, and methacrylic acid halides.

The compound of the above formula [IV] can be further produced by the second production method as described below.
That is, it can be obtained by addition-reacting acrylic acid or methacrylic acid with a polycyclic olefin represented by the above general formula [IV] -b having a structure corresponding to the desired polycyclic acrylate compound.

The polycyclic olefin represented by the above general formula [IV] -b is an aromatic olefin (or a norbornene ring carbon atom having a reactive double bond site) with a cyclopentadiene compound as described below. And a norbornene derivative having an aromatic group) are subjected to a Diels-Alder reaction.

This reaction is specifically represented by the following formula. In the polycyclic olefin represented by the above general formula [IV] -b, when p is 0, it is represented by the following formula.

[0199]

[Chemical 74]

In the polycyclic olefin represented by the above general formula [IV] -b, when p is 1 or more, it is represented by the following formula.

[0201]

[Chemical 75]

The reaction of the compound represented by the general formula [IV] -b with acrylic acid or methacrylic acid is carried out at 60 ° C. to 150 ° C. for several hours at atmospheric pressure or under pressure with an acidic catalyst.

Specific examples of the acidic catalyst include sulfuric acid, boron trifluoride, perfluoroacetic acid, polyphosphoric acid, activated clay, and acidic ion exchange resins. The polycyclic acrylate or methacrylate having an aromatic group represented by the general formula [IV] according to the present invention can be obtained by the first or second production method as described above.

The following compounds can be mentioned as specific examples of the compound represented by the above formula [V].

[0205]

[Chemical 76]

The above formulas [III], [IV] and [V]
The compound represented by is obtained by reacting the corresponding alicyclic alcohol or its ester-forming derivative with acrylic acid, methacrylic acid or their ester-forming derivative, or by reacting the corresponding alicyclic olefin with acrylic acid or By the addition reaction of methacrylic acid,
Let it be manufactured.

The above formulas [III], [IV] and [V]
At least one kind of acrylate or methacrylate monomer having an alicyclic skeleton selected from the group consisting of compounds represented by the following formulas is used alone or in another monomer such as a monovinyl aromatic monomer (b-1). ), And a monomer or monomer mixture consisting of another monovinyl monomer (b-2 ′) and a polyfunctional monomer (b-3) copolymerizable therewith. As the monovinyl aromatic monomer (b-1) and the polyfunctional monomer (b-3), the same ones as described above for the component [B] can be exemplified. As the other copolymerizable monovinyl-based monomer (b-2 ′), for example, (meth) acrylate, α, β-unsaturated carboxylic acid, vinyl ether and ethylene derivative having a halogen atom or a cyano group are preferable. Can be mentioned. As the (meth) acrylate, the same ones as described above for the component [B] can be exemplified.

Specific examples of the α, β-unsaturated carboxylic acid or its derivative include the following compounds. Acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endocis-bicyclo [2.2.1] hept-
5-ene-2,3-dicarboxylic acid (Nadic acid TM),
Methyl-endocis-bicyclo [2.2.1] hept-5
-Ene-2,3-dicarboxylic acid (methyl nadic acid T
M) or the above carboxylic acid halide.

Examples of the α, β-unsaturated carboxylic acid derivative include amides, imides and acid anhydrides of α, β-unsaturated carboxylic acids. Specific examples include maleenyl chloride and
Maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, etc. can be mentioned. Compounds such as the above may be used alone or
Used in combination of two or more species.

As the vinyl ether, a monomer represented by the following formula can be exemplified. CH ₂ ═CH—O—R ^{57 In the} above formula, R ⁵⁷ is an alkyl group having 1 to 20 carbon atoms. Specific examples of such vinyl ethers include the following compounds.

Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, isoamyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, 2-ethylhexyl vinyl ether, n- Decyl vinyl ether, 2,2-dimethylhexyl vinyl ether, 2,2-dimethyloctyl vinyl ether, 2,2-dimethyldecyl vinyl ether,
2,2-dimethyl dodecyl vinyl ether, 2,2-dimethyl tetradecyl vinyl ether, sec-butyl vinyl ether, n-amyl vinyl ether, 1-methyl-
2-methylpropyl vinyl ether, 1-methyl-2,
2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, diisopropylmethyl vinyl ether, 1,3-dimethylbutyl vinyl ether, 2,2-dimethylbutyl vinyl ether, neopentyl vinyl ether, 1-methylheptyl vinyl ether, n-nonyl vinyl ether, 1-methyl -4-ethyloctyl vinyl ether, n-tetradecyl vinyl ether, n-hexadecyl vinyl ether, n-octadecyl vinyl ether, n-dodecyl vinyl ether, n-heptadecyl vinyl ether, n-tridecyl vinyl ether, n
-Pentyl vinyl ether and the like. The above compounds may be used alone or in combination of two or more.

Examples of the ethylene derivative having a halogen or cyano group include monomers represented by the following formula.

[0213]

[Chemical 77]

In the above formula, one or both of G and J is F, Cl, Br, I or -C≡N, and the other is H or CH ₃ . Specific examples of such a monomer include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, and vinylidene fluoride. The above compounds may be used alone or in combination of two or more.

The (co) polymerization of at least one of the above-mentioned acrylate and methacrylate monomers, or (co) polymerization thereof with other monomers, is generally carried out by a polymerization method widely used in the production of poly (methyl methacrylate). be able to. For example, a polymerization method such as a suspension polymerization method, an emulsion polymerization method, a solution polymerization method and a bulk polymerization method can be adopted.

For example, when the polymerization is carried out by the bulk polymerization method, it is usually 60 to 250 ° C., preferably 150 to 250 ° C.
A method of polymerizing at 230 ° C. or a reaction temperature of, for example, from 60 ° C. to 180-
A method of terminating the polymerization at 230 ° C can be adopted. Such a method can be performed in the presence of a radical polymerization initiator. Examples of radical initiators used herein include di-tert-butyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, tert-butyl perphthalate, tert-butyl perbenzoate, di-tert-butyl peracetate and te
Mention may be made of organic peroxides such as rt-butyl perisobutyrate and azo compounds such as 1,1'-azobiscyclohexanecarbonitrile and 2-cyano-2-propylazoformamide. The radical initiator is usually used in an amount of 1 mol% or less based on the monomers.

In the copolymerization, in order to control the molecular weight of the polycyclic (meth) acrylate (co) polymer produced, tert-butyl mercaptan, n-butylmethyl mercaptan and n-octyl mercaptan, n-octyl mercaptan Chain transfer agents such as dodecyl mercaptan can also be used. This chain transfer agent is usually used in an amount of 1 mol% or less based on the monomers.

The above (co) polymer can also be prepared by a photopolymerization method in which an energy ray such as ultraviolet rays is irradiated. In this method, the radical initiator as described above can also be used.

Regarding such a polymerization method, further,
For example, it is described in detail in JP-A-63-243108, and these methods can be used in the present invention. The (co) polymer of the component [C] thus obtained contains 20 to 100% by weight of at least one of the acrylate or methacrylate monomers represented by the above formulas [III], [IV] and [V]. %, Preferably 30 to 100% by weight, more preferably 40 to 90
It is contained by weight%. Examples of the (co) polymer of the component [C] include a homopolymer of an acrylate or methacrylate monomer represented by the above formula [III], an acrylate or methacrylate monomer represented by the above formula [III] and an alkyl. Copolymer with (meth) acrylate or monovinyl aromatic monomer, the above formula [II
I] a copolymer of an acrylate or methacrylate monomer, an alkyl (meth) acrylate and a monovinyl aromatic monomer, or a homopolymer of the acrylate or methacrylate monomer represented by the above formula [IV]. Polymers are particularly preferred.

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

In the cycloolefin polymer composition of the present invention, the above [A] component and [B] component are replaced by [A] component /
The component (B) is contained in a weight ratio of 40/60 to 95/5, preferably 60/40 to 90/10. In addition, [C] component is a total of 10 components of [A] component and [B] component
It is contained in an amount of 3 to 40 parts by weight, preferably 3 to 25 parts by weight, based on 0 parts by weight. The cycloolefin polymer composition of the present invention is improved in compatibility between the [A] component and the [B] component due to the presence of the [C] component, is excellent in transparency and impact resistance, and is transparent. Good balance of heat resistance and impact strength.

Further, the above 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. May be.

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

As the organic peroxide used here, ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; 1,1-
Bis (tert-butylperoxy) cyclohexane, 2,
Peroxyketals such as 2-bis (tert-butylperoxy) octane; tert-butylhydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroxyperoxide, 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 Diacyl peroxides such as oxide and benzoyl peroxide; peroxyesters such as tert-butyl peroxyacetate, tert-butyl peroxybenzoate and 2,5-dimethyl-2,5-di (benzoylperoxy) hexane Can be mentioned.

Examples of the radical-polymerizable polyfunctional monomer used as necessary include, for example, divinylbenzene, vinyl acrylate, vinyl methacrylate, triaryl isocyanurate, diaryl phthalate, ethylene dimethacrylate trimethylolpropane trimetameth. An acrylate etc. can be mentioned.

When the composition is prepared by radically reacting the above components in the presence of an organic peroxide and optionally a radically polymerizable polyfunctional monomer, the composition is prepared by using one reactor. May be prepared, or by using a plurality of reactors, the above components are reacted in one reactor, the three are similarly reacted in the other reactor, and then the two are blended, It may be the final composition.

In such a radical reaction, the organic peroxide is usually added in an amount of 0.1 parts by weight based on 100 parts by weight of each component.
The radical-polymerizable polyfunctional monomer used in an amount of 01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, and used as necessary, is usually used based on 100 parts by weight of each component. 0.01 to 15 parts by weight, preferably 0.1 to 10
Used in parts by weight.

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

To mix the components, a method of melt blending the separately prepared components with an extruder or a suitable solvent (eg, heptane, hexane, decane,
Saturated hydrocarbons such as cyclohexane; aromatic hydrocarbons such as toluene, benzene, xylene, etc.) can be sufficiently dissolved or dispersed and blended.

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

Such a radical reaction can be carried out in a molten state of the mixture of raw materials, or in a solution state in which the mixture of raw materials is dissolved or dispersed in a solvent. When the radical reaction is carried out in the molten state, a kneading device such as a mixing roll, a Banbury mixer, an extruder, a kneader, a continuous mixer or the like is used to melt and mix the mixture of raw materials to react. The radical reaction is carried out at a temperature equal to or higher than the one-minute half-life of the organic peroxide, usually 150 to 300.
C., preferably 170 to 270.degree. C., usually 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 the solvent, the same solvent as that used in the solution blending method can be used. The radical reaction is preferably carried out at a temperature not lower than the 10-minute half-life of the organic peroxide, usually at a temperature of 50 to 300 ° C., usually for 10 seconds to 2 hours.

This composition can be used alone or as a blend with another transparent resin. The cyclic olefin-based polymer composition thus provided is molded and processed by a known method. For example, single-screw extruder, vented extruder, twin-screw extruder, conical twin-screw extruder, co-kneader, practicator, mixer, twin-screw conical screw extruder, planetary screw extruder, gear type extruder Extrusion molding, injection molding, blow molding, and rotation molding with a screwless extruder.

A rubber component is added to such a cyclic olefin polymer composition in order to further improve the impact strength of the composition, and a heat stabilizer, a weather stabilizer, an antistatic agent and a slip agent are added. , 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 added.

For example, as the stabilizer to be added as an optional component, phenolic antioxidants, sulfur antioxidants, phosphorus antioxidants, fatty acid metal salts and fatty acid esters of polyhydric alcohols are preferably used. To be Examples of the phenol-based antioxidant include the following formula A
n-1

[0236]

[Chemical 78]

(Here, R _{1 and} R ₂ are each 1 to 1 carbon atoms.
4, an alkyl group having a straight chain or a side chain, R ₃ is an alkyl group having a straight chain or a side chain having 8 to 20 carbon atoms, or —CH ₂ —CH ₂ —COOX, and X is a C 8 to 20 carbon atom. A compound represented by the following formula: An-2, which is an alkyl group having a straight chain or a side chain)

[0238]

[Chemical 79]

(Here, the definition of R ₁ and R ₂ is defined by the above formula A
same as n-1), and R ₄ and R ₅ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or

[0240]

[Chemical 80]

Examples thereof include compounds represented by: The compound represented by the above formula An-1 is 2,
6-di-t-butyl-4-nonylphenol, 2,6-di-t-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-t-butylphenyl) -n-dodecyl propionate, 3- (4'-hydroxy-3', 5 ' -Di-t-butylphenyl) propionic acid-hexadecyl, 3- (4'-hydroxy-3 ', 5'-
Di-t-butylphenyl) -n-octadecyl propionate, 3- (4'-hydroxy-3'-t-butyl-5'-
Isopropylphenyl) -n-octadecyl propionate, 3- (4'-hydroxy-3'-t-butyl-3'-
Methylphenyl) propionate-n octadecyl and the like.

As an example of the compound represented by the above formula An-2, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane (registered trademark "Topanol CA") is used. Commercially available) and 4,4′-butylidene bis (6-t-butyl-m-cresol) (registered trademark “Sant
(commercially available as “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′-
Oxamide bis [ethyl-3 (3,5-di-t-butyl-4-hydroxyphenyl)] propionate and the like can be mentioned.

As the sulfur antioxidant, the following formula An can be used.
-3

[0244]

[Chemical 81]

(Where m and n are integers of 1 to 4 and R ₆
And R ₇ is an alkyl group having a straight chain or a side chain having 8 to 20 carbon atoms). Examples of the compound represented by the above 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 and 2,4-
Bis (n-octylthio) -6- (4-hydroxy-
3,5-di-t-butylanilino) -1,3,5-triazine and the like can be mentioned.

As the phosphorus-based antioxidant, the following formula A is used.
n-4

[0247]

[Chemical formula 82]

(Wherein X is an oxygen atom or a lone pair of electrons, and R ₈ , R ₉ and R ₁₀ are independently of each other a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a mono- or di- (carbon A compound represented by the formula 1 to 20) which is alkyl) -substituted phenyl). Examples of the phosphorus compound represented by the above formula An-4 include phosphoric acid and tris (nonylphenyl) phosphite.

Examples of the fatty acid metal salt include zinc stearate, calcium stearate, and 12-hydroxy calcium stearate. Examples of fatty acid esters of polyhydric alcohols include glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate and the like. . These may be blended alone or may be blended in combination, for example, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, zinc stearate and glycerin. Examples thereof include a combination with monostearate.

Particularly, it is preferable to use a phenolic antioxidant and a fatty acid ester of a polyhydric alcohol in combination, and the fatty acid ester of the polyhydric alcohol is 3
It is preferable that the polyhydric alcohol fatty acid in which a part of the alcoholic hydroxyl groups of the polyhydric alcohol having a valency or higher is esterified is used. As such fatty acid ester of polyhydric alcohol, specifically, glycerin monostearate, glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin distearate, glycerin fatty acid ester 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, and more preferably 0 to 1 part by weight, based on 100 parts by weight of the cyclic olefin polymer composition. . The sulfur 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-based antioxidant is 0 to 5 parts by weight, preferably 0.01 to 2 parts by weight, and more preferably 0.01 to 1 part by weight based on 100 parts by weight of the cyclic olefin polymer composition.
Used in parts by weight.

The fatty acid metal salt is 0 to 5 parts by weight, preferably 0 to 100 parts by weight of the cyclic olefin polymer composition.
˜2 parts by weight, more preferably 0 to 1 part by weight. The fatty acid ester of 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, silica, diatomaceous earth, alumina, titanium oxide, a cyclic olefin copolymer composition,
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 α-olefin fibers, polypropylene fibers, polyester fibers, and polyamide fibers can also be blended.

[0253]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples. In the present invention, various physical property values were measured and evaluated as follows.

Various Physical Properties of Core / Shell Elastomer (1) Copolymerization Component Constituting Core / Shell Elastomer
The amount was calculated from the charged amount and the yield. (2) Refractive index Abbe's refractometer (D line, 589 nm) is used at 25 ° C.
It was measured at. (3) Average particle size of primary particles of core / shell elastomato Laser diffractometry particle size distribution measuring device (manufactured by Shimadzu Corporation, SA
LD-200) was used for the measurement.

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

Core / Shell Elastomer / Circular Oleph
Measurement and evaluation methods for various physical properties of the fin copolymer composition (1) Preparation predetermined amount of the core-shell elastomer and the cyclic olefin copolymer compositions were well mixed under a nitrogen atmosphere under a plastic bag The atmosphere was replaced with nitrogen for 2 hours. Using a twin-screw extruder (TW100 type manufactured by Haake Co.), the mixture was heated to a cylinder maximum temperature of 230 ° C.
The mixture was melt-blended with a residence time of 1 minute and pelletized with a pelletizer. (2) Preparation of test piece Using an injection molding machine IS50EPN manufactured by Toshiba Machine Co., Ltd. and a predetermined test piece mold, molding was performed under the following molding conditions. The test piece was subjected to measurement after being left at room temperature for 48 hours after molding. Molding conditions: Cylinder temperature: 260 ° C., mold temperature: 60 ° C., injection pressure primary / secondary = 1000/800 kg / cm ² (3) Haze value According to ASTM DDD-1003, using an Abbe refractometer manufactured by Atago. A press sheet having a thickness of 2 mm was measured as a sample. (4) Izod impact strength Measured according to ASTM D256. Test piece shape: 5/2 × 1/8 × 1/2 ^t inch (with notch) Test temperature: 23 ° C. (5) Heat distortion temperature (HDT) It was performed according to ASTM D648. Test piece shape: 5 x 1/4 x 1/2 ^t inch Load: 264 psi

Production Example [Synthesis Example of Cyclic Olefin Copolymer I (hereinafter referred to as Copolymer I)] 258 ml of cyclohexane was charged in 1
Norbornene (hereinafter sometimes abbreviated as [NB]) (118 g) was added to a liter-stainless steel autoclave at room temperature under a nitrogen stream, and the mixture was stirred for 5 minutes. Furthermore, the concentration of triisobutylaluminum in the system is 1.0
It was added so as to be mmol / liter. Subsequently, ethylene was circulated at normal pressure while stirring to create an ethylene atmosphere in the system. The internal temperature of the autoclave was maintained at 70 ° C., and ethylene was applied so that the internal pressure was 6 kg / cm ^{2 as a} gauge pressure. After stirring for 10 minutes, 5.0 ml of a toluene solution containing isopropylidene (cyclopentadienyl) (indenyl) zirconium dichloride and methylalumoxane prepared in advance was added to the system to carry out the copolymerization reaction of ethylene and NB. Let it start. The catalyst concentration at this time was 0.015 mmol / liter for isopropylidene (cyclopentadienyl) (indenyl) zirconium dichloride and 7.5 mmol / liter for methylalumoxane, based on the total system.

During the polymerization, the temperature was kept at 70 ° C. with an internal pressure of 6 kg / gauge by continuously supplying ethylene to the system.
It was held at cm ² . After 60 minutes, the polymerization reaction was stopped by adding isopropyl alcohol. After depressurization, the polymer solution was taken out and concentrated hydrochloric acid 5m to 1 liter of water
The mixture was brought into contact with the aqueous solution containing 1 at a ratio of 1: 1 using a homomixer under vigorous stirring to transfer the catalyst residue to the aqueous phase.
After the contact mixed solution was allowed to stand, the aqueous phase was separated and removed, and further washed with distilled water twice to purify and separate the polymerization liquid phase.

Then, the purified and separated polymerization liquid was contacted with 3 times amount of acetone under strong stirring to precipitate a copolymer, and then a solid portion (copolymer) was collected by filtration and washed sufficiently with acetone. did. Further, in order to extract unreacted NB existing in the polymer, this solid part was put into acetone at 40 g / liter, and then extraction operation was performed at 60 ° C. for 2 hours. After the extraction treatment, the solid part is collected by filtration, under nitrogen flow, at 130 ° C., 350 mmH
dried for 12 hours. The polymer yield was 36 g.

The ethylene-norbornene copolymer (copolymer I) thus obtained has an intrinsic viscosity [η]; 0.60 dl / g, Tg; 148 ° C., N
The B content was 49.0 mol%. Furthermore, the iodine value of the obtained copolymer was 0.2. The refractive index (n _D ) of the copolymer I was 1.532.

[0261] using a vanadium catalyst [cyclic olefin copolymer II (hereinafter referred to as copolymer II) Synthesis example], and ethylene, tetracyclo [4.4.0.1 ^{2, 5} .1 ^{7
, 10} ] -3-Dodecene (hereinafter sometimes abbreviated as “TCD”) was continuously copolymerized by the following method.

A cyclohexane solution of TCD was continuously fed from the upper portion of a 1-liter glass-made polymerization vessel equipped with a stirring blade so that the concentration of TCD supplied in the polymerization vessel was 40 g / liter. In addition, a cyclohexane solution of VO (O.ethyl) Cl ₂ was used as a catalyst from the upper portion of the polymerization vessel so that the concentration of vanadium in the polymerization vessel was 0.5 mmol / liter of ethylaluminum sesquichloride (Al (C ₂ H _{2 5} ) A cyclohexane solution of _1.5 Cl _1.5 ) was continuously supplied to each of the polymerization vessels so that the aluminum concentration in the polymerization vessel was 4.0 mmol / liter. In addition, ethylene was added to the polymerization system by 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 outside the polymerization vessel at 10 ° C. The polymerization solution of the copolymer produced by the above-mentioned copolymerization reaction is continuously conducted from the upper part of the polymerization vessel so that the polymerization solution in the polymerization vessel is always 1 liter (that is, the average residence time is 0.5 hours). I pulled it out. A cyclohexane / isopropyl alcohol (1: 1) mixed solution was added to the extracted polymerization solution to stop the polymerization reaction. Then, an aqueous solution prepared by adding 5 ml of concentrated hydrochloric acid to 1 liter of water was mixed with the polymerization solution at a ratio of 1 :. The catalyst residue was brought into contact with the homomixer at a ratio of 1 under strong stirring to transfer the catalyst residue to the aqueous phase.
After leaving this contact mixture still, after separating and removing the aqueous phase,
Further, it was washed twice with distilled water to purify and separate the polymerization liquid phase. Then, the purified and separated polymerization liquid was contacted with 3 times amount of acetone under strong stirring to precipitate a copolymer, and then this solid part was collected by filtration and sufficiently washed with acetone. Further, in order to extract unreacted TCD existing in the copolymer, this solid part was put into acetone at 40 g / liter, and then extraction operation was performed at 60 ° C. for 2 hours. After the extraction treatment, the solid part was collected by filtration and dried at 130 ° C. and 350 mmHg for 12 hours under a nitrogen flow.

Ethylene.T obtained as described above
The CD copolymer (hereinafter referred to as copolymer II) has an intrinsic viscosity [η] of 0.65 dl / g, Tg; 82 ° C., and a T
CD content is 28.1 mol% and iodine value is 0.1 g
It was iodine / 100 g. The refractive index (n _D ) of the copolymer II was 1.538.

[Synthesis Example of Component of Core / Shell Elastomer [B]] (1) An autoclave equipped with a stirrer, which had been sufficiently substituted with nitrogen, was charged with the raw materials so as to have the following composition and reacted at 50 ° C. for 15 hours while stirring. Let 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 0.006 parts Ferrous sulfate heptahydrate 0.002 parts Sodium pyrophosphate 0.3 parts Sodium oleate 2.0 parts Ion-exchanged water 200 parts Conversion of rubber 98%, average particle diameter 80nm (hereinafter referred to as latex A) )was gotten.

(2) The obtained latex was charged into an autoclave with a stirrer, which was sufficiently nitrogen-substituted as described above, so as to have the following composition, and 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 Ion-exchanged 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 obtained rubber latex (hereinafter referred to as latex B) had an average particle diameter of 170 nm. When latex B was observed with an electron microscope,
There were no latex particles with a particle size below 100 nm and above 300 nm. As described above, styrene-butadiene rubber latex (= 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 substituting nitrogen, raw materials were charged into a glass container so as to have the following composition and 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 To the mixture, The composition was continuously added over 2 hours. Methyl methacrylate (MMA) 17 parts Polyethylene glycol dimethacrylate 1.0 part Diisopropylbenzene hydroperoxide 0.1 part

When the stirring was continued for another hour after the addition was completed, the conversion was 98%. Furthermore, the following composition was continuously added over 2 hours. Styrene 13 parts Diisopropylbenzene hydroperoxide 0.2 part After the addition was complete, diisopropylbenzene hydroperoxide 0.1 part was added and stirring was continued for another 3 hours. The conversion rate was 98%. , Latex D) had an average particle diameter of 180 nm. As a result of observing the latex C with an electron microscope, 1
There were no latex particles with particle sizes below 00 nm and above 300 nm. The obtained latex D
1,2 parts of 2,6-ditertiarybutyl-p-cresol (BHT) and 0.5 parts of dilauryl thiodipropionate as a stabilizer were added to the mixture, and after sufficient stirring, an aqueous hydrochloric acid solution was added to coagulate, dehydrate and dry. It was

[0270] [Production Example of the component C] tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecyl -3
-Acrylate (TD-A) homopolymer (hereinafter referred to as C-
(Referred to as components) Tetracyclo [4.4.0.1] purified by vacuum distillation
^{2,5.1 7,10} ] Dodecyl-3-acrylate (= TD-
A) 99 parts, n-octyl mercaptan 0.05 parts, 2,
A monomer mixture consisting of 0.05 parts of 2'-azobisisobutyronitrile and 300 parts of toluene was mixed in the absence of oxygen and polymerized at 80 ° C for 24 hours. The produced polymer was poured into a large excess of methanol to cause precipitation, and then dried under reduced pressure. The polymer obtained is 3
Intrinsic viscosity [η] determined with toluene solution at 0 ° C is 0.58
dl / g, Tg measured by DSC was 122 ° C., and refractive index n _D by Abbe refractometer was 1.536.

Copolymerization of TD-A and methyl methacrylate
Synthesis of combined product (hereinafter referred to as C-component) Tetracyclo [4.4.0.1] purified by vacuum distillation
^{2,5.1 7,10} ] Dodecyl-3-acrylate (= TD-
A) A monomer mixture consisting of 90 parts, 10 parts of methyl methacrylate, 0.05 part of n-octyl mercaptan, 0.05 part of 2,2'-azobisisobutyronitrile and 300 parts of toluene was added in the absence of oxygen. Mix at 70 ℃, 24
Polymerization was completed in time. The produced polymer is precipitated by throwing it in a large excess of methanol, and then,
Dried under reduced pressure. The polymer obtained had an intrinsic viscosity [η] of 0.50 dl / g at 30 ° C. in a toluene solution, D
The Tg measured by SC was 120 ° C., and the refractive index n _D by an Abbe refractometer was 1.531.

[0272]5 (or 6) -phenyl-bicyclo
[2.2.1] Heptyl-2-acrylate ^*(= Ph-
NB-A) homopolymer (hereinafter referred to as C-component)
Synthesis

[0273]

[Chemical 83]

5 (or 6) purified by vacuum distillation
-Phenyl-bicyclo [2.2.1] heptyl-2-acrylate 99 parts, n-octyl mercaptan 0.05
Part, 2,2'-azobisisobutyronitrile (0.05 part) and toluene (300 parts) were mixed in the absence of oxygen, and the mixture was polymerized at 80 ° C for 24 hours. The produced polymer was poured into a large excess of methanol to cause precipitation, and then dried under reduced pressure. The polymer obtained had an intrinsic viscosity [η] determined at 30 ° C. of a toluene solution of 0.67 dl / g, and a Tg measured by DSC of 102 ° C.
The refractive index n _D by the Abbe refractometer was 1.582.

TD-A, methyl methacrylate and styrene
Synthesis of ren terpolymer (hereinafter referred to as C-component) 50 parts of TD-A purified by vacuum distillation, 30 parts of methyl methacrylate, 20 parts of styrene, 0.05 part of n-octyl mercaptan, 2,2 A monomer mixture consisting of 0.05 part of'-azobisisobutyronitrile and 300 parts of toluene was mixed in the absence of oxygen, and the polymerization was completed at 70 ° C. for 24 hours. The produced polymer was poured into a large excess of methanol to cause precipitation, and then dried under reduced pressure. The obtained polymer had an intrinsic viscosity [η] determined with a toluene solution of 30 ° C. of 0.63 dl / g, a Tg measured by DSC of 112 ° C., and a refractive index n _D by an Abbe refractometer of 1.533. .

A copolymer of TD-A and styrene (hereinafter referred to as C
(Referred to as “component”) 50 parts of TD-A and styrene 50 purified by vacuum distillation.
Part, n-octyl mercaptan 0.05 part, 2,2′-azobisisobutyronitrile 0.05 part and toluene 3
A monomer mixture consisting of 00 parts was mixed in the absence of oxygen,
Polymerization was completed at 70 ° C. for 24 hours. The produced polymer was poured into a large excess of methanol to cause precipitation, and then dried under reduced pressure. The polymer obtained is 3
Intrinsic viscosity [η] obtained with a toluene solution at 0 ° C is 0.78.
dl / g, Tg measured by DSC was 113 ° C., and refractive index n _D by Abbe refractometer was 1.563.

Example 1 80 parts by weight of the cyclic olefin copolymer (Copolymer I) shown in the above production example, 20 parts by weight of the core-shell elastomer shown in the production example of component B, and 5 parts by weight of C-component. Mix well in a plastic bag under a nitrogen atmosphere,
Nitrogen was replaced for an hour. Using a twin-screw extruder (Haake Co., TW100 type), the mixture has a maximum cylinder temperature of 23.
The mixture was melt-blended at 0 ° C. for a residence time of 1 minute and pelletized with a pelletizer. The obtained results are shown in Table 1.

Examples 2 to 7 and Comparative Examples 1 and 2 Compositions were prepared in the same manner as in Example 1 with the components and addition amounts shown in Table 1. The results are shown in Table 1.

[0279]

[Table 1]

[0280]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 45/00 LKB 51/04 LKY (72) Inventor Masayuki Okabe Waki Roku, Waki-cho, Yamaguchi Prefecture Chome 1-2 Mitsui Petrochemical Industry Co., Ltd. (72) Masahiro Kishine 6-1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Co., Ltd.

Claims (5)

[Claims] 1. At least one of [A]. [A-1] (i) an 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.
Is an integer, w is 0 or 1, and R⁶¹~ R⁷⁸Nara
Bini R^a1And R^b1Are each independently a hydrogen atom,
Rogen atom or hydrocarbon group, R⁷⁵~ R⁷⁸Are mutual
May be bonded to each other to form a monocycle or polycycle, or
The monocycle or polycycle may have a double bond,
R⁷⁵And R⁷⁶Or with or R⁷⁷And R⁷⁸And Alkylidene
A group may be formed), and(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, R⁸¹~ R⁹⁹
Are independently hydrogen atom, halogen atom, and aliphatic carbon
Hydrogen group, alicyclic hydrocarbon group, aromatic hydrocarbon group or
Rukoxy group, R⁸⁹Or R⁹⁰Carbon to which is bound
Atom and R⁸³The carbon atom to which is bound or R⁹¹Is joined
The carbon atoms used are either directly or having 1 to 3 carbon atoms.
May be bonded via an alkylene group of
When z = 0, R⁸⁵And R⁸²Or R ⁸⁵And R⁹⁹And each other
May combine to form a monocyclic or polycyclic aromatic ring
At least one cyclic olefin represented by
Random Copolymer of Cyclic Olefin Obtained by Copolymerizing
A combination, [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
So, the intrinsic viscosity [η] in decalin at 135 ℃ is
0.05-5.0 dl / g, measured by DSC
Glass transition temperature (Tg) is 70 ℃ or more, at 25 ℃
Measured refractive index n_DWith 1.500 to 1.650
Olefin polymer, [B]. [B-1] 40 to 85 parts by weight of a core component consisting of styrene-butadiene rubber having a styrene unit content of 50% by weight or less, and [B-2] (b-1) monovinyl polymer Aromatic monomer 20 to 80% by weight (b-2) 20 to 80% by weight of alkyl (meth) acrylate monomer copolymerizable therewith and (b-3) Polyfunctional monomer 0 to 3% by weight Is a copolymer composed of a monomer mixture consisting of
15 to 60 parts by weight of a shell component consisting of
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
Characterized by being in the 300 nm range
Core / shell elastomer and [C]. [C-1] the following general formula [III](In the formula [III], n is 0 or 1, m is 0 or
Is a positive integer, q is 0 or 1, and R is¹~ R¹⁸
And R^aAnd R^bAre each independently a hydrogen atom,
A halogen atom or a hydrocarbon group, R¹⁵~ R¹⁸Are mutual
May be bonded to each other to form a monocycle or polycycle, or
The monocycle or polycycle may have a double bond,
R¹⁵And R¹⁶Or with or R¹⁷And R¹⁸And Alkylidene
May form a group, X¹And X²One of
Is an acryloyloxy group represented by the following formula [X]:
Is a methacryloyloxy group and the other is a hydrogen atom
Or an alkyl group),(Wherein R is a hydrogen atom or a methyl group)
Compound represented by the following general formula [IV](In the formula [IV], p and l are 0 or 1 or more.
Is an integer, r and s are 0, 1 or 2, and R^{twenty one}
~ R³⁹Are each independently hydrogen atom, halogen atom, fat
Group hydrocarbon groups, aromatic hydrocarbon groups and alkoxy groups
Represents an atom or group selected from the group consisting of²⁹Oh
And R³⁰The carbon atom to which is bound and R³³Are bound
Carbon atom or R³¹The carbon atom to which
Or a bond through an alkylene group having 1 to 3 carbon atoms
R, when r = s = 0, R³⁵And R³²Well
Or R³⁵And R³⁹And are linked to each other to form a monocyclic or polycyclic
X may form an aromatic ring, X³And X^FourOne of
One is acryloyloxy represented by the above formula [X]
Group or a methacryloyloxy group, the other is hydrogen
An atom or an alkyl group),
And the following formula [V](In the formula [V], t is 4 or 5, and R is⁴¹~ R⁴³Haso
Each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group.
X^FiveIs an acryloyloxy group represented by the following formula [X]
Si group or methacryloyloxy group),
Having an alicyclic skeleton selected from the group consisting of
At least acrylate or methacrylate monomer
Monomer or single amount containing 20 to 100% by weight of one kind
A (co) polymer composed of a body mixture as a constituent
And the weight ratio of the component [A] to the component [B] is 40.
/ 60-95 / 5 range and these [A] component
[C] component is 3 to 4 per 100 parts by weight of [B] component in total.
Cyclic olefins characterized by being in the range of 0 parts by weight
Polymer composition. 2. The cyclic olefin polymer composition according to claim 1, wherein the component [C] is a homopolymer of the acrylate or methacrylate monomer represented by the formula [III]. 3. The cyclic olefin system according to claim 1, wherein the component [C] is a copolymer of an acrylate or methacrylate monomer represented by the formula [III] and an alkyl (meth) acrylate or styrene. Polymer composition. 4. The cyclic olefin system according to claim 1, wherein the component [C] is a copolymer of an acrylate or methacrylate monomer represented by the formula [III], an alkyl (meth) acrylate and styrene. Polymer composition. 5. The cyclic olefin polymer composition according to claim 1, wherein the component [C] is a homopolymer of the acrylate or methacrylate monomer represented by the formula [IV].