JPH06228377A - Cycloolefin copolymer composition - Google Patents

Abstract

PURPOSE:To obtain a compsn. having improved impact strength, transparency, and heat resistance by subjecting two specific cycloolefin random copolymers to a free-radical reaction with each other. CONSTITUTION:A 2C or higher alpha-olefin (a), a cycloolefin (b) of formula I or II, and a diene compd. (c), if necessary, are copolymerized to give a cycloolefin random copolymer (A) having an intrinsic viscosity (eta, 135 deg.C) of 0.1-5.0dl/g and a glass transition point (Tg, DSC) of 70-200 deg.C, 60-99wt.% copolymer A is subjected to a free-radical reaction with 40-1wt.% copolymer (B) obtd. by copolymerizing the above-mentioned monomers (a), (b) and (c) and having an etaof 0.1-10.0dl/g and a Tg of 30-10 deg.C in the presence of an org. peroxide and as necessary in the presence of a radical-polymerizable polyfunctional monomer, giving a compsn. which has such melt flow properties that the MFR after the reaction, MFR (1), and that just after blended, MFR (2), satisfy the formula III.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a cyclic olefin-based copolymer composition, more specifically, impact resistance, transparency,
The present invention relates to a cyclic olefin copolymer composition having excellent heat resistance.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION The present applicant has previously found that a cyclic olefin random copolymer obtained by copolymerizing ethylene and a cyclic olefin such as tetracyclododecene is excellent in transparency and heat resistance. Resistance, heat aging resistance, chemical resistance,
It has been found that it is a synthetic resin having well-balanced solvent resistance, dielectric properties, and rigidity, and exhibits excellent performance in the field of optical materials such as optical memory disks and optical fibers, and has already been disclosed in JP-A-60-168708. JP, JP-A-61-98780, JP-A-61-11591
No. 2, JP 61-115916, and JP 6
It is proposed in JP-A No. 1-120816 and JP-A No. 62-252407. 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 are particularly excellent in heat resistance and rigidity, there is room for improvement in impact resistance, and the transparency possessed by these cyclic olefin-based copolymers is provided. It is required to further improve impact resistance while maintaining the same.

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.

Therefore, the present inventors have used two kinds of cyclic olefin-based random copolymers having a specific glass transition temperature, an organic peroxide and, if necessary, a radical-polymerizable polyfunctional monomer. Addition, the cyclic olefin random copolymer composition obtained by reacting radically so as to have a specific reactivity, found that impact resistance, transparency, excellent heat resistance balance, The present invention has been completed.

[0008]

OBJECTS OF THE INVENTION It is an object of the present invention to provide a cyclic olefin copolymer composition having an excellent balance of impact resistance, transparency and heat resistance.

[0009]

SUMMARY OF THE INVENTION A cyclic olefin copolymer composition according to the present invention is represented by [A] (i) an α-olefin having 2 or more carbon atoms, and (ii) the following formula [I] or [II]. Obtained by copolymerizing at least one cyclic olefin and (iii) a diene compound, if necessary, and having an intrinsic viscosity [η] in decalin at 135 ° C. of 0.1 to 5.0 dl / g. And DS
Glass transition temperature (Tg) measured by C is 70 to 20
Cyclic olefin-based random copolymer at 0 ° C .: 60 to
99% by weight, [B] (i) an α-olefin having 2 or more carbon atoms, (ii) at least one cyclic olefin represented by the following formula [I] or [II], and optionally ( iii) Obtained by copolymerizing with a diene compound, the intrinsic viscosity [η] in decalin at 135 ° C. is 0.1 to 10.0 dl / g, and D
Glass transition temperature (Tg) measured by SC is -30 ° C
Cycloolefin-based random copolymer having a temperature of -10 ° C: 1
260 wt% was obtained by radically reacting ˜40 wt% with an organic peroxide and optionally a radically polymerizable polyfunctional monomer in the presence of a load of 2.16 kg.
Melt flow rate [MFR
(1)] and the melt flow rate [MFR (2)] when the [A] component and the [B] component are blended in the same weight ratio as the composition. (1)
It is characterized by the relationship of.

0.001 ≦ MFR (1) / MFR (2) ≦ 0.5 Formula (1)

[0011]

[Chemical 3]

(However, in the above formula [I], n is 0.
Or 1, m is 0 or a positive integer, and q is 0
Or 1 and R ^{1 to} R ¹⁸ and R ^a and R ^b
Are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, and R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring is It may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group. )

[0013]

[Chemical 4]

(In the above formula [II], p and q are 0 or a positive integer, and m and n are 0, 1
Or a 2, R ¹ to R ¹⁹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group, the carbon atom to which R ⁹ or R ¹⁰ is attached, R ¹³
May be bonded to the carbon atom to which R is bonded or to the carbon atom to which R ¹¹ is bonded, directly or through an alkylene group having 1 to 3 carbon atoms, and when n = m = 0, R ¹⁵
And R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. )

[0015]

DETAILED DESCRIPTION OF THE INVENTION The cycloolefin copolymer composition according to the present invention will be described below. The cyclic olefin-based copolymer composition according to the present invention contains a specific cyclic olefin-based random copolymer [A] and a specific cyclic olefin-based random copolymer [B] at a specific ratio. It can be obtained by radically reacting (interpolymer binding reaction) in the presence of an oxide and, if necessary, a radically polymerizable polyfunctional monomer.

The cyclic olefin random copolymer [A] and the cyclic olefin random copolymer [B] used in the present invention are both (i) an α-olefin having 2 or more carbon atoms, and (ii) A cyclic olefin random copolymer obtained by copolymerizing at least one cyclic olefin represented by the formula [I] or [II] and, if necessary, (iii) a diene compound.

In the present invention, an α-olefin having 2 or more carbon atoms is used as the olefin component. Specific examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1- Hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like α having 2 to 20 carbon atoms
-Examples include olefins. Of these, ethylene is particularly preferably used.

First, the cyclic olefin used for producing the above cyclic olefin random copolymer is represented by the following formula [I] or [II].

[0019]

[Chemical 5]

In the above formula [I], n is 0 or 1, m is 0 or a positive integer, and q is 0 or 1. When q is 1, R ^a and R ^b each independently represent the following atom or hydrocarbon group, and q
When is 0, the respective bonds bond to each other to form a 5-membered ring.

In the above formula [I], R ^{1 to} R ¹⁸
And R ^a and R ^b 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 usually has 1 carbon atom.
To 20 alkyl groups, C3 to C15 cycloalkyl groups or aromatic hydrocarbon groups. 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 ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ , R ¹⁵ and R
¹⁷ and R ¹⁶ and R ¹⁸ , R ¹⁵ and R ¹⁸ , or R
¹⁶ and R ¹⁷ may be bonded to each other (cooperate with each other) to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring thus formed has a double bond. May be.

Specific examples of the monocycle or polycycle formed here include the following.

[0025]

[Chemical 6]

In the above example, the carbon atoms with the numbers 1 and 2 are respectively represented by R in the formula [I].
^It represents a carbon atom to which ¹⁵ (R ¹⁶ ) or R ¹⁷ (R ¹⁸ ) is bonded.

In addition, R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸
And 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.

[0028]

[Chemical 7]

In the above formula [II], p and q are 0.
Alternatively, it is a positive integer, and m and n are 0, 1 or 2. R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group.

Here, the halogen atom is the same as the halogen atom in the above formula [I]. The hydrocarbon group is usually an alkyl group having 1 to 20 carbon atoms, or 3 to carbon atoms.
There may be mentioned 15 cycloalkyl groups or aromatic hydrocarbon groups. 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 include a phenyl group, a tolyl group, a naphthyl group, a benzyl group, Examples thereof include a phenylethyl group.

Examples of the alkoxy group include methoxy group, ethoxy group and propoxy group. Where R ⁹
Or the carbon atom to which R ¹⁰ is bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded,
They may be bonded directly or via an alkylene group having 1 to 3 carbon atoms. That is, when the above two carbon atoms are bonded via an alkylene group, R ⁹ and R ¹³ or R ¹⁰ and R ¹¹ cooperate with each other to form a methylene group (—CH ₂ — ), An ethylene group (—CH ₂ CH ₂ —) or a propylene group (—CH ₂ CH ₂ CH ₂ —), which forms an alkylene group.

Further, when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. Specifically, n = m = 0
In this case, the following aromatic ring formed by R ¹⁵ and R ¹² can be mentioned.

[0034]

[Chemical 8]

Here, q is the same as q in the formula [II]. Specific examples of the cyclic olefin represented by the above formula [I] or [II] include a bicyclo [2.2.1] -2-heptene derivative (bicyclo [2.2.1] hept-2-ene derivative). , Tricyclo [4.3.0.1 ^2,5 ] -3-decene derivative, tricyclo [4.4.0.1 ^2,5 ] -3-undecene derivative, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene derivative , Pentacyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] -4-
Pentadecene derivative, pentacyclo [7.4.0.1 ^2,5 .
1 ^9,12 .0 ^8,13] -3-pentadecene derivatives, penta cyclopentadiene decadiene derivative, pentacyclo [8.4.0.1 ^2,5 .1
^9,12 .0 ^8,13] -3-hexadecene derivative, pentacyclo ^{[6.6.1.1 3,6 .0 2,7 .0 9,14]} -4- hexadecene derivative, hexacyclo [6.6.1.1 ^{3, 6} .1 ^10,13 .0 ^2,7 .0 ^9,14] -4-heptadecene derivatives, heptacyclo-5-eicosene derivatives,
Heptacyclo ^{[8.7.0.1 3,6 .1 10,17 .1 12,15 .0} 2,7.
0 ^11,16] -4-eicosene derivatives, heptacyclo-5-heneicosene derivatives, heptacyclo [8.8.0.1 ^4,7 .1 ^11,18.
1 ^13,16 .0 ^3,8 .0 ^12,17] -5-heneicosene derivatives, octacyclo ^{[8.8.0.1 2,9 .1 4,7 .1 11,18 .1} 13,16 .0 3,8. 0
^12,17 ] -5-Dococene derivative, nonacyclo [10.9.1.
1 ^4,7 .1 ^13,20 .1 ^15,18 .0 ^3,8 .0 ^2,10 .0 ^12,21 .0 ^14,19] -5-pentacosene derivatives, Nonashikuro [10.10.1.1 ^5,8. 1 ^14,21 .
1 ^16,19 .0 ^2,11 .0 ^4,9 .0 ^{13, 22} .0 ^15,20] -6-hexacosenoic derivatives, cyclopentadiene - acenaphthylene adduct, 1,
4-methano-1,4,4a, 9a-tetrahydrofluorene derivative,
1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene derivative and the like can be mentioned.

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

[0037]

[Chemical 9]

[0038]

[Chemical 10]

[0039]

[Chemical 11]

[0040]

[Chemical 12]

[0041]

[Chemical 13]

[0042]

[Chemical 14]

[0043]

[Chemical 15]

[0044]

[Chemical 16]

[0045]

[Chemical 17]

[0046]

[Chemical 18]

[0047]

[Chemical 19]

[0048]

[Chemical 20]

[0049]

[Chemical 21]

[0050]

[Chemical formula 22]

[0051]

[Chemical formula 23]

[0052]

[Chemical formula 24]

[0053]

[Chemical 25]

[0054]

[Chemical formula 26]

[0055]

[Chemical 27]

[0056]

[Chemical 28]

[0057]

[Chemical 29]

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

These cyclic olefins can be used alone or in combination of two or more kinds. Specific examples of the diene-based compound used in the present invention include non-conjugated dienes having 5 to 20 carbon atoms represented by the following formulas [III] to [VI]. .

[0060]

[Chemical 30]

As the non-conjugated diene represented by the above formula [III], 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1, 9-
Dekaji et emissions, 1,11 dodecadiene, and the like can be exemplified 1,19 Eikojien.

As the diene compound represented by the above formula [IV],

[0063]

[Chemical 31]

And the like. As the non-conjugated diene represented by the above formula [V],

[0065]

[Chemical 32]

Examples thereof include The above formula [V
As the non-conjugated diene represented by [I],

[0067]

[Chemical 33]

Examples thereof include: In the diene compound as described above, the hydrogen atom bonded to carbon other than carbon forming the carbon-carbon double bond may be substituted with a hydrocarbon group.

Among the diene compounds represented by the above formulas [III] to [VI], 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 5-vinyl-bicyclo [2.2.
1] Hept-2-ene, 8-vinyl-tetracyclo [4.4.0.1
^2,5 .1 ^7,10 ] -3-Dodecene, bicyclo [2.2.1] hept-
2,5-dienes, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3,8-
Dodecadiene is preferably used.

Further, in the present invention, the following compounds can be used as the (iii) diene compound. 1,
4-hexadiene, 2-methyl-1,5-hexadiene, 4-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-
Chained dienes such as methyl-1,6-octadiene; 5-
Cyclic dienes such as ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, norbornadiene, and 6-chloromethyl-5-isopropenyl-2-norbornene.

Among these, 1,4-hexadiene, 1,5-hexadiene, 1,9-decadiene, 5-vinylnorbornene, 5-
Ethylidene-2-norbornene and the like are preferable. The cyclic olefin random copolymers [A] and [B] used in the present invention have the above-mentioned (i) α of 2 or more carbon atoms.
-A soluble vanadium compound as described below, containing an olefin, (ii) at least one cyclic olefin represented by the above formula [I] or [II], and optionally (iii) a diene compound And organoaluminum compound (A)
A catalyst formed from (a), or IVB of the periodic table
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 forming such 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
A vanadium compound such as 7OH 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.

Examples of such electron donors include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, organic acid or inorganic acid esters, ethers, diethers and acid amides. , Acid anhydrides, oxygen-containing electron donors such as alkoxysilane, and nitrogen-containing electron donors such as ammonia, 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, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzoate Benzyl acid, methyl toluate,
2 to 2 carbon atoms such as ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethyl carbonate
18 organic acid esters; C2 to C15 acid halides such as acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride; methyl ether,
Ethers having 2 to 20 carbon atoms such as ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether; acid anhydrides such as acetic anhydride, phthalic anhydride, benzoic anhydride; ethyl silicate, diphenyldimethoxysilane Acid amides such as acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluic acid N, N-dimethylamide; trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylethylenediamine, etc. Amines; nitriles such as acetonitrile, benzonitrile, trinitrile;
Pyridines such as pyridine, methylpyridine, ethylpyridine and dimethylpyridine can be exemplified.

In preparing the electron donor adduct of the 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 (a) and (b) It is represented by a formula.

(A) General formula R ¹ _m Al (OR ² ) _n H _p X _q (In the formula, R ¹ and R ² usually have 1 to 15 carbon atoms,
It is preferably 1 to 4 hydrocarbon groups, which 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 and q are numbers 0 ≦ q <3, and m + n + p +
q = 3) (b) Complex of a Group 1 metal represented by the general formula M ¹ AlR ¹ (wherein M ¹ is Li, Na and K, and R ¹ is the same as above) with aluminum. Alkylated Compounds Specific examples of the organoaluminum compound represented by the above (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, the organoaluminum compound (A) represented by (a) can be exemplified by the following compounds.

Examples of the organoaluminum compound represented by (1) are 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; ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide and the like. Alkyl aluminum sesquihalides; 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 dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; partially hydrogenated alkylaluminums such as ethylaluminum dihydride and propylaluminum dihydride. Can be mentioned.

Examples of the organoaluminum compound represented by (4) include partially aluminum-alkoxylated and halogenated alkylaluminums such as ethylaluminum 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 aluminums are bonded via an oxygen atom or a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ and (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 and an organoaluminum oxy compound, and optionally an organoaluminum compound (B) will be described. To do.

As the transition metal compound of Group IVB or lanthanide of the periodic table containing such a ligand having a cyclopentadienyl skeleton, compounds represented by the following general formula [VII] are exemplified. it can.

ML _X ... [VII] In the above general formula [VII], 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 [VII] contains two or more groups having a cyclopentadienyl skeleton, the two groups having a cyclopentadienyl skeleton are alkylene groups such as ethylene and propylene, It may be bonded via a substituted alkylene group such as isopropylidene 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 a methoxy group, an ethoxy group and a butoxy group. A phenoxy group etc. are illustrated as an aryloxy group.

Halogen includes fluorine, chlorine, bromine,
Examples thereof include iodine. Examples of the ligand represented by SO ₃ R include a p-toluenesulfonato group, a methanesulfonato group, and a trifluoromethanesulfonato group.

Examples of the compound represented by the above general formula [IV] include
For example, when the valence of the transition metal is 4, more specifically,
It is represented by the following general formula [VII ']. R¹ _aR² _bR³ _cR^Four _dM ... [VII '] (In the formula [VII'], M is zirconium, titanium, or hafnium.
Mu, Neodymium, Samarium or Ytterbium
R¹Is a group having a cyclopentadienyl skeleton
R², R³And R^FourIs the cyclopentadienyl skeleton
Group having, alkyl group, cycloalkyl group, aryl
Group, aralkyl group, alkoxy group, aryloxy group, ha
Rogen atom, trialkylsilyl group, SO₃R or water
Elementary atom, a is an integer of 1 or more, and a + b + c +
d = 4. In the present invention, R in the above general formula [VII ′] is², R³And
And R^FourOne of them has a cyclopentadienyl skeleton
A group of transition metal compounds such as R¹And R ²Siku
A transition metal compound having a lopentadienyl skeleton
Is preferably used. These cyclopentadienyl
The group having a skeleton is an alkylene such as ethylene or propylene.
Group, alkylidene group such as isopropylidene, diphenyl group
Substituted alkylene group such as nylmethylene, silylene group or
Is dimethylsilylene, diphenylsilylene, methylphen
Bonded via a substituted silylene group such as a nylsilylene group
It may have been done. Also, R³And R^FourIs a cyclopen
A group having a tadienyl skeleton, an alkyl group, a cycloalkyl group
Group, aryl group, aralkyl group, alkoxy group, ari
-Roxy group, halogen atom, trialkylsilyl group, S
O₃R 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 (methanesulfonate), ethylenebis (Indenyl) zirconium bis (p-toluenesulfonato), ethylenebis (indenyl) zirconium bis (trifluoromethanesulfonato), ethylenebis (4,5, 6,7-Tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) ) Dimethyl zirconium, dimethyl silylene bis (cyclopentadienyl) zirconium dichloride, dimethyl silylene bis (methyl cyclopentadienyl) zirconium dichloride, dimethyl silylene bis (dimethyl cyclopentadienyl) zirconium dichloride, dimethyl silylene bis (trimethylcyclopentadiene) (Enyl) zirconium dichloride, dimethyl silylene bis (indenyl) zirconium dichloride, dimethyl silylene bis (Indenyl) zirconium bis (trifluoromethanesulfonato), dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) Zirconium dichloride, methylphenylsilylene bis (indenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide,
Bis (cyclopentadienyl) methyl zirconium monochloride, bis (cyclopentadienyl) ethyl zirconium monochloride, bis (cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride,
Bis (cyclopentadienyl) benzylzirconium monochloride, bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclo Pentadienyl) diphenylzirconium, bis (cyclopentadienyl) dibenzylzirconium,
Bis (cyclopentadienyl) zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluene) Sulfonato), bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) Zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (dimethylcyclopentadienyl) dimethyl zirconium, bis (eth Rucyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadiene (Enyl) 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 cyclopentadienyl ring is 1,2- and 1,2.
3-substitutes are included, and tri-substitutes include 1,2,3- and 1,2,4-substitutes. In addition, alkyl groups such as propyl and butyl are
It includes isomers such as n-, i-, sec-, and tert-.

In the present invention, in the above zirconium compound, a transition metal compound in which 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.

[0099]

[Chemical 34]

(In the formula, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group, preferably a methyl group and an ethyl group, particularly preferably a methyl group, and m
Is an integer of 2 or more, preferably 5 to 40. ) Here, the aluminoxane is an alkyloxyaluminum unit represented by the formula (OAl (R ¹ )) and a formula (O
Al (R ² )) alkyloxyaluminum unit [wherein R ¹ and R ² can be the same hydrocarbon groups as R, and R ¹ and R ² represent different groups] May be formed from a mixed alkyloxyaluminum unit consisting of

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, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method in which an organoaluminum compound such as trialkylaluminum is added to an aromatic hydrocarbon solvent in which is suspended and reacted to recover a solution of the aromatic hydrocarbon 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.

Among these methods, it is preferable to adopt the method (1). As the organoaluminum compound used in preparing the solution of aluminoxane, specifically, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec- Butyl aluminum, tri
Trialkyl aluminum such as tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, and tridecyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; dimethyl aluminum chloride, diethyl aluminum chloride, diethyl Aluminum bromide,
Dialkyl aluminum halides such as 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; Dialkyl aluminum aryloxides such as diethyl aluminum phenoxide be able to.

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

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

The benzene-insoluble organoaluminum oxy compound used in the present invention is, for example, a method of bringing a solution of aluminoxane into contact with water or an active hydrogen-containing compound, or an organoaluminum compound and water as described above. It can be obtained by a method of contacting.

[0108] 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 above benzene-insoluble organoaluminum oxy compound is presumed to have an alkyloxy aluminum unit represented by the following formula.

[0110]

[Chemical 35]

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.
Examples thereof include a butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, cyclohexyl group and 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.

[0113]

[Chemical 36]

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 from each other.

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. Organoaluminum compound (B) optionally used in the catalyst (B)
For example, an organoaluminum compound represented by the following general formula [VIII] can be exemplified.

R ⁵ _n AlX _3-n ... [VIII] (In the formula [VIII], 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 [VIII], R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms such as 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, tri2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminium 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 [IX] can also be used. During ^{_{R 5 n AlY 3-n ...}} [IX] ( wherein [IX], R ⁵ are as defined above, Y is -OR ⁶
Group, -OSiR ⁷ ₃ group, -OAlR ⁸ ₂ group, -NR ⁹ ₂ group, -
SiR ¹⁰ ₃ group or —N (R ¹¹ ) AlR ¹² ₂ group, and n is 1
To R 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, and R ⁹ is a hydrogen atom, a methyl group, an ethyl group, It is 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 , for example Et ₂ Al (OSi Me ₃ ), (iso-Bu) ₂ A
l (OSiMe ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), etc.
(Iii) a compound represented by R ⁵ _n Al (OAlR ⁸ ₂ ) _3-n ,
For example, Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOA
l (iso-Bu) _{2 and} other compounds represented by (iv) R ⁵ _n Al (NR ⁹ ₂ ) _3-n , such as Me ₂ AlNEt ₂ and Et ₂ AlN.
_{HMe, Me 2 AlNHEtEt 2 AlN (} SiMe 3) 2, (iso
-Bu) ₂ AlN (SiMe ₃ ) ₂ etc., (v) R ⁵ _n Al (SiR
A compound represented by ¹⁰ ₃ ) _3-n , for example (iso-Bu) ₂ Al
Si Me ₃ etc., (vi) R ⁵ _n Al (N (R ¹¹ ) Al
A compound represented by R ¹² ₂ ) _3-n , such as Et ₂ AlN (M
e) AlEt ₂ , (iso-Bu) ₂ AlN (Et) Al (iso-
Bu) ₂ etc.

Among the organoaluminum compounds represented by the above general formulas [VIII] and [IX], the general formula R ⁵ ₃ Al,
The organoaluminum compounds represented by R ⁵ _n Al (OR ⁶ ) _3-n and R ⁵ _n Al (OAlR ⁸ ₂ ) _3-n can be given as preferred examples, wherein R ⁵ is an isoalkyl group and n = 2 is particularly preferable. These organoaluminum compounds are
It is also possible to use a mixture of two or more kinds.

The cyclic olefin random copolymer [A] used in the present invention has an intrinsic viscosity [η] measured in decalin of 135 ° C. of 0.1 to 5.0 dl / g, preferably 0.15. It is in the range of 4.5 dl / g.

The cyclic olefin random copolymer [A] has a glass transition temperature (Tg) measured by DSC of 70 to 200 ° C., preferably 90 to 180 ° C.
Is within the range of.

In such a cyclic olefin random copolymer [A], the repeating unit derived from the α-olefin component having 2 or more carbon atoms is usually 40 to 85 mol%, preferably 42 mol to 80 mol%. The repeating unit which exists in the range and is derived from the cyclic olefin is usually 15 to 60.
It is present in the range of mol%, preferably 20 to 58 mol%. The diene compound used as necessary is 10
It exists in a proportion of not more than mol%.

The cyclic olefin random copolymer [A] as described above preferably has an iodine value of 30 or less. On the other hand, the cyclic olefin random copolymer [B] used in the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.1 to 10.0 dl / g, preferably 0.5 to 5. Within the range of 0.0 dl / g.

The cyclic olefin random copolymer [B] has a glass transition temperature (Tg) measured by DSC in the range of -30 to 10 ° C. Such a cyclic olefin random copolymer [B] has 2 carbon atoms.
Repeating units derived from the above α-olefin component,
It is usually present in the range of 60 to 97 mol%, preferably 70 to 95 mol%, and the repeating unit derived from a cyclic olefin is usually 3 to 40 mol%, preferably 30 to
It is present in the range of 5 mol%. The diene compound used as necessary is present in a proportion of 10 mol% or less.

The cyclic olefin random copolymer [B] as described above preferably has an iodine value of 30 or less. In the cyclic olefin-based copolymer composition according to the present invention, the cyclic olefin-based random copolymer [A] is 9
The cyclic olefin-based random copolymer [B] is used in an amount of 9 to 60% by weight, preferably 90 to 70% by weight.
It is used in an amount of 1 to 40% by weight, preferably 10 to 30% by weight. The total amount of these is 100% by weight.

The cyclic olefin copolymer composition according to the present invention comprises the above cyclic olefin random copolymer [A] and the above cyclic olefin random copolymer [B]. It can be obtained by heating and reacting radically (bonding reaction between polymers) in the presence of an organic peroxide and, if necessary, a radically polymerizable polyfunctional monomer.

Specific examples of the organic peroxide include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; 1,1-bis (tert-butylperoxy) cyclohexane and 2,2- Peroxyketals such as bis (tert-butylperoxy) octane; tert-butylhydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroxyperoxide, 1,1,3,3 -Hydroperoxides such as tetramethylbutyl hydroperoxide; di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-diethyl-2, 5-di (tert
-Butylperoxy) hexyne-3 and other dialkyl peroxides; lauroyl peroxide, benzoyl peroxide and other diacyl peroxides; tert-butylperoxyacetate, tert-butylperoxybenzoate, 2,5-dimethyl-2 Examples include peroxyesters such as 1,5-di (benzoylperoxy) hexane.

In the present invention, the organic peroxide is usually added in an amount of 0.01 to 10 relative to 100 parts by weight of the total of the cyclic olefin random copolymer [A] and the cyclic olefin random copolymer [B]. It is used in an amount of parts by weight, preferably 0.05 to 5 parts by weight.

Specific examples of the radically polymerizable polyfunctional monomer include divinylbenzene, vinyl acrylate, vinyl methacrylate, triaryl isocyanurate, diaryl phthalate, ethylene dimethacrylate and trimethylolpropane trimethacrylate. Can be mentioned.

In the present invention, when the radical-polymerizable polyfunctional monomer is used, the radical-polymerizable polyfunctional monomer is a cyclic olefin random copolymer [A] and a cyclic olefin random copolymer. It is usually used in an amount of 0.01 to 15 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight in total with [B].

Such cyclic olefin random copolymer [A] and cyclic olefin random copolymer [B]
And a cyclic olefin random copolymer composition obtained by radically reacting with and in the presence of an organic peroxide and, if necessary, a radically polymerizable polyfunctional monomer, a load of 2.16 kg is measured. In the case of blending the melt flow rate [MFR (1)] of the composition at 260 ° C., the [A] component and the [B] component in the same weight ratio as the composition. Rate [MFR
(2)], the relationship of the following expression (1) is established.

0.005 ≤ MFR (1) / MFR (2) ≤ 0.5 Formula (1) Further, formula (2) 0.005 ≤ MFR (1) / MFR (2) ≤ 0.2 formula (2 It is more preferable that the relationship such as

Melt flow rate of the composition [MFR
The value of (1)] depends on Tg of the component [A], but is 5 g /
It is preferably 10 minutes to 0.001 g / 10 minutes,
The case of 3 g / 10 minutes to 0.01 g / 10 minutes is more preferable.

Regarding the transparency of the cycloolefin copolymer composition according to the present invention, the 2 mm thick sheet obtained by molding the composition has a light transmittance at 780 nm of 50% or more, preferably 60% or more, More preferably, it is desirable to be 70% or more.

The cyclic olefin-based copolymer composition according to the present invention comprises a part of the cyclic olefin-based random copolymer [A] and a part of the cyclic olefin-based random copolymer [B]. Radically react with the product obtained by radically reacting with the rest of the cyclic olefin-based random copolymer [A] and the rest of the cyclic olefin-based random copolymer [B]. It can also be obtained by blending with the product thus obtained.

The cyclic olefin-based copolymer composition according to the present invention decomposes the above cyclic olefin-based random copolymer [A] and cyclic olefin-based random copolymer [B] into organic peroxide. Or a radically polymerizable polyfunctional monomer is added to the organic olefin-based random copolymer [A], the cyclic olefin-based random copolymer [B] and the radical-polymerizable polyfunctional monomer. It can be produced by heating to a temperature at which the substance decomposes and reacting radically.

In the above reaction, each raw material may be mixed and reacted at the same time, but after the cyclic olefin random copolymer [A] and the cyclic olefin random copolymer [B] are mixed, A method in which an organic peroxide, or an organic peroxide and a radically polymerizable polyfunctional monomer are mixed and reacted with the obtained mixture is preferable. The organic peroxide is preferably reacted in a state of being sufficiently mixed with the cyclic olefin random copolymer [A] and the cyclic olefin random copolymer [B].

Cyclic Olefin Random Copolymer [A]
As a method for mixing the cyclic olefin random copolymer [B] with each other, a method for producing these copolymers separately and blending both copolymers with an extruder or the like, or a method for blending these copolymers A so-called solution blending method in which a suitable solvent, for example, a saturated hydrocarbon such as heptane, hexane, decane, cyclohexane; an aromatic hydrocarbon such as toluene, benzene, xylene, etc. is sufficiently dissolved and mixed, and further, a copolymer thereof. Are synthesized in separate polymerization vessels, and each of the obtained copolymers is blended in another container.

An organic peroxide, or an organic peroxide and a radically polymerizable polyfunctional monomer are added to the mixture of the copolymers obtained as described above and blended to obtain an organic peroxide. The reaction is preferably carried out at a decomposition temperature.

The above reaction can be carried out in the molten state of the mixture of the raw materials, or in the solution state in which the mixture of the raw materials is dissolved in a solvent. When the above reaction is carried out in a molten state, the mixture of raw materials is melted and reacted using a kneading device such as a mixing roll, a Banbury mixer, an extruder, a kneader or a continuous mixer. The reaction is carried out at a temperature not lower than the one-minute half-life of the organic peroxide, usually 150 to 300 ° C, preferably 170 to 270 ° C.
It is usually carried out for 10 seconds to 30 minutes, preferably 3 to 10 minutes.

When the above reaction is carried out in a solution state, the solvent used may be the same solvent as that used in the above solution blending method. The reaction is carried out at a temperature not lower than the 10-minute half-life of the organic peroxide, usually 50 to 300.
C., preferably 70 to 250.degree. C., usually 10 seconds to 3 hours, preferably 3 minutes to 2 hours.

The reaction product obtained as described above is
The target cyclic olefin-based copolymer composition can be obtained as it is or by removing the solvent by a method such as distillation.

The cyclic olefin-based copolymer composition according to the present invention is excellent in transparency and impact resistance. This is because the organic peroxide is decomposed in the above reaction to cause a radical reaction. It is presumed that the olefin random copolymer [A] and the cyclic olefin random copolymer [B] were partially bonded to each other by interpolymer bonding.

A cyclic olefin random copolymer [A] and a cyclic olefin random copolymer [B]
When a double bond is present in the compound, or when a radical-polymerizable polyfunctional monomer is present, the bonding reaction is more likely to occur, and a cyclic olefin-based copolymer having excellent transparency and impact resistance is obtained. It is supposed that

The cyclic olefin copolymer composition according to the present invention obtained as described above may be used alone or may be blended with another transparent resin.

[0148]

The cyclic olefin copolymer composition according to the present invention comprises a specific cyclic olefin random copolymer [A] and a specific cyclic olefin random copolymer [B]. In a proportion, the composition is reacted radically in the presence of an organic peroxide and optionally a radically polymerizable polyfunctional monomer, and the melt flow rate [MFR (1)] and [AFR ] And the component [B] are blended in the same weight ratio as that of the composition, the polymer and the melt flow rate [MFR (2)] have a specific relationship. Since the degree of inter-bonding reaction is controlled, it has excellent heat resistance, chemical resistance, rigidity, etc., and also has excellent transparency and impact resistance.

The present invention will be described below with reference to examples.
The present invention is not limited to these examples. First, methods for measuring and evaluating various physical property values in Examples and Comparative Examples are shown below. (1) Intrinsic viscosity [η] It was measured using a Ubbelohde viscometer in a decalin solution at 135 ° C. (2) Glass transition point (Tg) The glass transition point was measured using a DSC-220C manufactured by Seiko Instruments Inc. in a nitrogen atmosphere at a temperature rising rate of 10 ° C / min. (3) Monomer composition ratio in polymer Measured by ¹³ C-NMR. (4) Iodine value According to JIS K 3331, it was measured by the iodine monochloride method. (5) According to MFR ASTM D 1238, 260 ° C., 2.16 kg
It was measured under load. (6) Preparation of test piece Using an injection molding machine manufactured by Toshiba Machine Co., Ltd., IS50EPN and a predetermined test piece mold, molding was performed under the following molding conditions. After molding, the test piece was left for 48 hours at room temperature and then subjected to measurement.

(Molding conditions) Cylinder temperature: 260 ° C. Mold temperature: 60 ° C. Injection pressure: Primary / Secondary = 1000/800 kg / cm ² (7) Light transmittance Using Shimadzu spectrophotometer MPS-2000 The light transmittance was defined as the transmittance at a wavelength of 780 nm in the visible spectrum measured using a press sheet having a thickness of 2 mm as a sample. (8) Izod impact strength It was measured according to ASTM D 256.

Test piece shape: 5/2 in. × 1/8 in. × thickness 1/2 in. (With notch) Test temperature: 23 ° C. (9) Heat distortion temperature (HDT) The test was performed according to ASTM D648.

Test piece shape: 5 in. × 1/4 in. × 1 / thickness 2 in. Load: 264 psi

[0153]

[Synthesis example of cyclic olefin copolymer]

[0154]

Reference Example 1 [Synthesis of Copolymer a] Using a 1 liter capacity glass polymerization vessel equipped with a stirring blade, ethylene tetracyclo [4.4.0.1 ^2,5 ] using a vanadium-based catalyst was used. ． 1 ^7,10 ]-
3-dodecene (hereinafter, tetracyclo [4.4.0.1
^2,5 . Copolymerization of 1 ^7,10 ] -3-dodecene is abbreviated as TCD) was continuously carried out by the following method.

From the top of the polymerization vessel, dissolve TCD in cyclohexane.
The liquid has a TCD concentration of 60 g / liter in the polymerization vessel.
And as a catalyst from the top of the polymerization vessel, VO
(OC ₂H_Five) Cl₂ The cyclohexane solution of
Vanadium concentration at 0.5 mmol / liter
, Ethyl aluminum sesquichloride [Al (C
₂H_Five)_1.5Cl_1.5] Cyclohexane solution in a polymerization vessel
Aluminum concentration of 4.0 mmol / liter
Thus, each was continuously fed into the polymerization vessel. Also,
Use a bubbling tube for the polymerization system to remove ethylene at 36.0 liters.
Torr / hour, nitrogen 35.0 liters / hour, hydrogen
The amount was 1.0 liter / hour.

A copolymerization reaction was carried out while the polymerization system was kept at 10 ° C. by circulating a heating medium in a jacket attached to the outside of the polymerization vessel. Generated by the above copolymerization reaction,
The polymerization solution of the cyclic olefin-based copolymer was continuously withdrawn from the upper part of the polymerization vessel so that the polymerization solution in the polymerization vessel was always 1 liter (that is, the average residence time was 0.5 hours). A cyclohexane / isopropyl alcohol (1: 1) mixed solution was added to the extracted polymerization solution to terminate the polymerization reaction. Then, the aqueous solution prepared by adding 5 ml of concentrated hydrochloric acid to 1 liter of water and the polymerization solution were mixed in a ratio of 1: 1.
The mixture was contacted with a homomixer with strong stirring under strong stirring to transfer the catalyst residue to the aqueous phase. After the contact mixed solution was allowed to stand still, the aqueous phase was separated and removed, and then washed twice with distilled water to purify and separate the polymerization liquid phase.

Next, the purified and separated polymerization liquid was contacted with 3 times the amount of acetone under strong stirring to precipitate a copolymer, and then the solid part (copolymer) was collected by filtration, and acetone was sufficient. Washed. Further, in order to extract unreacted TCD existing in the copolymer, this solid part was put into acetone so as to have a concentration of 40 g / liter, and then extraction operation was performed at 60 ° C. for 2 hours. After the extraction process, the solid part is collected by filtration, under nitrogen flow, at 130 ° C., 350 mm
It was dried with Hg for 12 hours.

Ethylene.T obtained as described above
The CD copolymer has an intrinsic viscosity [η] of 0.59 dl / g,
Tg is 140 ° C and TCD content is 37.0 mol%
And the iodine value was 0.1.

The results are shown in Table 1.

[0160]

[Reference Example 2] [Synthesis of Copolymer b] In Reference Example 1, ethylidene norbornene (hereinafter abbreviated as ENB) as a diene compound was adjusted to 4.0 g / liter, and ethylene was added to 30.0 liters. / Hour, 10.0 liters / hour of nitrogen, and 2.0 liters / hour of hydrogen were supplied in the same manner as in Reference Example 1 to prepare an ethylene / TCD / ENB copolymer. Then, various physical properties were determined by the above methods.

The results are shown in Table 1.

[0162]

Reference Example 3 [Synthesis of Copolymer c] 134 g of norbornene (hereinafter abbreviated as NB) was charged into a 1-liter stainless steel autoclave containing 239 ml of toluene at room temperature under a nitrogen stream and stirred for 5 minutes. I did. Subsequently, ethylene was circulated at normal pressure while stirring to create an ethylene atmosphere in the system.

Then, the internal temperature of the autoclave was maintained at 70 ° C., and ethylene was applied so that the internal pressure became 4 kg / cm ² . After stirring the autoclave for 10 minutes,
The copolymerization reaction of ethylene and NB was started by adding 5.2 ml of a toluene solution containing ethylenebis (indenyl) zirconium dichloride prepared earlier and methylalumoxane to the system. The catalyst concentration at this time was 0.10 mmol / liter of ethylenebis (indenyl) zirconium dichloride with respect to the whole system,
Methylalumoxane is 20 mmol / liter.
During the polymerization, the internal pressure was maintained at 4 kg / cm ² by continuously supplying ethylene into the system. After 20 minutes, the polymerization reaction was stopped by adding isopropyl alcohol. After depressurization, the polymer solution was taken out and brought into contact with an aqueous solution prepared by adding 5 ml of concentrated hydrochloric acid to 1 liter of water with a homomixer at a ratio of 1: 1 under vigorous stirring to transfer the catalyst residue to the aqueous phase. After leaving this contact mixture still, the aqueous phase was separated and removed, and further washed twice with distilled water to purify and separate the polymerization liquid phase.

Next, the purified and separated polymerization liquid was contacted with 3 times the amount of acetone under strong stirring to precipitate a copolymer, and then the solid part (copolymer) was collected by filtration, and acetone was sufficient. Washed. 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 process, the solid part is collected by filtration, and under nitrogen flow, 130 ° C., 350 mmH
dried for 12 hours.

Ethylene.N obtained as described above
The B copolymer has an intrinsic viscosity [η] of 0.60 dl / g, a Tg of 151 ° C., and an NB content of 47.0 mol%.
Met. Furthermore, the iodine value of the obtained copolymer is 0.
It was 2.

The results are shown in Table 1.

[0167]

[Reference Examples 4 to 7] [Synthesis of Copolymers d to g] Copolymers were prepared in the same manner as in Reference Example 1 except that the conditions were changed as shown in Table 1. d to g were prepared, and various physical properties were determined by the above methods.

The results are shown in Table 1.

[0169]

[Table 1]

[0170]

Example 1 Under a dry nitrogen atmosphere, 12.0 g of an ethylene / TCD copolymer (copolymer a of Reference Example 1) having a Tg of 140 ° C. and Tg were placed in a glass flask having a volume of 1 liter.
After charging 3.0 g of an ethylene / NB copolymer (copolymer d of Reference Example 4) having a temperature of 0 ° C., ortho-dichlorobenzene 4
40 ml was added and heated to 160 ° C. to completely dissolve it to obtain a polymer solution.

30 m of 0.45 g of Perkmill D (dicumyl peroxide; hereinafter abbreviated as DCP) manufactured by NOF CORPORATION
30 g of divinylbenzene (hereinafter abbreviated as DVB) manufactured by Wako Pure Chemical Industries, Ltd.
Each was dissolved in ml of orthodichlorobenzene.

While stirring the polymer solution at 160 ° C.
After the DCP solution and the DVB solution were added dropwise to the polymer solution over 30 minutes, the liquid temperature was maintained at 160 ° C., heating was stopped 2 hours after the completion of the addition, and the mixture was allowed to cool to room temperature. Then, the polymer solution is brought into contact with a large amount of acetone under strong stirring to precipitate a reaction product, and then only a white solid is separated by filtration and washed with a large amount of acetone to remain. Unreacted DCP and DVB were removed.
Then, the solid part was collected by filtration, and was put under nitrogen flow to
It was dried at 0 ° C. and 350 mmHg for 12 hours.

The cyclic olefin copolymer composition thus obtained has an MFR of 0.
It was 1 g / 10 minutes, the light transmittance was 87%, the Izod impact strength was 2.2 kg · cm / cm, and the heat distortion temperature was 122 ° C.

The results are shown in Table 2.

[0175]

Example 2 Example 2 was repeated except that the mixing ratio of the copolymer a and the copolymer d was changed to 70:30 by weight.
A cyclic olefin-based copolymer composition was produced in the same manner as in Example 1, and its physical properties were determined in the same manner as in Example 1.

The results are shown in Table 2. It can be seen from Table 2 that the transparency is good and the heat distortion temperature is not lowered even when the ratio of the cyclic olefin random copolymer [B] is increased.

[0177]

Comparative Examples 1 and 2 In the same manner as in Example 1, except that the blending amounts of the organic peroxide and the polyfunctional monomer were reduced or not used at all, the cyclic olefin-based copolymerization was performed. A combined composition was produced and its physical properties were determined in the same manner as in Example 1.

The results are shown in Table 2. It can be seen from Table 2 that the transparency is remarkably impaired when the degree of the interpolymer bonding reaction is considered to be small or not occurring, that is, when the MFR of the obtained copolymer composition is high.

[0179]

Example 3 In Example 1, the copolymer b of Reference Example 2 was used instead of the copolymer a as the cyclic olefin random copolymer [A], and the cyclic olefin random copolymer [B] was used. As a result, a cyclic olefin-based copolymer composition was produced in the same manner as in Example 1 except that the copolymer e of Reference Example 5 was used in place of the copolymer d and no polyfunctional monomer was used. Then, various physical properties were obtained in the same manner as in Example 1.

The results are shown in Table 2. From Table 2, even if the cyclic olefin-based random copolymers [A] and [B] are copolymers having a double bond, transparency, impact resistance,
It can be seen that a cyclic olefin-based copolymer composition having an excellent balance of heat resistance can be obtained.

[0181]

Comparative Example 3 A cyclic olefin copolymer composition was produced in the same manner as in Example 3 except that the organic peroxide was not used, and its various physical properties were obtained in the same manner as in Example 3. I asked.

The results are shown in Table 2. From Table 2, also in this comparative example, the transparency is remarkably impaired when the degree of interpolymer bonding reaction is considered to be small or not occurring, that is, when the MFR of the obtained copolymer is high. I understand.

[0183]

Example 4 A cyclic olefin-based copolymer composition was produced in the same manner as in Example 1 except that the amounts of the organic peroxide and polyfunctional compound used were changed. The various physical properties were obtained in the same manner as in.

The results are shown in Table 2.

[0185]

[Example 5] The same as Example 1 except that the copolymer c of Reference Example 3 was used as the cyclic olefin random copolymer [A] in place of the copolymer a. Then, a cyclic olefin copolymer composition was produced, and its physical properties were determined in the same manner as in Example 1.

The results are shown in Table 2. From Table 2, the cyclic olefin random copolymer [A] is ethylene / N
It can be seen that even in the case of the B copolymer, a cyclic olefin-based copolymer composition having an excellent balance of transparency, impact resistance and heat resistance can be obtained.

[0187]

[Comparative Example 4] In Example 1, except that the copolymer f (Tg: 34 ° C) of Reference Example 6 was used instead of the copolymer d as the cyclic olefin random copolymer [B].
A cyclic olefin-based copolymer composition was produced in the same manner as in Example 1, and its physical properties were determined in the same manner as in Example 1.

The results are shown in Table 2. From Table 2, the Tg of the cyclic olefin random copolymer [B] is -30.
It is found that when the temperature is out of the range of 10 ° C, the resulting cyclic olefin-based copolymer composition has low impact strength.

[0189]

COMPARATIVE EXAMPLE 5 Except that in Example 1, the mixing ratio of the copolymer a and the copolymer d was changed to 30:70 by weight.
A cyclic olefin-based copolymer composition was produced in the same manner as in Example 1, and its physical properties were determined in the same manner as in Example 1.

The results are shown in Table 2. From Table 2, the compounding amount of the cyclic olefin random copolymer [B] is 40
It can be seen that when the content is more than the amount by weight, the heat resistance of the obtained cycloolefin copolymer composition is significantly impaired.

[0191]

Comparative Example 6 In Example 1, the cyclic olefin random copolymer [B] was replaced by T instead of the copolymer d.
A cycloolefin copolymer composition was produced in the same manner as in Example 1 except that an ethylene / propylene copolymer (copolymer h) having g of −31 ° C. was used. I asked for their physical properties.

The results are shown in Table 2. From Table 2, when a copolymer containing no cyclic olefin was used in place of the cyclic olefin random copolymer [B] of the present invention, the obtained copolymer composition had a remarkable transparency. It turns out that it is damaged.

[0193]

Comparative Example 7 Various physical properties of the copolymer a alone were determined by the above methods. The results are shown in Table 2.

From Table 2, it is understood that the Izod impact strength is remarkably inferior for the copolymer a alone.

[0195]

Example 6 In Example 1, instead of the solution reaction,
A melting reaction was performed. That is, after thoroughly mixing 4 kg of the pellets of the copolymer a and 1 kg of the pellets of the copolymer d, a twin-screw extruder (BT-3 manufactured by Plastic Engineering Laboratory)
According to 0), the mixture was melt-blended at a cylinder maximum temperature of 260 ° C. and pelletized by a pelletizer.

Next, 1 kg of the pellets obtained as described above was treated as an organic peroxide with NOF Corporation.
Perhexin 25B (registered trademark) (2 g) and DVB as a polyfunctional monomer (4 g) were added at a ratio of 4 g, and after sufficiently mixing, the mixture was mixed using the above twin-screw extruder (cylinder maximum temperature: 260 ° C.) The reaction was performed in a molten state, and pellets of a cyclic olefin-based copolymer composition were obtained with a pelletizer.

Various physical properties of the obtained cyclic olefin-based copolymer composition were determined by the above methods. The results are shown in Table 2. It can be seen from Table 2 that a cycloolefin copolymer composition having an excellent balance of transparency and impact resistance can be obtained even when it is produced by a melt reaction.

The relationship between the light transmittance and the Izod impact strength in Examples and Comparative Examples other than Comparative Example 5 is shown in FIG. From FIG. 1, it can be seen that the cyclic olefin copolymer composition of the present invention has a good balance between impact resistance and transparency as compared with the conventional cyclic olefin copolymer or composition.

[0199]

[Table 2]

[0200]

[Table 3]

[Brief description of drawings]

FIG. 1 is a diagram showing a relationship between light transmittance and Izod impact strength in Comparative Examples except Examples and Comparative Example 5.

Claims (1)

[Claims] 1. [A] (i) an α-olefin having 2 or more carbon atoms, (ii) at least one cyclic olefin represented by the following formula [I] or [II], and optionally ( iii) It is obtained by copolymerizing with a diene compound, has an intrinsic viscosity [η] in decalin at 135 ° C. of 0.1 to 5.0 dl / g, and DS
Glass transition temperature (Tg) measured by C is 70 to 20
Cyclic olefin-based random copolymer at 0 ° C .: 60 to
99% by weight, [B] (i) an α-olefin having 2 or more carbon atoms, and (ii)
It is obtained by copolymerizing at least one cyclic olefin represented by the following formula [I] or [II] and (iii) a diene compound, if necessary, and has an intrinsic viscosity in decalin at 135 ° C. η] is 0.1 to 10.0 dl / g, and the glass transition temperature (Tg) measured by DSC is −.
A cyclic olefin-based random copolymer having a temperature of 30 ° C to 10 ° C: 1 to 40% by weight is reacted radically in the presence of an organic peroxide and, if necessary, a radically polymerizable polyfunctional monomer. Obtained with a load of 2.16 kg,
Melt flow rate of the composition at 260 ° C. [MF
R (1)] and the melt flow rate [MFR (2)] when the [A] component and the [B] component are blended in the same weight ratio as the composition. Cyclic olefin-based copolymer composition characterized by the relationship of formula (1); 0.001 ≤ MFR (1) / MFR (2) ≤ 0.5 formula (1) (However, in the above formula [I], 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, it is a hydrogen atom, a halogen atom or a hydrocarbon group, and R ^{15 to} R ¹⁸ may be bonded to each other to form a monocycle or a polycycle, and the monocycle or the polycycle is a double bond. R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group), (However, in the above formula [II], p and q are 0 or a positive integer, m and n are 0, 1 or 2, and R ^{1 to} R ¹⁹ are each independently a hydrogen atom or a halogen atom. , A hydrocarbon group or an alkoxy group, wherein the carbon atom to which R ⁹ or R ¹⁰ is bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are directly or have 1 carbon atom. 3 to 3 may be bonded via an alkylene group, and when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ are bonded to each other to form a monocyclic or polycyclic aromatic ring. May be formed).