KR0132729B1 - Cyclo-olefin copolymer composition - Google Patents

Abstract

The present invention does not have a polymerizable carbon-carbon double bond, and has 8 to 40% by weight of a cycloolefin elastomer component [Aα] consisting of α-olefin, a specific cycloolefin and a non-conjugated diene, and in the presence of the elastomer component [Aα]. It is composed of 92 to 60% by weight of a cycloolefin copolymer component [Bα] obtained by copolymerizing an α-olefin and a specific cycloolefin, and has a refractive index (N _D (Aα)) of the component [Aα] and a refractive index of the component [Bα]. While the difference between (N _D (Bα)) (ΔN _D = N _D (Aα) -N _D (Bα) is 0.015 or less and has the inherent superior properties of cycloolefin random copolymers, it does not impair transparency, in particular impact resistance It provides a cycloolefin copolymer composition improved.

Description

Cycloolefin copolymer composition

The present invention relates to a cycloolefin copolymer composition, and more particularly, to a cycloolefin copolymer composition having excellent impact resistance, heat resistance, and transparency and well-balanced these properties.

Applicant of the present invention is that the cycloolefin random copolymer obtained by copolymerizing cycloolefin such as ethylene and tetracyclododecene is well balanced in various properties such as heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties and stiffness. It has been found to be a synthetic resin and shows excellent performance in optical materials such as optical memory disks and optical fibers. Japanese Patent Laid-Open Nos. 60-168708, 61-98780, 61-115912, 61-115912 It is filed as 115916, Unexamined-Japanese-Patent No. 61-120816, and 62-252407.

It is known that the copolymers described in these publications exhibit excellent performance also in the field of structural materials.

These cycloolefin copolymers are particularly good in stiffness and heat resistance, but there is room for impact resistance improvement.

Therefore, improvement of impact resistance is desired, maintaining transparency inherent to a cycloolefin copolymer.

In addition, the applicant of the present invention improves the impact resistance of the composition of the cycloolefin random copolymer having a specific softening temperature (TMA) and the specific α-olefin elastic copolymer without damaging other excellent properties such as heat resistance, heat aging resistance and chemical resistance Was found and filed in Japanese Patent Application Laid-Open No. 1-163241.

In addition, the present applicant has proposed a cycloolefin polymer composition having improved impact resistance obtained by reacting a specific soft copolymer with a specific cycloolefin random copolymer in the presence of an organic peroxide without damage to Japanese Patent Laid-Open No. 2-167318.

However, the cycloolefin polymer compositions proposed in Japanese Patent Laid-Open Nos. 1-163241 and 2-167318 do not necessarily have improved impact resistance or satisfactory transparency, and there is room for improvement.

Applicant has proposed a cycloolefin random copolymer composition obtained by copolymerizing a soft polymer (rubber), a cycloolefin (eg, tetracyclododecene) and ethylene in Japanese Patent Application Laid-Open No. 2-52971.

However, these resin compositions have higher impact resistance than cycloolefin random copolymers, but require improvement in impact strength and often impair transparency.

In addition, the present applicant has proposed a cycloolefin copolymer obtained by copolymerizing a cycloolefin with an α-olefin in the presence of a hydrocarbon elastomer having a double bond polymerizable in Japanese Patent Application Laid-Open No. 4-133822.

However, the cycloolefin copolymer has good impact resistance but requires improvement in transparency.

The present inventors have obtained a cycloolefin copolymer obtained by copolymerizing an alpha -olefin having 2 or more carbon atoms such as ethylene and a cycloolefin in the presence of a specific cycloolefin elastomer component [Aα] and the elastomer component [Aα] having no polymerizable double bond. A cycloolefin composed of component [Bα] and containing a specific amount of component [Aα] in which a difference between refractive index N _D (Aα) of component [Aα] and refractive index N _D (Bα) of component [Bα] is within a specific range. The copolymer composition was found to be particularly excellent in transparency and impact resistance, thus completing the present invention.

It is an object of the present invention to provide a cycloolefin copolymer composition which is excellent in impact resistance, transparency and heat resistance and well balanced in these properties to solve the problems of the prior art as described above.

It is another object of the present invention to provide a cycloolefin copolymer composition with particularly improved impact resistance and transparency without compromising the inherent good properties of the cycloolefin random copolymer.

The cycloolefin copolymer composition according to the present invention is obtained by copolymerizing [alpha] -olefin (i) having 2 or more carbon atoms and at least one cycloolefin (ii) represented by the following formula (I) or (II), The cycloolefin unit content is 3 mol% or more, the ultimate viscosity measured in decalin at 135 ° C is 0.5 to 5.0 dl / g, the glass transition temperature (Tg) is 15 ° C or less, and polymerizable carbon-carbon double A cycloolefin elastomer component having no bond and having a refractive index (N _D (Aα)) of 1.500 to 1.650 measured at 25 ° C., -olefin (i) having 2 or more carbon atoms of [Bα], and the following formula (I) or A cycloolefin copolymer component obtained by copolymerizing one or more cycloolefins (ii) represented by (II) in the presence of the elastomer component [Aα], and the refractive index (N _D (Aa)) of the component [Aα] and the component The difference ΔN _D = N _D (Aα) −N _D (Bα) between the refractive indices ND (Bα) of [Bα] is 0.015 or less.

Wherein n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ¹ to R ¹⁸ , Ra and Rb are each independently a hydrogen atom, a halogen atom or an aliphatic, alicyclic or aromatic hydrocarbon R ¹⁵ to R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic group which may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may together form an alkylidene group.

Wherein p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R ¹ to R ¹⁹ are each independently a hydrogen atom, a halogen atom or an aliphatic, alicyclic or aromatic hydrocarbon group or an alkoxy group R ⁹ and R ¹⁰ may be bonded to a carbon atom having R ¹³ or a carbon atom having R ¹¹ bonded thereto, or may be directly bonded with an alkylene group having 1 to 3 carbon atoms, and R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded together to form a monocyclic or polycyclic aromatic ring when n and m are zero.

In the present invention, the elastomer component [Aα] is preferably a copolymer of cycloolefin represented by the formula (II), and the cycloolefin copolymer component [Bα] is preferably a copolymer of cycloolefin represented by the formula (I). .

The cycloolefin copolymer composition of the present invention also has the inherent superior properties of cycloolefin random copolymers, in particular the impact resistance is improved without compromising its transparency.

Hereinafter, the cycloolefin polymer composition of this invention is further demonstrated.

The meaning of the term polymer as used herein is not limited to homopolymers and may be a copolymer.

In addition, the term polymerization used herein is not limited to homopolymerization but may be copolymerization.

The cycloolefin copolymer composition according to the present invention comprises a cycloolefin elastomer component [Aα] and a cycloolefin copolymer component [Bα], and the cycloolefin elastomer component [Aα] is composed of two or more carbon atoms having α-olefin (i) and Obtained by copolymerizing the cycloolefin (ii) of the formula (I) or (II), the cycloolefin copolymer component [Bα] is α-olefin (i) and cycloolefin (ii) in the presence of the cycloolefin elastomer component [Aα]. ) Is obtained by copolymerization.

The α-olefin (i) having 2 or more carbon atoms used in the production of the cycloolefin elastomer component [Aα] and the cycloolefin copolymer component [Bα] may be linear or branched, and preferably has 2 to 20 carbon atoms.

Examples of α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1- Hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene.

Of these, ethylene or propylene is preferred, and ethylene is particularly preferred.

These alpha -olefins can be used individually or in combination of 2 or more.

The cycloolefin (ii) used for the production of the cycloolefin elastomer component [Aα] and the cycloolefin copolymer component [Bα] is a cycloolefin represented by the formula (I) or (II).

The cycloolefin represented by the formula (I) or (II) will be described in detail below.

In formula (I), n is 0 or 1, m is 0 or a positive integer, q is 0 or 1.

When q is 1, the ring represented by q is a 6-membered ring, when q is 0, this ring is a 5-membered ring, and in the formula (I), R ¹ to R ¹⁸ , Ra and Rb are each independently. Hydrogen atom or an aliphatic, alicyclic or aromatic hydrocarbon.

Halogen atoms are, for example, fluorine, chlorine, bromine and iodine atoms.

The hydrocarbon group is, for example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group.

Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl and octadecyl.

These alkyl groups may be substituted with halogen atoms.

Specific examples of the cycloalkyl group include cyclohexyl groups.

Specific examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.

In Formula (I), R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ , R ¹⁵ and R ¹⁷ , R ¹⁶ and R ¹⁸ , R ¹⁵ and R ¹⁸ or R ¹⁵ and R ¹⁷ are bonded together to form a monocyclic or polycyclic group. To form a monocyclic or polycyclic group so formed may have a double bond.

Examples of monocyclic or polycyclic groups are as follows.

The carbon atoms to which the numbers 1 and 2 are attached in these annular groups are those to which the substituent R ¹⁵ (R ¹⁶ ) or R ¹⁸ (R ¹⁹ ) is attached.

In formula (I), R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may together form an alkylene group.

The alkylene group generally has 2 to 20 carbon atoms, and examples of such alkylidene groups include ethylidene group, propylidene group and isopropylidene group.

In the formula (II), p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R ¹ to R ¹⁹ are each independently a hydrogen atom. Halogen atom or aliphatic, alicyclic or aromatic hydrocarbon group or alkoxy group.

In the formula (II), the halogen atom has the same meaning as in the formula (I).

Hydrocarbon groups are generally an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group or aromatic hydrocarbon group having 3 to 15 carbon atoms.

Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl and octadecyl.

These alkyl groups may be substituted with halogen atoms.

Examples of cycloalkyl groups include cyclohexyl groups.

Examples of aromatic hydrocarbon groups include aryl groups and aralkyl groups.

Specific examples include phenyl group, tolyl group, naphthyl group, benzyl group and phenylethyl group.

Specific examples of the alkoxy group include methoxy group, ethoxy group and propoxy group.

The carbon atom to which R ⁹ and R ¹⁰ are bonded may be bonded directly or by an alkylene group of 1 to 3 carbon atoms to a carbon atom to which R ¹³ is bonded or to a carbon atom to which R ¹¹ is bonded.

In the latter case, R ⁹ and R ¹³ , or R ¹⁰ and R ¹¹ together form a methylene group (-CH _2- ), an ethylene group (-CH ₂ CH _2- ) or a propylene group (-CH ₂ CH ₂ CH _2- And alkylene groups such as

In addition, when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded together to form a monocyclic or polycyclic aromatic ring.

For example, the aromatic rings formed as R ¹⁵ and R ¹² in the case of n = m = 0 are as follows.

Wherein q is the same as defined in formula (II) above.

Examples of the cycloolefin represented by the above formula (I) or (II) are as follows.

Bicyclo-2-heptene derivative (bicyclohept-2-ene derivative), tricyclo-3-decene derivative, tricyclo-3-undecene derivative, tetracyclo-3-dodecene derivative, pentacyclo-4-penta Decene derivatives, pentacyclopentadecadiene derivatives, pentacyclo-3-pentadecene derivatives, pentacyclo-4-hexadecene derivatives, pentacyclo-3-hexadecene derivatives, hexacyclo-4-heptadecene derivatives, heptacyclo-5 -Eicosene derivatives, heptacyclo-4-eicosene derivatives, heptacyclo-5-heneicosene derivatives, octacyclo-5-dococene derivatives, nonacyclo-5-pentacocene derivatives, nonacyclo-6-nuxacosene derivatives , Cyclopentadiene-acenaphthylene adduct, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene derivative, 1,4-methano-1,4,4a, 5,10,10a Examples of the hexahydroanthracene derivative and the cycloolefin represented by the formula (I) or (II) are as follows.

Bicyclo [2.2.1] hept-2-ene derivatives as follows;

Tricyclo [4.3.0.1 ^2,5 ] -3-decene derivatives as follows:

Tricyclo [4.4.0.1 ^2,5 ] -3-undecene derivatives as follows:

Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene derivatives as follows:

^Pentacyclo [6.5.1.1 ^{3,6 2,7 9,13} ] -4- ^pentadecene derivatives as follows:

Pentacyclo [7.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13 ] -3-pentadiene derivatives as follows:

Pentacyclo pentadecadiene compounds as follows:

Pentacyclo [8.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13 ] -3-hexadecene derivatives as follows:

^Pentacyclo [6.6.1.1 ^{3,6 2,7 9,14} ] -4-hexadecene derivatives as follows:

To the same penta-bicyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] -4- hexadecene derivatives:

Heptacyclo-5-eicosene derivatives as follows:

Pentacyclo [8.7.0.1 ^3,6 .1 ^10,17 .1 ^12,15 .0 ^2,7 .0 ^11,6 ] -4-eicosene derivatives as follows:

Heptacyclo-5-heneicosene derivatives as follows:

Na like to bicyclo ^{[10.9.1.1 4,7 .1 13,20 .1 15,18 .0} 2,10 .0 3,8 .0 12,21 .0 14,19] -5- penta Hill derivatives:

Octacyclo [8.8.0.1 ^2,9 .1 ^4,7 .1 ^11,18 .1 ^13,16 .0 ^3,8 .0 ^12,17 ] -5- ^docosene derivatives as follows:

^Nonacyclo [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-hexacosene derivatives as follows:

The cycloolefins of formulas (I) and (II) can be prepared by the Diels-Alder reaction of cyclopentadiene and the corresponding olefins.

In the cycloolefin elastomer component [Aα] and the cycloolefin copolymer component [Bα], the cycloolefin of the above formula (I) or (II) forms repeating units represented by the following formula (I ') or (II'). It is thought to be:

Wherein m, n, q, R ¹ to R ¹⁸ , Ra and Rb are the same as defined in formula (I),

Wherein m, n, q and R ¹ to R ¹⁹ are as defined in formula (II) above.

These cycloolefins can be used individually or in combination of 2 or more types.

The cycloolefin elastomer component [Aα] used in the present invention is a catalyst (α) formed from a soluble vanadium compound and an organoaluminum compound (A) described below in detail, or a metallocene compound of a transition metal selected from Group IV B and lanthanide of the periodic table. In the presence of an organoaluminum oxy compound and, if necessary, a catalyst (β) formed from an organoaluminum compound (B), α-olefin (i) having 2 or more carbon atoms and 1 represented by the above formula (I) or (II) The above cycloolefin (ii) can be copolymerized and manufactured.

The soluble vanadium compound which forms the catalyst (α) can be specifically represented by the following formula.

VO (OR) _a V _b or V (OR) _a X _b

Wherein R is a hydrocarbon group, a, b, c and d are 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4 and 3 ≦ The relationship of c + d ≦ 4 is satisfied.

Examples of the soluble vanadium compound are as follows.

VOCI ₃ , VO (OC ₂ H ₅ ) Cl ₂ , VO (OC ₂ H ₅ ) ₂ CI, VO (O-iso-CH ₇ ) C1 ₂ , VO (OnC ₄ H ₉ ) CI ₂ , VO (OC ₂ H ₅ ) ₃ , VOBr ₂ , VCI ₄ , VOCI ₂ , VO (OnC ₄ H ₉ ) ₃ and VOCI ₃ · 2 (OC ₈ H ₁₇ OH).

These compounds may be used alone or in combination of two or more.

The soluble vanadium compound described above can be used in the form of an electron donor adduct obtained by placing it in contact with the electron donor.

Examples of such electron donors include oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, organic or inorganic acid esters, ethers, diethers, acid amides, acid acetic acid and alkoxysilanes, and ammonia. And nitrogen-containing electron donors such as ammonium salts, amines, nitriles, pyridine and isocyanates, and more specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 3-ethylhexanol, octanol, dodecanol, Alcohols having 1 to 18 carbon atoms, such as octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol, trichloromethanol, trichloroethanol and trichlorohexanol, etc. Substituted by lower alkyl groups such as halogenated alcohols having 1 to 18 carbon atoms and lower alkyl groups such as phenol cresol, ethylphenol, crerenol, propylphenol, nonylphenol, cumylphenol and naphthol Phenols of -20 carbon atoms, ketones of 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone, acetaldehyde, propionaldehyde, octyl aldehyde, benzaldehyde and tolulu Aldehydes having 2 to 15 carbon atoms such as aldehydes and naphthaldehydes, methyl formate, methyl acetate and ethyl acetate. Vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate. Ethyl propionate, methyl butyrate, ethyl valerate, methylchloro acetate, ethyl dichloro acetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarbonate, methyl benzoate, benzyl benzoate, methyl toluate, ethyl tol 2, such as leulate, amyl toluate, ethyl ethyl benzoate, methyl aniseate, ethyl aniseate, ethoxy ethyl benzate, γ-butyrolactone, δ-valerolactone, cumin, phthalide and ethyl carbonate Organic acid esters of -18 hydrocarbons, acid halides of 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, and aniseic acid chloride, methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, Ethers of 2 to 20 carbon atoms such as tetrahydro hulan, anisole and diphenyl ether; Acid anhydrides such as water, phthalic anhydride and benzoic anhydride, alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane, N, N-dimethylamide acetate, N, N-diethylamide benzoate and N toluic acid Acid amides such as, N-dimethylamide, amines such as trimethylamine, triethylamine, tributylamine, tribenzylamine and tetramethylethyldiamine, nitriles such as acetonitrile and benzonitrile trinitrile, pyridine and methyl Pyridine and pyridine such as ethylpyridine and dimethyl pyridine.

In the preparation of electron donor adducts of soluble vanadium compounds, the electron donors exemplified above can be used alone or in combination.

Examples of the organoaluminum compound (A) usable with the soluble vanadium compound for the catalyst (α) include compounds containing one or more Al-C bonds in the molecule.

Examples of the organoaluminum compound include compounds represented by the following formulas (a) and (b).

(a) R _m ² Al (OR ² ) n HpXq.

Wherein R ¹ and R ² are usually 1 to 15, preferably 1 to 4 carbon atoms hydrocarbon groups, they may be the same or different from each other, X is a halogen atom, m, n, p and q are 0 ≦ It is a number which satisfy | fills the conditions of m <= 3, 0 <= n <= 3, 0 <= p <= 3, 0 <= q <= 3, and m + n + q = 3.

(b) M ² AlR ₄ ^{1. In the} above formula M1 is Li, Na or k, R1 is as defined above.

For example, specific examples of the organoaluminum compound represented by the formula (a):

(1) R _m ¹ Al (OR ² ) _3-m . Wherein R ¹ and R ² have the same meaning as defined in the formula (VII) above, X is halogen and m is 1.5 ≦ m ≦ 3.

(2) R _m ¹ Al _3-m . In which R ¹ has the same meaning as defined in formula (VII) above, m is a number of 0 ≦ m ≦ 3.

(3) R _m ¹ Al _3-m . Wherein R ¹ has the same meaning as defined in formula VII above, X is halogen and m is a number of 2 ≦ m ≦ 3.

(4) R _m ¹ Al (OR ² ) _n X _q. Wherein R ¹ and R ² have the same meanings as defined in Formula VII, X is halogen, m, n and q are 0 ≦ m ≦ 3, 0 ≦ n ≦ 3, 0 ≦ q ≦ 3 and m + n A number satisfying the condition of + q = 3.

More specifically, as the organoaluminum compound (A) of the formulas VIII to VX, there are the following compounds.

As an organoaluminum compound of said Formula (I); Trialkyl aluminum such as triethyl aluminum and tributyl aluminum, trialkenyl aluminum such as triisopropenyl aluminum, dialkyl aluminum alkoxide such as diethyl aluminum ethoxide and dibutyl aluminum butoxide, and ethyl aluminum sesqui Toxoxides, butylaluminum sesquibutoxide and average compositions include, for example, some alkoxylated alkylaluminums represented by the formula R2.51 Al (OR ² ) 0.5.

As an organoaluminum compound of said Formula (2); Dialkyl aluminum halides such as diethyl aluminum chloride, dibutyl aluminum chloride and diethyl aluminum bromide, alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; And some halogenated alkyl aluminums such as ethyl aluminum dichloride, propyl aluminum dichloride, and butyl aluminum dichloride.

As an organoaluminum compound of said Formula (3); Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride, and some hydrogenated alkylaluminum aluminums such as ethylaluminum dihydride and propylaluminum dihydride.

As an organoaluminum compound of said Formula (4); And some alkoxylated and halogenated alkyl aluminum such as ethyl aluminum ethoxychloride, butyl aluminum butoxy chloride and ethyl aluminum ethoxy bromide.

As an example of a compound similar to that represented by the formula (a), an organoaluminum compound in which two or more aluminums are bonded through an oxygen atom or a nitrogen atom may be used.

Examples of such compounds are as follows.

Further, the compounds belonging to the formula (b) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

Of the organoaluminum compounds exemplified above, it is preferable to use alkylaluminum halides, alkylaluminum dihalides and mixtures thereof.

Next, a catalyst (β) formed of a metallocene compound of a transition metal selected from periodic table Group IV B or lanthanoid used for copolymerization, an organoaluminumoxy compound and an organoaluminum compound (B) to be used if necessary will be described.

Examples of the metallocene compound of the transition metal selected from group IV B or lanthanoid of the periodic table include compounds represented by the following formula (VII).

ML _X ............. (VII).

In formula (VII), M is a transition metal selected from group IV B of the periodic table, specific examples of M are zirconium, titanium, hafnium, neodymium, samarium and ytterbium, L is a ligand that coordinates with the transition metal, and The ligand (L) has a cyclo pandienyl skeleton, and the ligand (L) without a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, SO ₃ R group (R is for example a hydrocarbon group of 1 to 8 carbon atoms which may be substituted by halogen) or a hydrogen atom, and X is a transition metal atom.

The ligand (L) having a cyclopentadienyl skeleton is, for example, a cyclopentadienyl group, methylcyclopentadienyl group, trimethylcyclopentanienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl group, ethylcyclopenta Dienyl group, methylethylcyclopentadienyl, propylcyclopentadienyl group, methylpropylcyclopentadienyl, butylcyclopentadienyl group, methylbutylcyclopentadienyl group, hexylcyclopentadienyl group alkyl-substituted cyclopentadienyl group, 4, 5, 6, 7-tetrahydroindenyl group, and furoenyl group.

These ligands may be substituted with halogen atoms or trialkylsilyl groups.

Of the ligands exemplified above that are coordinated with the transition metal, alkylsubstituted cyclopentadienyl groups are particularly preferred.

When the compound of the formula (VII) contains two or more cyclopentadienyl groups, the 2 cyclopentadienyl groups are substituted with alkylene groups such as ethylene or propylene groups, alkylidene groups such as isopropylidene group, and diphenylmethyl group. It may be bonded via a substituted silylene group such as an alkylene group, a silylene group or a dimethylsilylene group, a diphenylsilylene group or a methylphenylsilylene group.

As ligands (L) having no cyclopentadienyl skeleton, hydrocarbon groups having 1 to 12 carbon atoms, specifically alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group, cycloalkyl groups such as cyclohexyl group, and phenyl group And aralkyl groups such as aryl groups such as tolyl groups, neofill groups, alkoxy groups such as methoxy groups, ethoxy groups and butoxy groups, aryloxy groups such as phenoxy groups, halogen atoms such as fluorine, chlorine, bromine and iodine, Ligands of formula SO ₃ R such as a P-toluenesulfonate group, a methanesulfonate group, and a trifluoromethanesulfonate group.

When the transition metal atom (M) in Formula (VII) is 4, for example, the transition metal compound of Formula (VII) may be represented by Formula (VII ') more specifically.

상기식에서, M은 지르코늄, 티타늄, 하프늄, 네오디뮴, 사마륨 또는 이터븀이고, R1은 시클로펜타디에닐 골격을 갖는 기이고, R², R³및 R⁴는 각각 시클로펜타디에닐 골격을 갖는 기, 알킬기, 시클로알킬기, 아릴기, 아랄킬기, 알콕실기, 아릴옥시기, 할로겐원자,트리알킬실일기, SO₃R기 또는 수소원자이고, a는 1이상의 정수이고, a+b+c+d=4 본 발명에서는 R², R³및 R⁴의 적어도 하나가 시클로펜타디에닐 골격을 갖는기, 예를들어 R¹과 R²가 시클로펜타디에닐 골격인 상술한 식 (VII')을 갖는 천이금속 화합물이 바람직하게 사용된다.

Wherein M is zirconium, titanium, hafnium, neodymium, samarium or ytterbium, R 1 is a group having a cyclopentadienyl skeleton, R ² , R ³ and R ⁴ are each a group having a cyclopentadienyl skeleton, Alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxyl group, aryloxy group, halogen atom, trialkylsilyl group, SO ₃ R group or hydrogen atom, a is an integer of 1 or more, a + b + c + d = 4 In the present invention, at least one of R ² , R ³ and R ⁴ has a group having a cyclopentadienyl skeleton, for example, a transition having the above formula (VII ′) wherein R ¹ and R ² are cyclopentadienyl skeletons Metal compounds are preferably used.

Groups having a cyclopentadienyl skeleton include alkylene groups such as ethylene or propylene, alkylidene groups such as isopropylidene, substituted alkylene groups such as diphenylmethylene, silylene groups or dimethylsilylene, diphenylsilylene or methylphenylsilyl It may be bonded through a substituted silylene group such as lene.

Examples of metallocene compounds of transition metals in which M is zirconium are as follows: bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (indenyl) zirconium bis (P-toluenesulfonate ), Bis (4, 5, 6, 7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide , Ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methyl zirconium monochloride, ethylenebis (indenyl) zirconiumbis (methanesulfonate), ethylenebis (indenyl Zirconium bis (P-toluenesulfonate), ethylene bis (indenyl) zirconium bis (trifluoromethanesulfonate), ethylene bis (4, 5, 6, 7-tetrahydroindenyl) zirconium dichloric , Isopropylidene (cyclopentadienyl-

Fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienylmethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienylfluorenyl) dimethylzirconium, dimethylsilylenebis (cyclopentadienyl Zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium difluoride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) -zirconium di Chloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconiumbis (trifluoromethanesulfonate), dimethylsilylenebis (4, 5, 6, 7-tetrahydroindenyl Zirconium dichloride, dimethylsilylene bis (cyclopentadienyl fluorenyl) zirconium dichloride, diphenylsilylene bis (indenyl) zirco Nium dichloride, methylphenylsilylenebis (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) benzyl zirconium monochloride, bis ( Cyclopentadienyl) zirconium monochloride monohalide. Bis (cyclopentadienyl) methyl zirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadiene Nil) zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonate), bis (cyclopentadienyl) zirconium bis (P-toluenesulfonate) Bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxychloride, bis (dimethylcyclopentadienyl) zirconium bis (tri Fluoromethanesulfonate), bis (diethylcyclopentadienyl) dimethylzirconium, bis (ethylcyclopentadienyl) zirconium dichloride, bis (meth Ethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methyl Butylcyclopentadienyl) zirconium, bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexyl) Clopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride, in the transition metal compounds exemplified above, the di-substituted cyclopentadienyl rings are 1,2- and 1,3-substituted. And tri-substituted cyclopentadienyl rings are 1, 2, 3-and 1, 2, 4 -substituted compounds and the like.

Moreover, alkyl groups, such as propyl or butyl, are n-, i-, sec-, tert- isomers, etc., for example.

In the present invention, other transition metal compounds in which the zirconium metal in the compounds exemplified above are substituted with titanium metal, hafnium metal, neodymium, samarium metal or ytterbium metal may also be used.

The organoaluminumoxy compound used to form the catalyst (β) together with the metallocene compound of the transition metals exemplified above from the Group IV B or lanthanoid series of the periodic table may be a known aluminoxane or benzene insoluble organoaluminum oxy. It may be a compound.

Known aluminoxanes can be specifically represented by the following formula.

In the above formula, R is a hydrocarbon group such as methyl group, ethyl group, propyl group or butyl group, preferably methyl group or ethyl group, particularly preferably methyl group, and m is an integer of 2 or more, preferably an integer of 5 to 40.

In the above formula, two or more R's may be different from each other, that is, the aluminoxane may include mixed alkyloxyaluminum units in which two or more (OAl (R)) s are different from each other.

Known aluminoxanes can be prepared, for example, by one of the following methods and are generally obtained in solution in aromatic hydrocarbon media.

(1) Addition of organoaluminum compounds such as trialkylaluminum to a suspension of containing compounds formed in an aromatic hydrocarbon medium or crystal water containing salts such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate or cerium chloride hydrate Reacting with each other to obtain aluminoxane in solution in an aromatic hydrocarbon medium, and (2) water, ice or steam to an organoaluminum compound such as trialkyl aluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) organoaluminum compounds such as trialkylaluminum in a solvent such as decane, benzene or toluene; and organic oxides such as dimethyltin oxide and dibutyltinoxide. How to react with.

Of these methods, method (1) is preferably used.

Specific examples of the organoaluminum compound that can be used to prepare the aluminoxane solution are as follows.

Trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, Such as trialkylaluminum such as trioctyl aluminum and tridecyl aluminum, tricyclo alkylaluminum such as tricyclonuclear aluminum and tricyclooctyl aluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride Dialkyl aluminum hydrides, such as dialkyl aluminum halide, diethyl aluminum hydride, and diisobutyl aluminum hydride, dialkyl aluminum alkoxides, such as dimethyl aluminum methoxide and diethyl aluminum ethoxide, diethyl aluminum phenoxide, etc. Of dialkylalu Titanium aryl oxide.

Of these, trialkylaluminum is particularly preferred.

Moreover, what can be used as an organoaluminum compound is isoprenyl aluminum represented by a following formula.

(iC ₄ H ₉ ) _x AI _y (C ₅ H ₁₀ ) _z wherein x, y and z are positive integers and z ≧ 2x.

The organoaluminum compounds exemplified above may be used alone or in combination.

The benzene-insoluble organoaluminumoxy compound can be obtained by contacting an aluminoxane solution with water or an active hydrogen-containing compound or by contacting the organoaluminum compound described above with water.

When analyzed by an infrared spectrometer (IR), the ratio (D ₁₂₆₀ / D ₁₂₂₀ ) of the absorbance at about ₁₂₆₀ cm ^-1 (D ₁₂₆₀ ) at about ₁₂₂₀ cm ^{-1 '} (D ₁₂₆₀ / D ₁₂₂₀ ) is preferably 0.09 or less, More preferably, a benzene insoluble organoaluminum oxy compound of 0.08 or less, particularly preferably 0.04 to 0.07, is preferably used.

The benzene-insoluble organoaluminumoxy compound as described above is assumed to have an alkyloxyaluminum unit represented by the following formula.

Wherein R ³ is a hydrocarbon group of 1-12 carbon atoms.

Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, cyclohexyl group and cyclooctyl group There is this.

Of these, the methyl and ethyl groups are good, especially the methyl group.

In addition to the alkyloxy aluminum unit represented by the above formula, the benzene insoluble organoaluminum oxy compound contains an oxyaluminum unit represented by the following formula.

Wherein R ⁴ represents a hydrocarbon group of 1-12 carbon atoms, a hydrocarbon group of 1-12 carbon atoms, an alkoxy group of 1-12 carbon atoms, an aryloxy group of 6-20 carbon atoms, a hydroxyl group, a halogen or a hydrogen atom And is different from the group R ³ of the above-described formula.

In the case where the organoaluminum oxy compound contains an oxyaluminum unit, the organoaluminum oxy compound contains at least 30 mol%, preferably at least 50 mol%, more preferably at least 70 mol% of an alkyloxyaluminum unit.

The term benzene-insoluble organoaluminum oxycompound means that the compound is insoluble or slightly soluble in benzene, and the amount of Al component dissolved in benzene at 60 ° C. is generally 10% or less, preferably 5% or less, particularly preferably in terms of Al atoms. Is less than 2%.

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.

As an organoaluminum compound (B) arbitrarily used for producing a catalyst ((beta)), the organoaluminum compound represented by following formula (VIII) is mentioned, for example.

R _n ⁵ AlX _3-n .... (VIII) wherein R ⁵ is a hydrocarbon group of 1-12 carbon atoms, X is a halogen atom or a hydrogen atom, n is 1-3, in the formula (VIII) , R ⁵ is an alkyl group, a cycloalkyl group, or an aryl group, specifically a methyl group, ethyl group, n-propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, It is a hydrocarbon group of 1-12 carbon atoms, such as a phenyl group and a tolyl group.

As organoaluminum compound (B), there are compounds as specifically mentioned later.

Trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, tri-2-ethylhexyl aluminum, alkenyl aluminum such as isoprenyl aluminum, dimethyl aluminum chloride, Dialkyl aluminum halides such as diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, dimethyl aluminum bromide, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, and butyl aluminum ses Alkyl aluminum sesquihalides, such as quichloride and ethyl aluminum sesquibromide, Alkyl aluminum dihalide, such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, and ethyl aluminum dibromide , Diethyl aluminum hydride and diisobutyl aluminum hydride, such as beads of an alkyl aluminum hydride.

As the organoaluminum compound (B), the compound represented by the following formula (IX) can also be used.

R _n ⁵ Al Y _3-n ...... (IX) In the above formula, R ⁵ is as defined above and Y is -OR ⁶ group, -SiR ₃ ⁷ group, -OA 1 R ₂ ⁸ group,- NR ₂ ⁹ group, —SiR ₃ ¹⁰ group or —N (R ¹¹ ) AlR ₂ ¹² , n is 1-2R ⁶ , R ⁷ , R ⁸ and R ¹² is methyl group, ethyl group, isopropyl group, isobutyl group, A cyclohexyl group, a phenyl group, a trimethylsilyl group and the like, R ⁹ is a hydrogen atom, a methyl group, an ethyl group, isopropyl group, a phenyl group, a trimethylsilyl group and the like, and R ¹⁰ and R ¹¹ are a methyl group and an ethyl group.

The organoaluminum compounds of the formula (IX) are specifically compounds to be described later.

(i) A compound of the formula R ⁵ _n Al (OR ⁶ ) _3-n such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, or the like.

(ii) Et ₂ AI (OSiMe ₃ ), (iso-Bu) ₂ AI (OSiMe ₃ ), (iso-Bu) ₂ AI (OSiEt ₃ ), etc. R ⁵ _n Al (OSiR ⁷ ₃ ) _3- compound of _n

(iii) a compound of the formula R ⁵ _n Al (OAIR ⁸ ₂ ) _3-n , such as Et ₂ AIOAIEt ₂ , (iso-Bu) ₂ AIOAI (iso-Bu) ₂ , and the like.

(iv) Me ₂ AINEt ₂ , Et ₂ AINHMe, Me ₂ AINHEt, Et ₂ AIN (SiMe ₃ ) ₂ , (iso-Bu) ₂ AIN (SiMe ₃ ) ₂ , etc.R ⁵ _n A l (NR ⁹ ₂ ) Compound of _3-n

(v) (iso-Bu) _{2 A} compound of the formula R ⁵ _n A l (SiR ¹⁰ ₃ ) _3-n such as AISiMe ₃

Among the organoaluminum compounds represented by the formulas (VIII) and (IV), R ⁵ ₃ Al, R ⁵ _n A l (OR ⁶ ) _3-n and R ⁵ _n A l (OAIR ⁸ ₂ ) _3-n are preferable. In particular, a compound in which R ⁵ is an isoalkyl group and n is 2 is preferable.

These organoaluminum compounds may be used alone or in combination.

In the cycloolefin copolymer composition of the present invention, the cyclool peffin elastomer component [Aα] and the cycloolefin copolymer component [Bα] are considered to be highly compatible with each other.

First, the cycloolefin elastomer component [Aα] having no polymerizable carbon-carbon double bond used in the present invention will be described below.

[Cycloolefin Elastomer Component [Aα]

The cycloolefin elastomer component [Aα] used in the present invention is an elastomer which does not have a polymerizable carbon-carbon double bond, and specifically, α-olefin (i) having two or more carbon atoms, and the formula (I) or (II) Copolymer of cycloolefin (ii).

Examples of the α-olefin (i) are the above-described α-olefins having 2 to 20 carbon atoms, and these may be used alone or in combination, and ethylene or propylene of them is preferable.

Those which can be used as the cycloolefin (ii) are the cycloolefins represented by the formulas (I) and / or (II) described above, which can be used alone or in combination.

For example, the cycloolefin elastomer component [A] having no polymerizable carbon-carbon double bond is as follows:

Ethylene / norbornene copolymer, ethylene / 5-methyl-2-norbornene copolymer, ethylene / 5-ethyl-2-norbornene copolymer, ethylene / 5-propyl-2-norbornene copolymer, Ethylene / 5-butyl-2-norbornene copolymer, ethylene / 5-pentyl-2-norbornene copolymer, ethylene / 5-hexyl-2-norbornene copolymer, ethylene / 5-heptyl-2- Norbornene copolymer, ethylene / 5-octyl-2-norbornene copolymer, ethylene / 5-nonyl-2-norbornene copolymer, ethylene / 5-decyl-2-norbornene copolymer, ethylene / 5-undecyl-2-norbornene copolymer, ethylene / 5-dodecyl-2-norbornene copolymer. Ethylene / 5-phenyl-2-norbornene copolymer, ethylene / 1,4-methano-1,4,4a, 9a-tetrahydrofluorene copolymer, ethylene / tetracyclododecene copolymer, ethylene / propylene / Norbornene copolymer, ethylene / propylene / 5-ethylidene-2-norbornene copolymer, ethylene / propylene / 5-methyl-2-norbornene copolymer, ethylene / propylene / 5-ethyl-2- Nomorene copolymer, ethylene / propylene / 5-propyl-2-norbornene copolymer, ethylene / propylene / 5-butyl-2-norbornene copolymer, ethylene / propylene / 5-pentyl-2-norborne Copolymer, ethylene / propylene / 5-heptyl-2-norbornene copolymer, ethylene / propylene / 5-heptyl-2-norbornene copolymer, ethylene / propylene / 5-octyl-2-norbornene air Copolymer, ethylene / propylene / 5-nonyl-2-norbornene copolymer, ethylene / propylene / 5-decyl-2-norbornene copolymer, ethylene / propylene / 5-undecyl-2-norbornene copolymer Ethylene / propylene / 5-degree Decyl-2-norbornene copolymer, ethylene / propylene / 5-phenyl-2-norbornene copolymer, ethylene / propylene / tetracyclododecene copolymer, ethylene / 1-butene / norbornene copolymer, ethylene / 1-butene / 5-ethylidene-2-norbornene copolymer, ethylene / 1-butene / methyl-2-norbornene copolymer, ethylene / 1-butene / 5-ethyl-2-norbornene air Copolymer, ethylene / 1-butene / 5-propyl-2-norbornene copolymer, ethylene / 1-butene / 5-butyl-2-norbornene copolymer, ethylene / 1-butene / 5-pentyl-2- Norbornene copolymer, ethylene / 1-butene / 5-hexyl-2-norbornene copolymer, ethylene / 1-butene / 5-heptyl-2-norbornene copolymer, ethylene / 1-butene / 5- Octyl-2-norbornene copolymer, ethylene / 1-butene / 5-nonyl-2-norbornene copolymer, ethylene / 1-butene / 5-decyl-2-norbornene copolymer, ethylene / 1- Butene / 5-undecyl-2-norbornene copolymer, ethylene / 1-butene / 5-dodecyl-2-

Norbornene copolymer, ethylene / 1-butene / 5-phenyl-2-norbornene copolymer, ethylene / 1-butene / tetracyclododecene copolymer, ethylene / 1-hexene / norbornene copolymer, ethylene / 1-hexene / 5-methyl-2-polymer, ethylene / 1-hexene / 5-ethyl-2-norbornene copolymer. Ethylene / 1-hexene / 5-propyl-2-norbornene copolymer, ethylene / 1-hexene / 5-butyl-2-norbornene copolymer, ethylene / 1-hexene / 5-pentyl-2-nobor Nene copolymer, ethylene / 1-hexene / 5-hexyl-2-norbornene copolymer, ethylene / 1-hexene / 5-heptyl-2-norbornene copolymer, ethylene / 1-hexene / 5-octyl- 2-norbornene copolymer, ethylene / 1-hexene / 5-nonyl-2-norbornene copolymer, ethylene / 1-hexene / 5-decyl-2-norbornene copolymer, ethylene / 1-hexene / 5-undecyl-2-norbornene copolymer, ethylene / 1-hexene / 5-dodecyl-2-norbornene copolymer, ethylene / 1-hexene / 5-phenyl-2-norbornene copolymer, Ethylene / 1-hexene / tetracyclododecene copolymer, ethylene / 1-octene / norbornene copolymer, ethylene / 1-octene / 5-methyl-2-norbornene copolymer, ethylene / 1-octene / 5 -Ethyl-2-norbornene copolymer, ethylene / 1-octene / 5-propyl-2-norbornene copolymer, ethylene / 1-octene / 5-butyl-2-norbornene copolymer, ethylene / 1 Octene / 5-pen -2-norbornene copolymer, ethylene / 1-octene / 5-hexyl-2-norbornene copolymer, ethylene / 1-octene / 5-heptyl-2-norbornene copolymer, ethylene / 1-octene / 5-octyl-2-norbornene copolymer, ethylene / 1-octene / 5-nonyl-2-norbornene copolymer, ethylene / 1-octene / 5-decyl-2-norbornene copolymer, ethylene / 1-octene / 5-undecyl-2-norbornene copolymer, ethylene / 1-octene / 5-dodecyl-2-norbornene copolymer. Ethylene / 1-Occene / 5-phenyl-2-norbornene copolymer, Ethylene / 1-octene / tetracyclododecene copolymer, Ethylene / 1-decene / norbornene copolymer, Ethylene / 1-decene / 5 -Methyl-2-norbornene copolymer, ethylene / 1-decene / 5-ethyl-2-norbornene copolymer, ethylene / 1-decene / 5-propyl-2-norbornene copolymer, ethylene / 1 -Decene / 5-butyl-2-norbornene copolymer, ethylene / 1-decene / 5-pentyl-2-norbornene copolymer, ethylene / 1-decene / 5-hexyl-2-norbornene copolymer , Ethylene / 1-decene / 5-heptyl-2-norbornene copolymer, ethylene / 1-decene / 5-nonyl-2-norbornene copolymer, ethylene / 1-decene / 5-decyl-2-no Bornen copolymers, ethylene / 1-decene / 5-undecyl-2-norbornene copolymers, ethylene / 1-decene / 5-dodecene-2-norbornene copolymers, ethylene / 1-decene / 5 Cycloolefin elastomer properties measured in -phenyl-2-norbornene copolymer, ethylene / 1-decene / 5-tetracyclododecene copolymer, and decalin at 135 ° C Intrinsic viscosity [Aα] [η] is the 0.5~5.0dl / g range, preferably 0.7~4.0dl / g range.

In the cycloolefin elastomer component [Aα], it is preferable to contain 3 mol% or more, preferably 5 mol% or more of the cycloolefin unit.

The glass transition temperature (Tg) of the cycloolefin elastomer component [Aα] is usually lower than 15 ° C, preferably lower than 12 ° C.

The cycloolefin elastomer component [Aα] refractive index (N _D (Aα)) measured at 25 ° C. is usually in the range of 1.500 to 1.650, preferably 1.510 to 1.600.

Next, the cycloolefin copolymer component [Bα] will be described below.

[Cycloolefin Copolymer Component [Ba]]

The cycloolefin copolymer component [Bα] used in the present invention is composed of at least two carbon atoms of α-olefin (i) and cycloolefin (in the presence of the cycloolefin elastomer component [Aα] which does not actually have a polymerizable double bond) It can be obtained by copolymerizing ii).

Examples of the α-olefins (i) having 2 or more carbon atoms include the α-olefins having 2 to 20 carbon atoms, and these may be used alone or in combination of two or more thereof.

Of these, ethylene or propylene is preferred, and more preferred is ethylene.

The cycloolefin (ii) which can be used is especially cycloolefins of said Formula (I) and / or (II), These can be used individually or in combination of 2 or more types.

The cycloolefin copolymer component [Bα] used in the present invention is composed of α-olefin (i) having 2 or more carbon atoms in the presence of the cycloolefin elastomer component [Aα] which does not have a polymerizable double bond and the above formula ( It is an addition type polymer obtained by superposing | polymerizing the cycloolefin (ii) of I) or (II).

In addition to the α-olefin (i) having two or more carbon atoms and the cycloolefin (ii), cycloolefins other than the cycloolefin of formula (I) or (II) do not impair the properties of the copolymer component [Bα]. Under the conditions, it may additionally polymerize in the cycloolefin copolymer component [Bα].

Term Used herein Another cycloolefin-based term is a broad concept encompassing the above unsaturated polycyclic hydrocarbon compounds.

For example, the same compound as that which can be used for the synthesis of the cycloolefin copolymer component [Bα] can be used.

[Cycloolefin copolymer composition]

The cycloolefin copolymer composition according to the present invention comprises the cycloolefin elastomer component [Aα] and the cycloolefin copolymer component [Bα], and the cycloolefin elastomer component [Aα] is preferably 8 to 40% by weight. It is contained in the said composition in the quantity of -35 weight%.

The cycloolefin elastomer component in the cycloolefin copolymer compositions of the present invention [Aα] refractive index difference between the (N _D (Aα)) and the cycloolefin copolymer component refractive index of _{[Bα] (N D (Bα} )) (△ N of _D ) In other words, IN _D (Aα) -N _D (Bα) is 0.015 or less.

It is preferable that the said cycloolefin elastomer component [Aα] is a copolymer of the cycloolefin shown by Formula (II), and it is preferable that the said cycloolefin copolymer component [Bα] is a cycloolefin copolymer of Formula (I).

In the present invention, the refractive indexes of the cycloolefin elastomer component [Aα] and the cycloolefin copolymer component [Bα] were measured using an Abbe refractometer (D-line, 589 nm) at a temperature of 25 ° C.

The cycloolefin copolymer composition of the present invention is characterized in that α-olefin (i) having two or more carbon atoms in the presence of the cycloolefin elastomer component [Aα] and the cycloolefin elastomer component [Aα] that does not actually have a polymerizable CC double bond To a cycloolefin copolymer component [Bα] obtained by copolymerizing cycloolefin (ii), in which the phase of the cycloolefin elastomer component [Aα] is formed of the α-olefin (i) and the cycloolefin (ii). It is finely dispersed in the phase of the cycloolefin copolymer component [Bα].

The cycloolefin copolymer composition of the present invention, in transparency and impact resistance, α-olefin (i) having two or more carbon atoms in the absence of the cycloolefin elastomer component [Aα] and the cycloolefin elastomer component [Aα] It is superior to the cycloolefin copolymer composition obtained by simply mixing the cycloolefin random copolymer component corresponding to the component [Bα] obtained by copolymerizing the cycloolefin (ii).

The difference between in the cycloolefin copolymer compositions of the present invention, the cycloolefin elastomer component refractive index of _{[Aα] (N D (Aα} )) and the refractive index (N _D (Bα)) of the cycloolefin copolymer component [Bα] ( ΔN _D , ie, N _D (Aα) —N _D (Bα) is 0.015 or less, preferably 0.12 or less, and more preferably 0.010 or less, as described above.

Wherein the cycloolefin copolymer component [Bα] is the component in the cycloolefin copolymer composition prepared by copolymerizing α-olefin (i) and the cycloolefin (ii) in the presence of the cycloolefin elastomer component [Aα]. It means other components other than Aα, but it is difficult to measure only the refractive index N _D (Bα) because the component [Bα] and component [Aα] have high compatibility with each other.

Accordingly, the refractive index (N _D (Bα)) of component [Bα] is the α-olefin (i under the same conditions as those for producing component [Bα] except that the cycloolefin elastomer component [Aα] is not present. ) And the value of the refractive index (N _D ) measured in the cycloolefin random copolymer prepared from the cycloolefin (ii).

In the preparation of the cycloolefin elastomer component [Aα] and the cycloolefin copolymer component [Bα], the following transition metal catalysts can be generally used.

a catalyst formed from (a) a soluble vanadium compound and an organoaluminum compound, or (beta) a metallocene compound of a transition metal selected from group IV B and lanthanoid series of the periodic table, an organoaluminum oxy compound and, if necessary, an organoaluminum compound Details of the catalysts (α) and (β) have been described above in the preparation of the cycloolefin elastomer component [Aα].

Copolymerization of the at least two carbon atom α-olefins (i) and the cycloolefin (ii) using the catalyst (α) or (β) described above in the presence of a cycloolefin elastomer component [Aα] is usually carried out in a liquid phase, Preferably, it is performed in a hydrocarbon solvent.

As the hydrocarbon solvent, those exemplified above can be used.

Moreover, the said liquid alpha-olefin or liquid cycloolefin itself can be used as a solvent.

Examples of preferred solvents used for the copolymerization reaction in the presence of the component [Aα] include mixed solvents such as cyclohexane, cyclohexane-heptane, cyclohexane-pentane, toluene-hexane, toluene-heptane and toluene-pentane. have.

The copolymerization can be carried out in a batch or continuous manner, but is preferably carried out continuously.

The catalyst concentration used is as follows.

In case of catalyst (α): A soluble vanadium compound is supplied to the polymerization system in an amount of usually 0.01 to 5 mmol, preferably 0.05 to 3 mmol per 1 liter of the polymerization solution, and then the organoaluminum compound is added to the aluminum atom to vanadium in the polymerization system. The ratio (Al / V) of the atoms is supplied to the polymerization system in an amount of 2 or more, preferably in the range of 2 to 50, more preferably in the range of 3 to 20.

In the continuous copolymerization, the soluble vanadium compound is supplied to the reaction system at a concentration of 10 times or more, preferably 1 to 7 times, more preferably 1 to 5 times the concentration of the soluble vanadium compound contained in the polymerization system.

Usually, the soluble vanadium compound and the organoaluminum compound are diluted with the liquid monomer and / or the hydrocarbon solvent and then supplied to the polymerization reactor.

In this case, it is preferable to dilute the soluble vanadium compound to the above concentration, while diluting the organoaluminum compound to a concentration of 50 times or less, and then supplying the polymerization system.

In the case of the catalyst (β): a metallocene compound is usually used in an amount of 0.00005 to 1.0 mmol, preferably 0.0001 to 0.3 mmol, per liter of the polymerization liquid; The organoaluminum oxy compound is used in an amount such that the aluminum atom contained therein is usually in the range of 1 to 10,000 mol, preferably 10 to 5000 mol, per mol of the transition metal atom in the metallocene compound.

The polymerization reaction in the presence of a catalyst (α) or (β) has a temperature of usually -50 to 200 ° C, preferably -30 to 150 ° C, more preferably -20 to 100 ° C, and a pressure of 0 to 50 kg. / cm2, preferably 0 to 20 kg / cm ² .

The reaction time (average residence time during continuous copolymerization) is changed depending on various conditions such as the type of monomer, catalyst concentration, polymerization temperature, etc., but is usually in the range of 5 minutes to 5 hours, preferably 10 minutes to 3 hours.

At the time of the copolymerization reaction in the presence of the component [Aα], the molar ratio (i) / (ii) is 10/90 to 90/10 of the α-olefin (i) having two or more carbon atoms and the cycloolefin (ii). It is preferably supplied to the polymerization system in an amount in the range of 10/90 to 50/50.

In the copolymerization, a chain transfer agent such as hydrogen may be used for molecular weight control.

Through the above method, in the presence of the cycloolefin elastomer component [Aα] and the cycloolefin elastomer component [Aα], α-olefin (i) having 2 or more carbon atoms and the cycloolefin of formula (I) or (II) The solution containing the said cycloolefin copolymer composition which becomes the said cycloolefin copolymer component [B (alpha)] obtained by copolymerizing (ii) is obtained.

In this solution, the cycloolefin copolymer composition can be obtained by treating the solution by a conventional method.

More specifically, in order to prepare the cycloolefin copolymer composition of the present invention, the above-mentioned cycloolefin elastomer component [Aα] prepared in the form of an elastomer pellet or an elastomer bale is dissolved in a hydrocarbon solvent to have 2 or more carbon atoms. It is possible to obtain a solution in which α-olefin (i) and the cycloolefin (ii) are copolymerized.

In addition, first, the cycloolefin elastomer [Aα] is prepared, and then copolymerization of two or more carbon atoms of α-olefin (i) and the cycloolefin (ii) by a series of two-step polymerization treatment in the product polymerization component [Aα] It is also possible.

The cycloolefin copolymer composition of the present invention can be used alone or in combination with other resins, especially transparent resins, as long as the excellent properties of the composition, especially transparency and impact resistance, are not reduced.

The cycloolefin polymer composition of the present invention is a conventional molding method, for example, extrusion molding, injection molding, blow molding and rotational molding of a single screw extruder, vent extruder, twin screw extruder, conical twin screw extruder, co-kneader, plastic It can be formed by a plasti-ficator, a mixed extruder, a biaxial conical extruder, a planetary screw extruder, a gear extruder, a screwless extruder.

The cycloolefin copolymer composition according to the present invention is a rubber component and / or various additives such as heat stabilizers, weather stabilizers, antistatic agents, anti slip agents, under conditions that do not impair the object of the present invention in order to further improve its impact strength. It may contain an antiblocking agent, an antifogging agent, a lubricant, a dye, a pigment, a natural oil, a synthetic oil, a wax and the like.

Stabilizers which can be added as needed are, for example, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate] methane, β- (3,5 Alkyl ester of -di-t-butyl-4-hydroxyphenyl) propionic acid and 2,2'-oxamidobis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl)] prop Phenolic antioxidants such as cypionate; fatty acid metal salts such as zinc stearate and potassium stearate: glycerin monostearate, glycerin monolaurate, glycerin distearate. The ester etc. are mentioned to fatty acid of polyhydric alcohols, such as a pentaerythritol monostearate, a pentaerythritol distearate, and a pentaerythritol tristearate.

These stabilizers can be used alone or in combination.

One example of the combination is a combination of tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate] methane and zinc stearate or glycerin monostearate .

In the present invention, it is particularly preferable to use a combination of a phenyl antioxidant and a fatty acid ester of dhaka alcohol.

Fatty acid ester of a polyhydric alcohol is preferably a portion of an alcoholic hydroxyl group of a trivalent or higher polyhydric alcohol.

Fatty acid esters of polyhydric alcohols include, for example, fatty acid esters of glycerin such as glycerin monostearate, glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin distearate and glycerin dilaurate; Pentaerythritol monostearate, pentaerythritol monolaurate. And fatty acid esters of pentaerythritol such as pentaerythritol dilaurate, pentaerythritol distearate, and pentaerythritol tristearate.

The phenolic antioxidant is used in an amount of 0 to 10 parts by weight, preferably 0 to 5 parts by weight, more preferably 0 to 2 parts by weight, based on 100 parts by weight of the cycloolefin resin.

The fatty acid ester of the polyhydric alcohol is used in an amount of 0 to 10 parts by weight, preferably 0 to 5 parts by weight, based on 100 parts by weight of the cycloolefin resin.

In addition, in the present invention, the cycloolefin copolymer composition does not impair the object of the present invention is silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice ballun, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, Doromite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, cray, mica, asbestos, glass fiber, glass flakes, glass beads, calcium silicate, bonmorillonite, bentonite, graphite, aluminum powder, rib sulfate And polymer fibers obtained from -olefins having two or more carbon atoms, such as den, boron fibers, silicon carbide fibers, and polypropylene fibers, polyester fibers, and polyamide fibers.

The cycloolefin copolymer composition of the present invention comprises a cycloolefin elastomer component [Aα] having substantially no polymerizable CC double bond and α-olefin (i) having two or more carbon atoms in the presence of the elastomer component [Aα]. It consists of the said cycloolefin copolymer component [B (alpha)] obtained by copolymerizing the said cycloolefin (ii), and the phase of the cycloolefin elastomer component [A (alpha)] is finely dispersed in the cycloolefin copolymer component [B (alpha) phase.

The difference in refractive index between the component [Aα] and the component [Bα] is as small as 0.0015 or less.

Therefore, the composition did not lose its transparency and in particular the impact resistance was improved.

EXAMPLE

Although the present invention will be described in more detail with reference to the following examples, it should be understood that the invention is not limited to these examples.

Measurements and evaluations of various properties were made according to the following methods.

[(1) Extreme Viscosity [η]]

The intrinsic viscosity was measured in decalin at 135 ° C. using an ubbelohde viscometer.

[(2) Glass Transition Temperature (Tg)]

The glass transition temperature (Tg) was measured at 10 degreeC of heating rate in N2 atmosphere using DSC-220C by Seiko Electron Co., Ltd.

[(3) Melt Flow Rate (MFR)]

The melts flow rate (MFR) was measured at a load of 2.16 kg and a temperature of 260 ° C. according to ASTM D1238.

[(4) refractive index]

The refractive index was measured at 25 ° C. using an Abbe refractometer (D-line, 589 nm).

[(5) Monomer Composition of Copolymer]

The monomer composition ratio was measured by ¹³ C-NMR.

[(6) iodine value]

The said iodine value was measured by the iodine monochloride method according to JIS K3331.

[(7) Sample Preparation]

The sample was manufactured using the injection molding machine IS50EPN by Toshiba Kaki Co., Ltd., and the molded object for a sample was manufactured on the following molding conditions.

After molding, the sample was measured after standing at room temperature for 48 hours.

[Molding conditions]

Cylinder temperature: 260 ℃, Molding temperature: 60 ℃, Injection pressure 1st / 2nd: 1,000 / 800kg / cm ²

[(8) Light transmittance]

The light transmittance was measured using the photometer MPS-200 by Shimasu Seisagu Sho Co., Ltd. using a compression sheet of 2 nm thickness as a sample at a wavelength of 780 nm.

[(9) Izod Impact Strength]

The Izod impact strength was measured according to ASTM D256.

Sample size: 5/2 1/8 1 / 2t inch (notch), test temperature: 23 ℃

[Production of cycloolefin elastomer component [Aα]]

Cycloolefin elastomer [Aα] was synthesize | combined by the following method in the 1 liter glass polymerization reactor equipped with the stirring blade.

A cyclohexane solution of 5-phenyl-bicyclo [2.2.1] hept-2-ene (PhBH) was fed to the polymerization reactor at a feed rate of 0.4 l / hr so that the PhBH concentration was 10.6 g / l in the reactor. .

In addition, a cyclonucleic acid solution of VO (OC ₂ H ₅ ) Cl ₂ as a catalyst to the reactor was supplied at a rate of 0.5 l / hr so that the vanadium concentration in the reactor was 0.5 mmol / l (the vanadium concentration supplied at this time was the vanadium species in the reactor). Of 2.86 times) of isobutylaluminum sesquichloride (Al (C ₄ H ₉ ) _1.5 Cl _1.5 ) at a feed rate of 0.4 l / hr so that the aluminum concentration in the copolymer is 4.0 mmol / l. The cyclonucleic acid solution was fed continuously.

In addition, ethylene was supplied to the polymerization reaction system through a bubble tube at a rate of 20.0 l / hr nitrogen at 10.0 l / hr and hydrogen at 0.5 l / hr.

The copolymerization reaction was carried out by circulating a refrigerant through a jacket provided outside the polymerization reactor while maintaining the temperature of the polymerization system at 10 ° C.

The polymerization liquid of the ethylene / PhBH copolymer produced from the copolymerization reaction was continuously taken out from the top of the reactor so that the amount of the polymerization liquid in the reactor was always 1 l (ie, the average residence time was 0.5 hour).

After adding a small amount of methyl alcohol to the polymerization solution, the polymerization reaction was terminated.

The homomixer was then stir-stirred and contacted with an aqueous solution containing 5 ml of concentrated hydrochloric acid in 1 l of water at 1.1 ratio to transfer the catalyst residue to the water phase.

After the contacted mixture was left to stand, the aqueous phase was separated and the polymer phase was washed twice with distillation and purified by separation.

The polymer solution thus separated is then stirred and poured into acetone in three times the amount of the polymer solution.

The solids were collected by filtration and washed thoroughly with acetone and dried at 130 ° C. for 12 hours at 350 mm Hg.

In the same manner as above, an ethylene / PhBH copolymer was obtained in an amount of 40.0 g / hr, that is, 20.0 g / l as the cycloolefin elastomer component [Aα].

The copolymer obtained above had an ethylene content of 87.8 mol%; PhBH content is 12.2 mol%; Intrinsic viscosity [η] is 1.91 dl / g; Glass transition temperature (Tg) measured by DSC is 2.4 degreeC; Iodine values are 0.2 g iodine / 100-g-polymer; The refractive index N _D (Aα) measured at 25 ° C. was 1.5416.

The polymerization reaction was carried out as described above, and the polymerization liquid was withdrawn from the top of the reactor, washed with acidic water and then purified with water to remove catalyst residues.

Magnesium sulfate anhydride was added to the polymerization solution in an amount of 10 g per liter of the polymerization solution, and the resultant mixture was shaken to remove water contained in the solution, thereby obtaining the polymerization solution for use in the polymerization reaction of Example 1.

Example 1

Ethylene and tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene in the presence of a cycloolefin elastomer component [Aα] having a CC double bond polymerizable in a 1 liter glass polymerization reactor equipped with a stirring blade. The polymerization of (TCD) was performed continuously by the following method.

The polymer solution obtained by removing the water comprises the above ethylene / PhBH copolymer ([η]: 1.91 dl / g, iodine value: 0.2 g-iodine / 100-g-polymer, Tg: 2.4 ° C.), The reactor was continuously fed at a feed rate of 0.5 l / h such that the ethylene / PhBH / VNB copolymer concentration in the reactor was 6.9 g / l.

Further, the TCD cyclohexane solution was continuously supplied to the reactor at a feed rate of 0.4 l / hr such that the TCD concentration in the polymerization reactor was 60.0 g / l.

In addition, a cyclohexane solution of VO (OC ₂ H ₅ ) C1 ₂ as a catalyst at the top of the reactor was fed at a rate of 0.7 l / hr so that the vanadium concentration in the reaction was 0.5 mmol / l. Isobutyl aluminum sesquichloride (Al (C ₄ H ₉ ) _1,5 ) at a feed rate of 0.4 l / hr so that the aluminum concentration in the reactor is 4.0 mmol / l. The cyclohexane solution of Cl _1,5 ) was fed continuously.

In addition, the polymerization reaction system was fed through a bubble tube at a rate of 30.6 l / hr ethylene, 40.6 l / hr nitrogen and 0.85 l / hr hydrogen.

The copolymerization reaction was carried out by circulating a refrigerant through a jacket provided outside the polymerization reactor while maintaining the temperature of the polymerization system at 10 ° C.

The polymer solution of the ethylene / TCD copolymer composition containing the ethylene / PhBH copolymer produced by the copolymerization reaction was used to improve the amount of the polymerization liquid in the reactor to 1 l (ie, the average residence time was 0.5 hour). It was taken out continuously from the top.

The polymerization reaction was terminated after adding a small amount of methanol to the polymerization solution.

After using a homomixer, the catalyst residue was transferred to an aqueous phase by stirring with a water solution containing 5 ml of concentrated hydrochloric acid in 1 liter of water in a 1: 1 ratio.

After the contacted mixture was left to stand, the aqueous phase was separated and the polymer phase was washed twice with distilled water to purify and separated.

Then, the polymerization liquid thus purified and separated is poured into acetone in three times the amount of the polymerization liquid with strong stirring.

The solids are collected by filtration and washed thoroughly with acetone.

The solids thus washed were introduced into acetone to 40 g / l, and TCD present in the polymer was extracted at a temperature of 60 ° C. for 2 hours.

After the extraction, the solid phase was collected by filtration and dried at 130 ° C. for 12 hours in a 350 mmHg nitrogen atmosphere.

In the same manner as above, the cycloolefin copolymer composition of the ethylene / (PhBH) copolymer and the ethylene / TCD copolymer was obtained in an amount of 53.4 g / hr, that is, 26.7 g / l.

In the copolymer composition thus prepared, the component [Aα] is included in an amount of 25.8% by weight.

The MFR of this copolymer composition measured at a temperature of 260 ° C. under 2.16 kg of load, was 2.9 g / 10 min.

Tg of the said component [B (alpha)] was 142 degreeC.

The results are shown in Table 1.

Example 2

In addition to changing to the conditions shown in Table 1, the procedure of Example 1 was repeated to prepare a cycloolefin copolymer composition of ethylene / PhBH copolymer and ethylene / TCD copolymer.

The results are shown in Table 1.

Example 3

7.8 g of ethylene / PhBH copolymer (intrinsic viscosity [η]: 2.02 dl / g, Tg: -6.0 ° C) obtained by filling a 1 liter stainless steel pressure vessel with 239 ml of toluene and preparing cycloolefin elastomer component [Aα] ) And 134 g of norbornene (NB) were fed at room temperature under a nitrogen atmosphere.

Next, ethylene was passed under atmospheric pressure while stirring to make the reaction system ethylene atmosphere.

Ethylene was supplied to the pressure vessel such that the internal pressure was 4 kg / cm ² while maintaining the pressure vessel at an internal temperature of 70 ° C.

After stirring for 10 minutes, a toluene solution containing ethylenebis (indenyl) zirconium dichloride and methylaluminoxane prepared above was added to the reaction system to initiate a copolymerization reaction of ethylene and NB.

At this time, the concentration of ethylenebis (indenyl) zirconium dichloride in this reaction system was 0.10 mmol / l, and the concentration of methylaluminoxane in the reaction system was 0.2 mmol / l.

Ethylene was continuously fed into the reaction system during the copolymerization to maintain an internal pressure of 4 kg / cm ² .

After 20 minutes, isopropyl alcohol was added to the reaction system to terminate the polymerization reaction.

After releasing the pressure, the polymer solution was withdrawn from the pressure vessel and contacted with an aqueous solution containing 5 ml of concentrated hydrochloric acid in 1 liter of water at a 1: 1 stirring ratio using a homomixer to transfer the contact residue to the aqueous phase.

The contacted mixture is allowed to stand, the aqueous phase is separated off, and the polymerization liquid phase is separated by washing and purifying twice with distilled water.

Then, the polymerized liquid thus separated was poured into acetone in three times the amount of the polymerized liquid, and the copolymer was stirred by hard stirring to precipitate the copolymer, and the solid phase (copolymer) was collected by filtration and washed thoroughly with acetone. .

Further, the solid phase was introduced into acetone to be 40 g / liter, and unreacted NB in the copolymer was extracted at 60 ° C. for 2 hours.

After extraction, the solid phase was collected by filtration and dried at a temperature of 130 ° C. for 12 hours in a nitrogen stream of 350 mmHg.

The cycloolefin copolymer composition of the above ethylene / PhBH copolymer and ethylene / NB copolymer was obtained by the above method.

In the copolymer composition thus prepared, the component [Aα] is contained 25.7% by weight.

The MFR of the copolymer composition measured at 260 ° C. under 2.16 kg load was 2.6 g / 10 min.

Tg of the said component [B (alpha)] was 135 degreeC.

The results are shown in Table 1.

Comparative Examples 1-3

In addition to changing to the conditions shown in Table 1, the procedure of Example 1 was repeated to prepare a cycloolefin copolymer composition.

The results are shown in Table 1.

As is evident from the results of Comparative Example 2, the impact strength of the composition of the olefin is reduced when the intrinsic viscosity [η] of the elastomer component [Aα] is less than 0.5 dl / g.

In addition, as apparent from the results of Comparative Example 3, the impact strength of the composition is reduced when the glass transition temperature (Tg) of the elastomer component [Aα] is 15 ° C or more.

Claims (2)

[Aa] A copolymer of α-olephine (i) having 2 or more carbon atoms and at least one cycloolefin (ii) represented by the following formula (I) or (II) is obtained, and the content of cycloolefin units is 3 mol%. As described above, the intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.5 to 5.0 dl / g, and the glass transition temperature (Tg) is 15 ° C. or less, and does not have a polymerizable carbon-carbon double bond and is measured at 25 ° C. Α-olefin (i) having 2 or more carbon atoms and the following formula (I) in the presence of a cycloolefin elastomer component having a refractive index (N _D (Aα)) of 1.500 to 1.650, and [Bα] the cycloolefin elastomer component [Aα]. ) Or a cycloolefin copolymer component obtained by copolymerizing the above cycloolefin (ii) represented by (II), wherein the component [Aα] is present in an amount of 8 to 40% by weight, and the refractive index (N _D ( Aα)) and refractive index (difference between the _{N D (Bα)) △ N} D = the above-mentioned components _{[Bα] | N D (Aα} ) -N D (Bα)) | is cyclohexane, characterized in that more than 0.015 -Olefin copolymer composition,

Wherein n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ¹ to R ¹⁸ , R ^a and R ^b are each independently a hydrogen atom, a halogen atom or an aliphatic, alicyclic or aromatic Hydrocarbon, R ¹⁵ to R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic group which may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may together form an alkylidene group.

Wherein p and q are 0 or an integer of 1 or more, m and n are 0, 1 or R ¹ to R ¹⁹ are each independently a hydrogen atom, a halogen atom or an aliphatic, alicyclic or aromatic hydrocarbon group or an alkoxy group The carbon atom bonded to R ⁹ and R ¹⁰ may be bonded directly or by an alkylene group having 1 to 3 carbon atoms to R ¹³ bonded carbon atom or R ¹¹ bonded carbon atom, or R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be combined together to form a monocyclic or polycyclic aromatic ring when n and m are zero. It is obtained by copolymerizing [alpha] -olefin (i) having 2 or more carbon atoms and at least one cycloolefin (ii) represented by the following formula (II), wherein the content of cycloolefin unit is 3 mol% or more and 135 占 폚. Refractive index (N _D) measured at 25 ° C. with an intrinsic viscosity [η] of 0.5-5.0 dl / g and a glass transition temperature (Tg) of 15 ° C. or less and without polymerizable carbon-carbon double bonds measured in decalin. (Aα)) in the presence of a cycloolefin elastomer component having 1.500 to 1.650, [Bα] and the cycloolefin elastomer component [Aα], at least two cyclo atoms represented by α-olefins (i) and the following formulas (I) A cycloolefin copolymer component obtained by combining olefin (ii), wherein the component [Aα] is present in an amount of 8 to 40% by weight, and the refractive index (N _D (Aα)) of the component [Aα] and the component [Bα] refractive index difference between △ N _D = _{(N D (Bα)) |} N D (Aα) -N D (Bα) | cycloolefin copolymer which is characterized by not more than 0.015 trillion Water

Wherein p and q are integers of 0 or 1 or more, m and n are 0, 1 or 2, and R ¹ to R ¹⁹ are each independently a hydrogen atom, a halogen atom or an aliphatic, alicyclic or aromatic hydrocarbon group or an alkoxy group R ⁹ and R ¹⁰ may be bonded to each other by a C ¹³ bonded carbon atom or R ¹¹ bonded carbon atom or an alkylene group of 1 to 3 carbon atoms bonded directly or R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded together to form a monocyclic or polycyclic aromatic ring when n and m are zero.

Wherein n is 0 or l, m is 0 or a positive integer, q is 0 or 1, and R ¹ to R ¹⁸ , R ^a and R ^b are each independently a hydrogen atom, a halogen atom or an aliphatic, alicyclic or aromatic A hydrocarbon, R ¹⁵ to R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic group which may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may together form an alkylidene group.