JP2008231361A - Cyclic olefinic compound addition copolymer, method for producing the same and application thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cyclic olefinic compound addition copolymer exhibiting characteristics such as melt molding processability and excellent transparency, heat resistance, the melt molding processability, low water absorbency and low dielectric constant, having extremely large elongation at break, and in particular, a large breaking energy, which is an index of the strength of a film and suitable for applications such as optical films, and to provide a method for producing the addition copolymer with high productivity. <P>SOLUTION: The cyclic olefinic compound addition copolymer has a structural unit (1) derived from a cyclic olefinic compound having a 6C alkyl group as a substituent, a structural unit (2) derived from a cyclic olefinic compound having a 7-12C alkyl group as a substituent and, as necessary, a structural unit (3) derived from other cyclic olefinic compounds. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a cyclic olefin addition copolymer, a method for producing the same, and a use thereof. Specifically, the present invention is obtained by addition copolymerization of a cyclic olefin compound having an alkyl substituent and a specific cyclic olefin compound, and has excellent transparency, heat resistance, melt molding processability, and low water absorption. The present invention relates to a cyclic olefin-based addition copolymer that exhibits properties such as properties and low dielectric constant and is suitable for applications such as optical films, its production method, and its applications.

  Optical materials such as lenses, backlights, light guide plates and optical films need to have excellent transparency, but they also have heat resistance, low water absorption, low dielectric constant, flexibility and toughness. The demand for sex is increasing.

  For example, polyester resins, acrylic resins, polycarbonate resins, polyarylate resins, polyethersulfone resins, and the like are known as transparent resins used for optical materials, but these resins have heat resistance, water absorption, and transparency. Characteristics such as sex were not sufficient.

  On the other hand, many hydrogenated products or addition polymers of ring-opening polymers of cyclic olefin compounds have been proposed as resins having excellent transparency and heat resistance. These polymers are useful because their main chain is composed of alicyclic hydrocarbons, and are less absorbed in the short wavelength region than aromatic resins.

  Many cyclic olefin ring-opening polymers and hydrogenated products thereof have been proposed as optical materials for producing lenses and optical disks (see, for example, Patent Documents 1 to 6). The ring-opening (co) polymer and its hydrogenated product have excellent heat resistance, low water absorption (wetness), excellent optical properties such as transparency, and excellent moldability such as injection molding. In addition, a ring-opening polymer of a cyclic olefin monomer having a polar group introduced in the molecule and a hydrogenated product thereof have been proposed (see, for example, Patent Documents 7 to 8), and heat resistance, optical properties, moldability are proposed. In addition, it has been found to be excellent in affinity with other materials and in excellent post-processability such as adhesion. However, since the cyclic olefin ring-opening polymer has a double bond in the main chain after the polymerization reaction, a hydrogenation step is required to improve the heat deterioration resistance, and the industrial productivity and economical points are required. There is a problem.

  On the other hand, it is known that a resin excellent in heat resistance and transparency can be obtained by addition polymerization of a cyclic olefin compound. In addition, since there is no double bond in the main chain after the polymerization reaction, it is excellent in heat deterioration resistance, and since hydrogenation is unnecessary, it is excellent in industrial productivity and economy. Many addition copolymers of cyclic olefin compounds and α-olefins have been reported as addition polymers of cyclic olefin compounds (see, for example, Patent Documents 9 to 10). However, in these copolymers, a chain of structural units derived from an α-olefin such as ethylene may crystallize, and the transparency is lowered, so that it is not always sufficient for use as an optical material. In addition, since the difference in polymerization reactivity between the cyclic olefin and the α-olefin is large, the composition of the copolymer is distributed, and the transparency may be lowered.

On the other hand, a cyclic olefin addition polymer formed only from a structural unit derived from a cyclic olefin compound can be produced using a titanium catalyst, a zirconium catalyst, a cobalt catalyst, a nickel catalyst, a palladium catalyst, etc., and has excellent heat resistance. It is known as a resin exhibiting properties and transparency. Here, the stereoregularity of the polymer produced by the selection of the catalyst to be used (atactic / erythro-disyndiotactic / erythro-diisotactic etc.) and the mode of addition polymerization (addition at the 2,3-position and 2, It has been known so far that the addition at the 7-position) and the controllability of the molecular weight are different. For example, it has been reported that a norbornene polymer polymerized using a zirconium-based metallocene catalyst is infusible and insoluble in common solvents (see Non-Patent Document 1). Further, norbornene addition polymer polymerized using a nickel-based catalyst shows good solubility in hydrocarbon solvents such as cyclohexane (see Patent Document 11), but is reported to be inferior in mechanical strength and brittle. (See Patent Document 12).

  On the other hand, it has been reported that by using a specific catalyst containing a palladium compound, a cyclic olefin addition polymer having high polymerization activity and excellent transparency, heat resistance and mechanical strength can be produced (patent) References 12-14). Patent Document 15 discloses that a cyclic olefin copolymer obtained using a catalyst containing a hydrolyzable silyl group-containing cyclic olefin and containing a palladium compound exhibits excellent heat resistance and dimensional stability. ing. However, while the addition polymers described therein exhibit very high heat resistance, they cannot be hot melt molded, and the molding method is limited to the solution casting method (cast method). Since the casting method uses a large amount of solvent and requires removal and recovery steps of the solvent, there are industrial problems such as an increase in equipment size, low productivity, and high cost.

  For this reason, a method for lowering the glass transition temperature has been studied so that the cyclic olefin-based addition polymer can be melt-molded. As the technique, a cyclic olefin compound having an alkyl substituent can be used as a monomer. Proposed. For example, Patent Document 16 describes an addition copolymer using 5-hexyl-2-norbornene. Patent Document 11 and Non-Patent Document 2 describe that norbornene having a long-chain alkyl group is used as a monomer, and the glass transition temperature of the addition copolymer can be controlled by the chain length and ratio. However, these prior arts do not describe the influence of the polymerization catalyst on the mechanical strength of the resulting molded article. In addition, the polymerization catalyst used in these methods is not satisfactory in its activity and requires a step of removing unreacted monomers and catalyst remaining after the reaction.

Furthermore, since the cyclic olefin having a long-chain alkyl group has a lower polymerization reactivity than norbornene, the copolymer composition is distributed during the copolymerization of the both. No. 16 and Non-Patent Document 2 do not mention the difference in monomer reactivity and the composition distribution. When the conversion rate is high, the composition distribution becomes remarkable, and the transparency and strength of the resulting molded product may be impaired, so that both high conversion rate and high transparency are problems. That is, a method for producing a cyclic olefin copolymer which is excellent in economic efficiency and productivity, exhibits good heat resistance and melt molding processability, and has a high conversion and high transparency is desired. The inventors of the present invention are based on a palladium catalyst of 5-butylbicyclo [2.2.1] hept-2-ene and 5-alkylbicyclo [2.2.1] hept-2-ene having 5 to 12 carbon atoms. An addition polymer has been proposed (see Patent Document 17). This addition polymer is a novel cyclic olefin addition copolymer suitable for applications such as optical films, which has a high conversion ratio and excellent melt moldability, transparency, low water absorption and low dielectric constant. However, it cannot be said that the balance between elongation (flexibility) and strength (breaking energy) is sufficient.
Japanese Unexamined Patent Publication No. 63-21878 JP-A-1-138257 JP-A-1-168725 Japanese Patent Laid-Open No. 2-102221 JP-A-2-133413 Japanese Patent Laid-Open No. 4-170425 JP 50-111200 A JP-A-1-132626 JP 61-292601 A US Pat. No. 2,883,372 Japanese National Patent Publication No. 9-508649 JP 2006-52347 A JP 2005-162990 A JP 2005-213435 A Japanese Patent Laid-Open No. 2005-48060 JP-A-8-198919 Japanese Patent Application No. 2006-188051 Makromol. Chem. Macromol. Symp., Vol. 47, 831 (1991) Proc. Am. Chem. Soc. Div. Polym. Mater .: Sci. Eng. Vol. 75, 56 (1997)

  The present invention exhibits melt molding processability and excellent properties such as transparency, heat resistance, melt molding processability, low water absorption and low dielectric constant, and has an extremely high breaking energy, particularly an index of film strength. It is an object of the present invention to provide a cyclic olefin addition copolymer suitable for applications such as an optical film and a method for producing the addition copolymer with high productivity.

  The cyclic olefin addition copolymer of the present invention is characterized by having a structural unit (1) represented by the following formula (1) and a structural unit (2) represented by the following formula (2).

（式（１）中、Ａ¹,Ａ²,Ａ³,Ａ⁴のうちのいずれか１つは炭素数が６のアルキル基であり
、その他はそれぞれ独立に、水素原子、ハロゲン原子、メチル基のいずれかである。ｐは０〜５の整数を示す。）

(In the formula (1), any ^one of A ¹ , A ² , A ³ and A ⁴ is an alkyl group having 6 carbon atoms, and the others are independently a hydrogen atom, a halogen atom or a methyl group. (P represents an integer of 0 to 5)

（式（２）中、Ｂ¹,Ｂ²,Ｂ³,Ｂ⁴のうちいずれか１つは炭素数が７〜１２のアルキル基で
あり、その他はそれぞれ独立に、水素原子、ハロゲン原子、メチル基のいずれかである。ｑは０〜５の整数を示す。）。

(In the formula (2), any one of B ¹ , B ² , B ³ and B ⁴ is an alkyl group having 7 to 12 carbon atoms, and the others are independently a hydrogen atom, a halogen atom or methyl. Q is an integer of 0 to 5).

  The molar ratio of the structural unit (1) to the structural unit (2) (structural unit (1) / structural unit (2)) is 10/90 to 90/10, and the structural unit (1) and the structural unit. The total with (2) is preferably in an amount of 80 to 100 mol% in all structural units.

  Furthermore, it is preferable that the structural unit (3) represented by the following formula (3) is contained in all structural units in an amount of 20 mol% or less.

（式（３）中、Ｃ¹〜Ｃ⁴は、それぞれ独立に、アルコキシカルボニル基、アルキルカルボニルオキシ基、アルケニルカルボニルオキシ基、酸無水物基、オキセタニル基および加水分解性シリル基よりなる群から選ばれる官能基；水素原子；メチル基；ならびにハロゲン原子から選ばれる原子もしくは基を表す。rは０〜５の整数を示す。）。

(In formula (3), C ^{1 to} C ⁴ are each independently selected from the group consisting of an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkenylcarbonyloxy group, an acid anhydride group, an oxetanyl group, and a hydrolyzable silyl group. A hydrogen atom; a methyl group; and an atom or group selected from a halogen atom, and r represents an integer of 0 to 5.

The cyclic olefin addition copolymer of the present invention preferably has a softening point of 80 to 210 ° C. and a number average molecular weight of 20,000 to 200,000.
The production method of the cyclic olefin of the present invention includes a monomer (1m) represented by the following formula (1m), a monomer (2m) represented by the following formula (2m), and the following formula as necessary. A monomer (3m) represented by (3m),
The molar ratio of monomer (1m) to monomer (2m) (monomer (1m) / monomer (2m)) satisfies 10/90 to 90/10, and
A monomer composition in which the total of the monomer (1m) and the monomer (2m) is in an amount of 80 to 100 mol% in all monomers,
It is characterized by addition copolymerization in the presence of a catalyst obtained using the following (a), (b) and (d) or a catalyst obtained using the following (c) and (d).

（式（１ｍ）中、Ａ¹,Ａ²,Ａ³,Ａ⁴のうちのいずれか１つは炭素数が６のアルキル基であ
り、その他はそれぞれ独立に、水素原子、ハロゲン原子、メチル基のいずれかである。ｐは０〜５の整数を示す。）

(In the formula (1m), any ^one of A ¹ , A ² , A ³ and A ⁴ is an alkyl group having 6 carbon atoms, and the others are independently a hydrogen atom, a halogen atom or a methyl group. (P represents an integer of 0 to 5)

（式（２ｍ）中、Ｂ¹,Ｂ²,Ｂ³,Ｂ⁴のうちいずれか１つは炭素数が７〜１２のアルキル基
であり、その他はそれぞれ独立に、水素原子、ハロゲン原子、メチル基のいずれかである。ｑは０〜５の整数を示す。）

(In the formula (2m), any one of B ¹ , B ² , B ³ and B ⁴ is an alkyl group having 7 to 12 carbon atoms, and the others are independently a hydrogen atom, a halogen atom or methyl. (Q represents an integer of 0 to 5)

（式（３ｍ）中、Ｃ¹〜Ｃ⁴は、それぞれ独立に、アルコキシカルボニル基、アルキルカルボニルオキシ基、アルケニルカルボニルオキシ基、酸無水物基、オキセタニル基および加水分解性シリル基よりなる群から選ばれる官能基；水素原子；メチル基；ならびにハロゲン原子から選ばれる原子もしくは基を表す。rは０〜５の整数を表す。）、
（ａ）パラジウムの有機酸塩またはパラジウムのβ−ジケトネート化合物；
（ｂ）下記式（ｂ）で表されるホスフィン化合物；
Ｐ（Ｒ¹）₂（Ｒ²） …（ｂ）
（式（ｂ）中、Ｒ¹はシクロペンチル基、シクロヘキシル基またはイソプロピル基から
選ばれる置換基であり、Ｒ²は炭素数３〜１０の炭化水素基を表す。）
（ｃ）下記式（ｃ）で表される２価パラジウムのホスフィン錯体；
Ｐｄ［Ｐ（Ｒ¹）₂（Ｒ²）］_nＸ₂ …（ｃ）
（式（ｃ）中、Ｒ¹はシクロペンチル基、シクロヘキシル基およびイソプロピル基より選
ばれる置換基であり、Ｒ²は炭素数３〜１０の炭化水素基を表す。Ｘは有機酸アニオンま
たはβ−ジケトネートアニオンである。ｎは１または２である。］
（ｄ）イオン性のホウ素化合物。

(In Formula (3m), C ^{1 to} C ⁴ are each independently selected from the group consisting of an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkenylcarbonyloxy group, an acid anhydride group, an oxetanyl group, and a hydrolyzable silyl group. Represents a hydrogen atom; a methyl group; and an atom or group selected from halogen atoms, r represents an integer of 0 to 5).
(A) an organic acid salt of palladium or a β-diketonate compound of palladium;
(B) a phosphine compound represented by the following formula (b);
P (R ¹ ) ₂ (R ² ) (b)
(In formula (b), R ¹ is a substituent selected from a cyclopentyl group, a cyclohexyl group or an isopropyl group, and R ² represents a hydrocarbon group having 3 to 10 carbon atoms.)
(C) a phosphine complex of divalent palladium represented by the following formula (c);
Pd [P (R ¹ ) ₂ (R ² )] _n X ₂ (c)
(In formula (c), R ¹ is a substituent selected from a cyclopentyl group, a cyclohexyl group and an isopropyl group, and R ² represents a hydrocarbon group having 3 to 10 carbon atoms. X is an organic acid anion or β-di- Ketonate anion, n is 1 or 2.]
(D) An ionic boron compound.

The optical film of the present invention is formed from the cyclic olefin addition copolymer by a solution casting method (cast method).
The optical film of the present invention is formed from a cyclic olefin addition copolymer by a melt molding method.

  According to the present invention, a novel cyclic olefin-based addition which is excellent in melt molding processability, transparency and heat resistance, has a low water absorption and dielectric constant, has a low metal content, and can be suitably used for optical parts such as optical films. Copolymers can be provided. Moreover, according to this invention, the manufacturing method of the cyclic olefin type addition copolymer which can manufacture such a novel cyclic olefin type addition copolymer with a small catalyst usage-amount and a high yield can be provided. . Furthermore, according to the present invention, it is obtained from a novel cyclic olefin-based addition copolymer, excellent in transparency and heat resistance, low in water absorption and dielectric constant, low in metal content, and excellent in flexibility and toughness. An optical film can be provided.

Hereinafter, the present invention will be specifically described.
[Cyclic olefin addition copolymer]
The cyclic olefin addition copolymer of the present invention has a structural unit (1) represented by the above formula (1) having a C 6 alkyl group as a substituent, and a C 7-12 alkyl group as a substituent. And having the structural unit (2) represented by the formula (2), and having the structural unit (3) represented by the formula (3) as necessary. The cyclic olefin-based addition copolymer of the present invention is preferably composed only of the structural unit (1), the structural unit (2), and the structural unit (3) as necessary.

Below, the monomer which comprises the cyclic olefin type addition copolymer of this invention is described.
<Monomer composition>
The cyclic olefin addition copolymer of the present invention is obtained by adding a monomer composition containing the monomer (1m), the monomer (2m), and, if necessary, the monomer (3m). It can be obtained by copolymerization.

  A preferred alkyl substituent in the structural unit (1) and the monomer (1m) is a 1-hexyl group, and a preferred alkyl substituent in the structural unit (2) and the monomer (2m) is a 1-heptyl group. Having a linear or branched alkyl group such as 1-octyl group, 1-nonyl group, 1-decyl group, 1-undecyl group, 1-dodecyl group, 2-decyl group and 8-methyl-1-nonyl group Among them, 1-decyl group and 1-dodecyl group are preferable.

Specific examples of the monomer (1m) include 5-hexylbicyclo [2.2.1] hept-2-ene and 8-hexyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3
-Ene and the like. As these monomers (1m), 5-hexylbicyclo [2.2.1] hept-2-ene in which p in the formula (1m) is 0 is more preferable.

Specific examples of the monomer (2m) include 5-heptylbicyclo [2.2.1] hept-2-ene, 5-octylbicyclo [2.2.1] hept-2-ene, 5- Nonylbicyclo [2.2.1] hept-2-ene, 5-decylbicyclo [2.2.1] hept-2-ene, 5-undecylbicyclo [2.2.1] hept-2-ene, 5-dodecylbicyclo [2.2.1] hept-2-ene, 8-heptyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-octyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-nonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3-
Ene, 8-decyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8
-Undecyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and 8
-Dodecyl-tetracyclo [4.4.0.1 ^2,5 . Having a linear alkyl group such as 1 ^7,10 ] dodec-3-ene; 2- (bicyclo [2.2.1] hept-2-en-5-yl) decene, 8-methyl-1- ( Examples thereof include those having a branched alkyl group such as bicyclo [2.2.1] hept-2-en-5-yl) nonane. As these monomers (2m), 5-alkylbicyclo [2.2.1] hept-2-ene having 7 to 12 carbon atoms in which q in the formula (2m) is 0 is more preferable. Of these, 5-decylbicyclo [2.2.1] hept-2-ene and 5-dodecylbicyclo [2.2.1] hept-2-ene are particularly preferable because the raw materials are easily available industrially. When an alkyl group having 7 or more carbon atoms is used as the monomer (2m), it has excellent melt molding processability and can be molded at a temperature that is not too high. It is possible to prevent the molded body from being deteriorated and colored due to the high temperature. On the other hand, when an alkyl group having more than 12 carbon atoms is used, the boiling point of 5-alkylbicyclo [2.2.1] hept-2-ene becomes too high, and purification during industrial production may be difficult. .

In the monomer (3m), C ^{1 to} C ⁴ in the formula (3m) are each independently an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkenylcarbonyloxy group, an acid anhydride group, an oxetanyl group, and a hydrolyzable group. It is a functional group selected from the group consisting of silyl groups, or an atom or group selected from a hydrogen atom, a methyl group and a halogen atom. In the case where the monomer (3m) has the above functional group, it is easy to introduce a crosslinking group when the monomer composition containing the monomer (3m) is subjected to addition copolymerization. Moreover, adhesiveness can be provided to the molded object obtained from an addition copolymer. For this reason, as the monomer (3m), at least one of C ^{1 to} C ⁴ in the formula (3m) is an alkoxycarbonyl group or an alkyl group for the purpose of introducing a crosslinking group or imparting adhesion to a molded body. It preferably has a functional group selected from the group consisting of a carbonyloxy group, an alkenylcarbonyloxy group, an acid anhydride group, an oxetanyl group, and a hydrolyzable silyl group.

Specific examples of the monomer (3m) having a functional group include methyl bicyclo [2.2.1] hept-5-ene-2-carboxylate and 2-methylbicyclo [2.2.1] hepta. Methyl 5-ene-2-carboxylate, 2-methylbicyclo [2.2.1] hepta-5-ene-2-carboxylate, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-9-ene-4-carboxylate, 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-9-ene-4-carboxylate, 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] t-butyl dodec-9-ene-4-carboxylate, acetic acid (bicyclo [2.2.1] hept-5-en-2-yl), acetic acid (bicyclo [2.2.1] Hept-5-en-2-methyl-2-yl), acetic acid (tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodec-9-en-4-yl), bicyclo [2. 2.1] hept-5-ene-2,3-carboxylic anhydride, 5-[(3-ethyl-3-octacenyl) methoxy] bicyclo [2.2.1] hept-2-ene, 5-[( 3-Oxetanyl) methoxy] bicyclo [2.2.1] hept-2-ene, bicyclo [2.2.1] hept-5-ene-2-carboxylic acid (3-ethyl-3-oxetanyl) methyl, 5 -Trimethoxysilylbicyclo [2.2.1] hept-2-ene and 5-triethoxysilyl Such as [2.2.1] hept-2-ene.

As these monomers (3m), those in which r in the formula (3m) is 0 are more preferable.
The monomer composition used in the present invention contains the monomer (1m) and the monomer (2m) as essential components, and may contain the monomer (3m) as necessary. When the proportion of the monomer (2m) is increased, the flexibility of a molded article such as a film and a sheet formed from the cyclic olefin addition copolymer tends to increase, and the softening point tends to decrease. Moreover, when the proportion of the monomer (3m) increases, the elastic modulus of a molded article such as a film and a sheet formed from the cyclic olefin addition copolymer is improved, but the flexibility (elongation) tends to decrease. is there. For this reason, there is a limit to the amount used. Moreover, when the ratio of the monomer (3m) which has a functional group is high, polymerization activity may fall and productivity may deteriorate.

  Therefore, in the monomer composition, the molar ratio of the monomer (1m) to the monomer (2m) (monomer (1m) / monomer (2m)) is usually 10/90 to 90/10, preferably 20/80 to 90/10, more preferably 40/60 to 90/10. When the ratio of the monomer (1m) to the total of the monomer (1m) and the monomer (2m) is less than 10 mol%, the softening point of the resulting addition copolymer becomes too low and the heat resistance is insufficient. It may become. On the other hand, when the ratio of the monomer (1m) to the total of the monomer (1m) and the monomer (2m) exceeds 90 mol%, there is a problem that the softening point becomes too high and the molding processability deteriorates. May occur.

  Moreover, in the monomer composition used by this invention, it is preferable that the sum total of a monomer (1m) and a monomer (2m) is 80-100 mol% in all the monomers. When the monomer composition contains a monomer other than the monomer (1m) and the monomer (2m) in an amount of 20 mol% or more, the molding processability of the resulting copolymer may deteriorate. In some cases, the strength of the molded product obtained from the copolymer may decrease. For this reason, when the monomer composition used in the present invention contains the monomer (3m), the amount of the monomer (3m) is contained in the monomer composition at a ratio of 20 mol% or less. Is desirable.

  Although the monomer composition used by this invention is not specifically limited, It is comprised from a monomer (1m), a monomer (2m), and a monomer (3m) as needed, and others It is preferable not to contain the monomer. A monomer (1m), a monomer (2m), and a monomer (3m) may be used individually by 1 type, respectively, and may be used in combination of 2 or more types.

<Cyclic olefin addition copolymer>
The cyclic olefin addition copolymer of the present invention is more preferably a structural unit (1) represented by the above formula (1) having an alkyl group having 6 carbon atoms as a substituent, and an alkyl group having 7 to 12 carbon atoms. Has a structural unit (2) represented by the above formula (2) having an alkyl group having 8 to 12 carbon atoms, particularly preferably an alkyl group having 10 to 12 carbon atoms as a substituent, and if necessary, the above It has a structural unit (3) represented by the formula (3).

  Here, the structural unit (1) is usually derived from the monomer (1m) represented by the above formula (1m), and the structural unit (2) is a monomer represented by the above formula (2m). The structural unit (3) derived from (2m) and included as necessary is derived from the structural unit (3m) represented by the above formula (3m).

  As described above, the structural unit (1) is usually derived from the monomer (1m) represented by the formula (1m), and the structural unit (2) is represented by the single unit represented by the formula (2m). The structural unit (3) derived from the monomer (2m) and included as necessary is derived from the structural unit (3m) represented by the formula (3m).

  The alkyl substituent that the structural unit (1) has is preferably a 1-hexyl group. In addition, examples of the alkyl substituent of the structural unit (2) include 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decyl group, 1-undecyl group, 1-dodecyl group, 2-decyl group, 8 Examples thereof include those having a linear or branched alkyl group such as a -methyl-1-nonyl group, among which a 1-decyl group and a 1-dodecyl group are preferable.

The structural unit (3) is a cyclic olefin-based structural unit other than the structural unit (1) and the structural unit (2), and includes an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkenylcarbonyloxy group, an acid anhydride group, an oxetanyl group, and A functional group selected from the group consisting of hydrolyzable silyl groups may or may not have a functional group. When these specific functional groups are present, the addition copolymer is crosslinkable. In addition, since the molded product such as a film obtained from the addition copolymer has excellent adhesion and adhesion, the cyclic olefin addition copolymer of the present invention requires such characteristics. When used for applications, it is preferable to include a structural unit (3) having one or more of the specific functional groups.

  Moreover, the elasticity modulus of an addition copolymer can be improved by having the structural unit (3) which does not have a functional group. In particular, it is preferable to have a structural unit (3) having no functional group for the purpose of this melt molding. The structural unit (3) is preferably contained in the addition copolymer in an amount of 20 mol% or less in all the structural units.

In the present invention, each of the structural units (1), (2) and (3) may be used alone or in combination of two or more.
The ratio of the structural unit (1) to the total of the structural unit (1) and the structural unit (2) is 10 to 90 mol%, more preferably 20 to 90 mol%, particularly preferably 40 to 90 mol%. The ratio of the structural unit (3) to the total structural units (the total of the structural unit (1), the structural unit (2), and the structural unit (3)) is 0 to 20 mol%, more preferably 10 to 20 mol%. is there. That is, in the cyclic olefin addition copolymer of the present invention, the molar ratio of the structural unit (1) to the structural unit (2) (structural unit (1) / structural unit (2)) is usually 10/90 to 90 / 10, more preferably 20/80 to 90/10, particularly preferably 40/60 to 90/10. Moreover, it is preferable that the sum total of a structural unit (1) and a structural unit (2) is the quantity of 80-100 mol% in all the structural units.

  When the ratio of the structural unit (2) to the total of the structural unit (1) and the structural unit (2) exceeds 90 mol%, the softening point is lowered and the heat resistance is inferior. This is not preferable because flexibility of a film and a sheet to be obtained is insufficient or molding processability is inferior. On the other hand, if the proportion of the structural unit (3) in all the structural units exceeds 20 mol%, the flexibility of the film and the sheet is insufficient, which is not preferable.

  In such a cyclic olefin addition copolymer of the present invention, as the proportion of the structural unit (2) increases, the flexibility of a molded article such as a film or a sheet obtained by using the copolymer increases and softens. There is a tendency for points to drop. Further, as the proportion of the structural unit (3) increases, the mechanical properties and toughness of a molded article such as a film or a sheet obtained using the copolymer tend to be improved.

  The cyclic olefin addition copolymer of the present invention has a softening point determined from an inflection point temperature of a temperature-thermal expansion curve measured by the TMA method, and is 80 to 210 ° C, more preferably 100 to 200 ° C. is there. When this softening point is less than 80 ° C., it is not suitable for applications requiring heat resistance. On the other hand, when the softening point exceeds 210 ° C., melt molding becomes difficult.

  As for the molecular weight of the cyclic olefin-based addition copolymer of the present invention, the polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatogram (GPC) is 20,000 to 200,000, more preferably 30,000. 000-100,000. When the number average molecular weight is less than 20,000, the mechanical strength of the formed film or sheet is lowered, and it may be easily cracked. On the other hand, when the number average molecular weight exceeds 200,000, the melt viscosity becomes too high, so that molding becomes difficult or the flatness of the molded product is often impaired. The molecular weight of the cyclic olefin-based addition copolymer can be adjusted by performing polymerization in the presence of an appropriate molecular weight regulator.

  The cyclic olefin-based addition copolymer of the present invention has excellent transparency, and the spectral light transmittance measured with a film having a thickness of 100 μm is usually 85% or more, more preferably 88% or more at a wavelength of 400 nm. Yes, the haze value is usually 2.0% or less, more preferably 1.0% or less.

<Additives>
Various additives can be blended with the cyclic olefin-based addition copolymer of the present invention as necessary. For example, antioxidants such as phenolic antioxidants, lactone antioxidants, phosphorus antioxidants and sulfur antioxidants can be blended to improve oxidation stability and prevent coloration and degradation. . These antioxidants can be mix | blended in the ratio of 0.001-5 weight part per 100 weight part of cyclic olefin type addition copolymers. As an antioxidant,
1) 2,6-di-t-butyl-4-methylphenol, 4,4′-thiobis- (6-t-
Butyl-3-methyl-phenyl), 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), tetrakis [methylene-3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate] methane, 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid stearate, 2,5-di-tert-butylhydroquinone and Phenolic antioxidants or hydroquinone antioxidants such as pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl)] propionate,
2) Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t -Butyl-5-methylphenyl) 4,4'-biphenylenediphosphonite, 3
, 5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tris (4-methoxy-3,5-diphenyl) phos Phosphorous secondary antioxidants such as phyto and tris (nonylphenyl) phosphite, and 3) sulfur secondary antioxidants such as dilauryl-3,3′-thiodipropionate and 2-mercaptobenzimidazole, etc. Can be mentioned.

A flame retardant can also be mix | blended with the cyclic olefin type addition copolymer of this invention. A well-known thing can be used as a flame retardant, For example, a halogen flame retardant, an antimony flame retardant, a phosphate ester flame retardant, a metal hydroxide, etc. can be mentioned. Among these, phosphate ester-based flame retardants that exhibit an effect only by blending a small amount and can minimize deterioration of water absorption, low dielectric constant, and transparency are preferable, and 1,3-bis (phenylphosphoryl) benzene, 1 , 3-bis (diphenylphosphoryl) benzene, 1,3-bis [di (alkylphenyl) phosphoryl] benzene, 1,3-bis [di (2 ′, 6′-dimethylphenyl)
Phosphoryl] benzene, 1,3-bis [di (2 ′, 6′-diethylphenyl) phosphoryl] benzene, 1,3-bis [di (2 ′, 6′-diisopropylphenyl) phosphoryl] benzene, 1,3- Bis [di (2 ′, 6′-dibutylphenyl) phosphoryl] benzene, 1,3-bis [di (2′-t-butylphenyl) phosphoryl] benzene, 1,3-bis [di (2′-isopropylphenyl) ) Phosphoryl] benzene 1,3-bis [di (2′-methylphenyl) phosphoryl] benzene, 1,4-bis (diphenylphosphoryl) benzene, 1,4-bis [di (2 ′, 6′-dimethylphenyl) Phosphoryl] benzene, 1,4-bis [di (2 ′, 6′-diethylphenyl) phosphoryl] benzene, 1,4-bis [di (2 ′, 6′-diisopropylphenyl) phosphoryl] , 1,4-bis [di (2′-t-butylphenyl) phosphoryl] benzene, 1,4-bis [di (2′-isopropylphenyl) phosphoryl] benzene, 1,4-bis [di (2 ′) Condensed phosphate ester flame retardants such as -methylphenyl) phosphoryl] benzene and 4,4'-bis [di (2 ", 6" -dimethylphenyl) phosphorylphenyl] dimethylmethane are more preferred. Although the blending amount varies depending on the type of flame retardant and the required degree of flame retardancy, it is preferable to blend the flame retardant in an amount of 0.5 to 40 parts by weight with respect to 100 parts by weight of the cyclic olefin copolymer, More preferably, it is blended in an amount of 2 to 30 parts by weight, particularly preferably 4 to 20 parts by weight. When the blending amount of the flame retardant is less than 0.5 parts by weight, the flame retardant effect is insufficient. On the other hand, when the blending amount of the flame retardant exceeds 40 parts by weight, transparency may be deteriorated, electrical characteristics such as dielectric constant may be deteriorated, water absorption may be increased, and heat resistance may be deteriorated.

In the cyclic olefin addition copolymer of the present invention, a leveling agent and a dye such as a known lubricant and an ultraviolet absorber can be further blended as required.
[Method for producing cyclic olefin addition copolymer]
<Addition copolymerization reaction>
In the present invention, the addition copolymerization reaction may be carried out batchwise, or may be carried out using, for example, a tubular continuous reactor equipped with a suitable monomer supply port. The addition copolymerization reaction is performed in a nitrogen or argon atmosphere as necessary, but may be performed in air. The reaction temperature is 0 to 150 ° C, more preferably 10 to 100 ° C, particularly preferably 20 to 80 ° C. The solvent used is not particularly limited, but alicyclic hydrocarbon solvents such as cyclohexane, cyclopentane and methylcyclopentane, aliphatic hydrocarbon solvents such as hexane, heptane and octane, toluene, benzene, xylene, ethylbenzene and mesitylene, etc. Aromatic hydrocarbon solvents, halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethylene, 1,1-dichloroethylene, tetrachloroethylene, chlorobenzene and dichlorobenzene may be used alone or in combination of two or more. it can. Of these, alicyclic hydrocarbon solvents and aromatic hydrocarbon solvents are more preferred. These solvents are usually used in the range of 0 to 2,000 parts by weight with respect to 100 parts by weight of the total monomers.

  In the method for producing a cyclic olefin-based addition copolymer of the present invention, the molecular weight of the resulting copolymer can be arbitrarily controlled by performing the addition copolymerization reaction in the presence of a molecular weight regulator, and as a result. The flow characteristics in melt molding can be controlled. Examples of the molecular weight regulator include α-olefin compounds such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, trimethylvinylsilane and trimethoxyvinylsilane, or substituted α-olefin compounds, and monocyclic monoolefins such as cyclopentene. A compound or an aromatic vinyl compound such as styrene or α-methylstyrene is used. Among these molecular weight regulators, it is more preferable to use an α-olefin compound or a monocyclic monoolefin compound, and ethylene is particularly preferable. The amount of molecular weight regulator used varies depending on the target molecular weight of the cyclic olefin-based addition copolymer, the type of catalyst component, polymerization temperature conditions, etc. The amount is preferably 0.001 to 0.5 times. Moreover, these molecular weight regulators may be used individually by 1 type, and may be used in combination of 2 or more type.

  Since the palladium-based polymerization catalyst used in the production method of the cyclic olefin-based addition copolymerization of the present invention is very highly active, the conversion rate should be 96% or more, more preferably 99% or more only by using a small amount. it can. Therefore, the removal process of the residual monomer and metal component is not necessarily required. If necessary, a known method may be appropriately used to remove a monomer or a metal component. For example, a polymerization reaction solution may be prepared using an oxycarboxylic acid such as lactic acid, glycolic acid, oxypropionic acid and oxybutyric acid, Extraction and separation using aqueous solutions such as ethanolamine, dialkylethanolamine and ethylenediaminetetraacetate, or methanol or ethanol solutions, or adsorption and adsorption using sorbents such as diatomaceous earth, silica, alumina, activated carbon and celite. A metal component can be removed by filtering with a filter. Alternatively, the polymerization reaction solution can be coagulated using alcohols such as methanol, ethanol and propanol, or ketones such as acetone and methyl ethyl ketone. The metal component contained in the cyclic olefin addition copolymer of the present invention is preferably 10 ppm or less, more preferably 5 ppm or less as a Pd atom.

A cyclic olefin addition copolymer is obtained from the polymerization reaction solution through a desorption step.
In that case, you may mix | blend an additive as needed. The desolubilization method is not particularly limited. For example, the solution may be heated and concentrated under reduced pressure, steam may be introduced, or dried and pelletized using an extruder or the like. The polymerization reaction solution may be cast as it is to form a film.

<Polymerization catalyst>
In the method for producing a cyclic olefin-based addition copolymer of the present invention, the above-described monomer composition is prepared by using a catalyst obtained by using the following (a), (b) and (d), or the following (c): And (d) are subjected to addition copolymerization in the presence of the catalyst obtained.

(A) an organic acid salt of palladium or a β-diketonate compound of palladium;
(B) a phosphine compound represented by the following formula (b);
P (R ¹ ) ₂ (R ² ) (b)
(In formula (b), R ¹ is a substituent selected from a cyclopentyl group, a cyclohexyl group and an isopropyl group, and R ² represents a hydrocarbon group having 3 to 10 carbon atoms.)
(C) a phosphine complex of divalent palladium represented by the following formula (c);
Pd [P (R ¹ ) ₂ (R ² )] _n X ₂ (c)
(In the formula (c), R ¹ is a substituent selected from a cyclopentyl group, a cyclohexyl group and an isopropyl group, and R ² represents a hydrocarbon group having 3 to 10 carbon atoms. X is an organic acid anion or β-di- (It is a ketonate anion. N represents 1 or 2.)
(D) An ionic boron compound.

  In the present invention, a molded article having excellent mechanical strength can be obtained by using a palladium-based catalyst obtained from the catalyst component. Furthermore, since it exhibits a very high polymerization activity, it is possible to produce an addition copolymer with a high conversion rate exceeding 95% by using an extremely small amount of a palladium compound, and it remains in the resulting addition copolymer. Monomer and metal component can be kept sufficiently low.

Hereinafter, each catalyst component will be described.
(A) An organic acid salt of palladium or a β-diketonate compound of palladium is, for example, a divalent palladium carboxylate, sulfonate, or β-diketonate compound,
1) Palladium acetate, palladium chloroacetate, palladium fluoroacetate, palladium trifluoroacetate, palladium propionate, palladium 3,3,3-trifluoropropionate, palladium butyrate, palladium 3-methylbutyrate, palladium pentanoate, palladium hexanoate , Palladium 2-ethylhexanoate, palladium octoate, palladium dodecanoate, palladium 2-methylpropenoate, palladium octadec-9-enoate, palladium cyclohexanecarboxylate, palladium benzoate, palladium 2-methylbenzoate, 4-methyl An organic monocarboxylate having 1 to 15 carbon atoms such as palladium benzoate and palladium naphthalenecarboxylate;
2) C1-C20 organic sulfonates such as palladium methanesulfonate, palladium trifluoromethanesulfonate, palladium p-toluenesulfonate, palladium benzenesulfonate, palladium naphthalenesulfonate and palladium dodecylbenzenesulfonate;
3) β-diketonate compounds having 5 to 15 carbon atoms such as 2,4-pentadione (acetylacetonate) of palladium, methyl acetoacetate, ethyl acetoacetate and hexafluoroacetylacetone are preferred. Among these, palladium acetate, palladium propionate, palladium 2-ethylhexanoate, and palladium bis (acetylacetonate) are more preferable, and palladium acetate is particularly preferable.

  (B) Examples of the phosphine compound represented by the formula (b) include tricyclopentylphosphine, dicyclopentyl (cyclohexyl) phosphine, dicyclopentyl (3-methylcyclohexyl) phosphine, dicyclopentyl (isopropyl) phosphine, dicyclopentyl (s- Butyl) phosphine, dicyclopentyl (t-butyl) phosphine, dicyclopentyl (2-methylphenyl) phosphine, tricyclohexylphosphine, dicyclohexyl (cyclopentyl) phosphine, dicyclohexyl (3-methylcyclohexyl) phosphine, dicyclohexyl (isopropyl) phosphine, dicyclohexyl ( 2-Methylphenyl) phosphine, triisopropylphosphine and the like are preferred. Of these, tricyclopentylphosphine and tricyclohexylphosphine are more preferably used.

  (C) Since the divalent palladium phosphine complex represented by the formula (c) has better solubility in hydrocarbon solvents than the palladium compound mentioned in the catalyst component (a), It is advantageous in the polymerization process. Moreover, it is advantageous in that the generation efficiency of active species is high and the induction period is hardly observed.

As a phosphine complex of palladium represented by the formula (c), for example,
(Tricyclopentylphosphine) palladium di (acetate),
[Bis (tricyclopentylphosphine)] palladium di (acetate),
[Dicyclopentyl (t-butyl) phosphine] palladium di (acetate),
[Dicyclopentyl (cyclohexyl) phosphine] palladium di (acetate),
[Dicyclopentyl (2-methylphenyl) phosphine] palladium di (acetate), (tricyclopentylphosphine) palladium bis (trifluoroacetate),
Bis (tricyclopentylphosphine) palladium bis (trifluoroacetate),
[Dicyclopentyl (cyclohexyl) phosphine] palladium bis (trifluoroacetate),
(Tricyclopentylphosphine) palladium di (propionate),
Bis (tricyclopentylphosphine) palladium di (propionate),
(Tricyclopentylphosphine) palladium bis (2-ethylhexanoate),
Bis (tricyclopentylphosphine) palladium bis (2-ethylhexanoate), (tricyclopentylphosphine) palladium bis (acetylacetonate),
Bis (tricyclopentylphosphine) palladium bis (acetylacetonate),
[Dicyclopentyl (cyclohexyl) phosphine] palladium bis (acetylacetonate),
(Tricyclopentylphosphine) palladium bis (trifluoromethanesulfonate),
Bis (tricyclopentylphosphine) palladium bis (trifluoromethanesulfonate),
(Tricyclohexylphosphine) palladium di (acetate),
[Bis (tricyclohexylphosphine)] palladium di (acetate),
[Dicyclohexyl (t-butyl) phosphine] palladium di (acetate),
[Dicyclohexyl (cyclopentyl) phosphine] palladium di (acetate),
[Dicyclohexyl (2-methylphenyl) phosphine] palladium di (acetate), (tricyclohexylphosphine) palladium bis (trifluoroacetate),
Bis (tricyclohexylphosphine) palladium bis (trifluoroacetate),
[Dicyclohexyl (cyclopentyl) phosphine] palladium bis (trifluoroacetate),
(Tricyclohexylphosphine) palladium di (propionate),
Bis (tricyclohexylphosphine) palladium di (propionate),
(Tricyclohexylphosphine) palladium bis (2-ethylhexanoate),
Bis (tricyclohexylphosphine) palladium bis (2-ethylhexanoate), (tricyclohexylphosphine) palladium bis (acetylacetonate),
Bis (tricyclohexylphosphine) palladium bis (acetylacetonate),
[Dicyclohexyl (cyclopentyl) phosphine] palladium bis (acetylacetonate),
(Tricyclohexylphosphine) palladium bis (trifluoromethanesulfonate),
And bis (tricyclohexylphosphine) palladium bis (trifluoromethanesulfonate). Among these,
(Tricyclopentylphosphine) palladium di (acetate),
(Tricyclopentylphosphine) palladium bis (trifluoroacetate),
(Tricyclopentylphosphine) palladium di (propionate),
(Tricyclopentylphosphine) palladium bis (2-ethylhexanoate),
(Tricyclopentylphosphine) palladium bis (acetylacetonate),
(Tricyclopentylphosphine) palladium bis (trifluoromethanesulfonate),
(Tricyclohexylphosphine) palladium di (acetate),
(Tricyclohexylphosphine) palladium bis (trifluoroacetate),
(Tricyclohexylphosphine) palladium di (propionate),
(Tricyclohexylphosphine) palladium bis (2-ethylhexanoate),
(Tricyclohexylphosphine) palladium bis (acetylacetonate),
(Tricyclohexylphosphine) palladium bis (trifluoromethanesulfonate),
Are more preferred, (tricyclopentylphosphine) palladium di (acetate), (tricyclopentylphosphine) palladium bis (acetylacetonate), (tricyclohexylphosphine) palladium di (acetate), (tricyclohexylphosphine) palladium bis (acetylacetonate) ) Is particularly preferred.

  For the synthesis of these phosphine complexes (c), a known method may be used as appropriate. After synthesis, the phosphine complex (c) may be used after being purified or isolated, or may be used without being isolated. For example, it is synthesized by reacting an appropriate palladium compound and a phosphine compound exemplified in the catalyst component (b) at a temperature of 0 to 70 ° C. in an aromatic hydrocarbon solvent or a halogenated hydrocarbon solvent. Also good.

(D) As the ionic boron compound, for example, a compound represented by the following formula (d) is used.
[R ^{3] +} [M (R ^{₄₎ 4] -} ... (d)
(In the formula (c), R ³ represents an organic cation having 4 to 25 carbon atoms selected from a carbenium cation, a phosphonium cation, an ammonium cation, or an anilinium cation. M represents a boron atom or an aluminum atom. R ⁴ represents Represents a phenyl group substituted with a fluorine atom or an alkyl fluoride.)
As the compound represented by the formula (d),
Triphenylcarbenium tetrakis (pentafluorophenyl) borate,
Tri (p-tolyl) carbenium tetrakis (pentafluorophenyl) borate,
Triphenylcarbenium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,
Tri (p-tolyl) carbenium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate,
Triphenylcarbenium tetrakis (2,4,6-trifluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate,
Diphenylphosphonium tetrakis (pentafluorophenyl) borate,
Tributylammonium tetrakis (pentafluorophenyl) borate,
N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,
N, N-diethylanilinium tetrakis (pentafluorophenyl) borate,
Etc. Among these, an ionic boron compound in which the cation is a carbenium cation and the anion is a tetrakis (pentafluorophenyl) borate anion or a tetrakis (perfluoroalkylphenyl) borate anion is more preferable, and triphenylcarbenium tetrakis (pentafluoro). Particularly preferred are phenyl) borate and triphenylcarbenium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate.

  (A) An organic acid salt of palladium or a β-diketonate compound of palladium, or (c) a phosphine complex of divalent palladium is 0.0005 to 0.02 mmol as a palladium atom per mole of monomer, more preferably When used in the range of 0.001 to 0.01 mmol, particularly preferably in the range of 0.001 to 0.005 mmol, a high conversion can be obtained, so that high economy and productivity are exhibited. In addition, since the metal component remaining in the addition copolymer can be kept low, it is possible to obtain a molded body with little coloring and excellent transparency, and the deashing step may be omitted in some cases.

  (B) The phosphine compound has a high polymerization activity when used in a range of 0.1 to 5 mol, more preferably 0.5 to 2 mol, with respect to 1 mol of palladium atom contained in the catalyst component (a). Become.

  With regard to the catalyst component (c) ionic boron compound, 0.5 to 10 moles, more preferably 0.7 to 5.0 moles, particularly preferably 1 to 1 mole of palladium atoms contained in the catalyst component (a). Preferably it is used in the range of 1.0-2.0 mol.

  Regarding each catalyst component of the above (a) to (d), in the present invention, there is no particular limitation on the preparation method and the usage method such as the order of addition, and simultaneously to the mixture of the monomer and solvent used for the polymerization reaction, Or you may add sequentially.

[Molded body]
The cyclic olefin addition copolymer of the present invention exhibits a softening point suitable for hot melt molding, and can be molded by methods such as injection molding, extrusion molding, and compression molding. Moreover, it can also shape | mold into shapes, such as a film and a sheet, by melt | dissolving in a suitable solvent and casting. Hot melt molding is particularly preferred because it does not require a solvent and is advantageous in terms of economy and productivity.

  The cyclic olefin addition copolymer of the present invention is excellent in optical properties such as transparency, chemical resistance, heat resistance, water resistance and moisture resistance, and has a softening point suitable for melt molding. Is suitably used for the production of optical films. The obtained optical film is excellent in balance in optical properties such as transparency, chemical resistance, heat resistance, water resistance and moisture resistance.

  In addition, the molded product of the cyclic olefin addition copolymer of the present invention includes a conductive film such as ITO, polythiophene, and polyaniline, a barrier film such as silicon dioxide, silicon nitride, and aluminum oxide as required, and other known hard A coat layer, an antireflection layer, an antifouling layer, an infrared filter layer, an ultraviolet filter layer, an adhesive layer and the like may be formed. Examples of means for forming these include coating, pasting, vacuum deposition, sputtering, and ion plating.

[Use]
The cyclic olefin-based addition copolymer of the present invention is excellent in transparency and heat resistance, and has low water absorption and dielectric constant, so that it can be suitably used for optical materials, electrical / electronic parts, medical equipment and the like.

  Optical materials include liquid crystal display elements, organic EL elements, plasma displays, electronic paper, display color filter substrates, nanoimprint substrates, and transparent conductive films and transparent conductive films laminated with ITO or conductive resin layers, touch panels, conductive materials, and so on. Optical plate, protective film, deflection film, retardation film, near infrared cut film, light diffusion film, antireflection film, high reflection film, transflective film, ND filter, dichroic filter, electromagnetic wave shielding film, beam splitter, optical communication Can be used for optical lenses and prisms such as filters, camera lenses, pickup lenses and F-θ lenses, and optical recording substrates such as MD, CD and DVD.

As electronic / electrical parts, they are used for containers, trays, carrier tapes, separation films, insulating films, printed circuit board materials, and the like.
As medical equipment, it is used for medical packaging materials, sterilization containers, syringes, pipes, tubes and ampoules.

〔Example〕
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. Various properties such as the molecular weight, softening point, transparency and strength of the film of the cyclic olefin addition copolymer were determined by the following methods.

(1) Molecular weight Molecular weight was calculated | required by standard polystyrene conversion using tetrahydrofuran (THF) for the mobile phase using gel permeation chromatography (GPC) (Shodex GPC-101; Showa Denko KK make).

(2) Softening point Using a TMA / SS6100 device (manufactured by Seiko Instruments),
Film size 4mm x 18mm,
10mm distance between chucks,
Tensile load 10g weight,
A tangent line was drawn on the curve before and after the inflection point of the temperature-thermal expansion curve measured at a temperature rising rate of 10 ° C./min, and the softening point was determined from the intersection of the tangent lines.

(3) Copolymer composition A part of the polymerization reaction solution was sampled, and the supernatant obtained by coagulating the polymer with excess isopropanol was gas chromatogram apparatus (GC-14B; manufactured by Shimadzu Corporation), capillary column (film thickness 1 μm; 25 mm; length 60 m), and the residual monomer was quantified to calculate the composition.
(4) Spectral light transmittance and haze The light transmittance at a wavelength of 400 nm was measured with a visible / ultraviolet spectrophotometer (U-2010 Spectro Photometer; manufactured by Hitachi, Ltd.) for a film having a thickness of 100 μm.

About haze, according to JIS K7105, Haze-Gard plus (B
YK-Gardner).
(5) Breaking strength, elongation, and breaking energy According to JIS K7113, the test piece was measured at a pulling speed of 3 mm / min.
(6) Water absorption The film was immersed in water at 23 ° C. for 24 hours, and the water absorption was determined from the change in weight before and after immersion.

In a 1.4 L stainless steel reactor under a nitrogen atmosphere, 600 g of toluene, 67 g (0.38 mol) of 5-hexylbicyclo [2.2.1] hept-2-ene and 5-decylbicyclo [2.2.1] 133 g (0.57 mol) of hepta-2-ene was charged, and ethylene was introduced to 0.010 MPa while stirring. The temperature in the vessel was raised to 30 ° C., and a toluene solution of (tricyclopentylphosphine) palladium di (acetate) 3.78 × 10 ⁻³ mmol and a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate 3. Polymerization was initiated by adding 78 × 10 ⁻³ mmol. As a result of carrying out the polymerization for a total of 12 hours, the conversion was 99% from the quantification of the unreacted monomer, and the 5-decylbicyclo [2.2.1] hept-2-ene content in the copolymer was 60 mol%. It was calculated. The reaction solution diluted with toluene was coagulated with 2 L of isopropyl alcohol and then heat-dried under vacuum to obtain 198 g of copolymer A. Copolymer A had Mn of 75,000 and Mw of 287,000. The ¹ H-NMR spectrum of copolymer A is shown in FIG.

To 100 parts by weight of this copolymer A, pentaerythrityltetox [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and tris (2,4-di-t-butylphenyl) 0.5 parts by weight of each phosphite was mixed, and then a film A having a thickness of 100 μm was prepared using a vacuum press at 240 ° C. The softening point of the film A is 145 ° C., and as shown in Table 1, it has excellent heat resistance, transparency and low water absorption, and the breaking elongation which is an index of the flexibility of the film and the breaking energy which is an index of the toughness It was found that the copolymer is very large and has excellent melt moldability.

In Example 1, 151 g (0.84 mol) of 5-hexylbicyclo [2.2.1] hept-2-ene and 49 g (0. 8 mol) of 5-decylbicyclo [2.2.1] hept-2-ene. 21 mol), a toluene solution of (tricyclopentylphosphine) palladium di (acetate) with 4.22 × 10 ⁻³ mmol and a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate with 4.22 × 10 ⁻³ mmol. Polymerization was carried out in the same manner as in Example 1 except that.

From the quantification of the unreacted monomer, the conversion rate was calculated to be 99%, and the 5-decylbicyclo [2.2.1] hept-2-ene content in the copolymer was calculated to be 20 mol%. The reaction solution diluted with toluene was coagulated with 2 L of isopropyl alcohol and then heat-dried under vacuum to obtain 198 g of copolymer B. Copolymer B had Mn of 72,000 and Mw of 279,000. The ¹ H-NMR spectrum of copolymer B is shown in FIG.

To 100 parts by weight of this copolymer B, pentaerythrityltetox [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and tris (2,4-di-t-butylphenyl) Each 0.5 parts by weight of phosphite was mixed, and then a film B having a thickness of 100 μm was prepared using a vacuum press at 280 ° C. The softening point of the film B is 185 ° C., and as shown in Table 1, it is excellent in heat resistance, transparency and low water absorption, and the breaking elongation which is an index of film flexibility and the breaking energy which is an index of toughness. It was found that the copolymer is very large and has excellent melt moldability.

In a 1.4 L stainless steel reactor in a nitrogen atmosphere, 589 g of toluene, 122 g (0.68 mol) of 5-hexylbicyclo [2.2.1] hept-2-ene, 5-decylbicyclo [2.2.1] Charge 59 g (0.25 mol) of hepta-2-ene and 26 g (0.20 mol) of bicyclo [2.2.1] hept-2-ene as a 75% by weight toluene solution, and add ethylene with stirring to 0 g. It introduced until it became 0.013MPa. The temperature inside the container was raised to 40 ° C., and a toluene solution of (tricyclopentylphosphine) palladium di (acetate) was added to a solution of 4.56 × 10 ⁻³ mmol and a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate was added. Polymerization was initiated by adding 56 × 10 ⁻³ mmol. As a result of carrying out the polymerization for a total of 10 hours, the conversion was 99% from the quantification of the unreacted monomer, and the 5-hexylbicyclo [2.2.1] hept-2-ene content in the copolymer was 60 mol%. The 5-decylbicyclo [2.2.1] hept-2-ene content was calculated to be 22 mol% and the bicyclo [2.2.1] hept-2-ene content was calculated to be 18 mol%. The reaction solution diluted with toluene was coagulated with 2 L of isopropyl alcohol, and then heat-dried under vacuum to obtain 198 g of copolymer C. Copolymer C had Mn of 69,000 and Mw of 264,000. The ¹ H-NMR spectrum of copolymer C is shown in FIG.

To 100 parts by weight of this copolymer C, pentaerythrityl tetokis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and tris (2,4-di-t-butylphenyl) Each 0.5 parts by weight of phosphite was mixed, and then a film C having a thickness of 100 μm was prepared using a vacuum press at 280 ° C. The softening point of the film C is 195 ° C., and as shown in Table 1, it has excellent heat resistance, transparency and low water absorption, and the elongation at break which is an index of the flexibility of the film and the breaking energy which is an index of toughness. It was found that the copolymer is very large and has excellent melt moldability.

[Comparative Example 1]
In a 1.4 L stainless steel reactor under nitrogen atmosphere, 565 g of toluene, 112 g (0.63 mol) of 5-hexylbicyclo [2.2.1] hept-2-ene and bicyclo [2 2.1] Hept-2-ene 118 g (0.94 mol)
The ethylene was introduced to 0.015 MPa while stirring. The temperature inside the container was raised to 50 ° C., and a toluene solution of (tricyclopentylphosphine) palladium di (acetate) 3.92 × 10 ⁻³ mmol and a toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate 3. Polymerization was initiated by adding 92 × 10 ⁻³ mmol. As a result of carrying out the polymerization for a total of 10 hours, the conversion was 99% from the quantification of the unreacted monomer, and the 5-hexylbicyclo [2.2.1] hept-2-ene content in the copolymer was 40 mol%. It was calculated. The reaction solution diluted with toluene was coagulated with 2 L of isopropyl alcohol and then heat-dried under vacuum to obtain 198 g of copolymer D. Copolymer D had Mn of 58,000 and Mw of 220,000.

To 100 parts by weight of this copolymer D, pentaerythrityl tetokis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and tris (2,4-di-t-butylphenyl) 0.5 parts by weight of each phosphite was mixed, and an attempt was made to produce a film using a vacuum press at 300 ° C., but no film was obtained.

Next, 100 parts by weight of this copolymer D was mixed with pentaerythrityltetox [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and tris (2,4-di-t- (Butylphenyl) phosphite was mixed with 0.5 parts by weight of each, then toluene was added to make a solution with a solid content of 20% by weight, cast on a PET film, dried at 100 ° C. for 1 hour and peeled off from the PET film. The peeled film was transferred onto a SUS plate and dried at 150 ° C. for 1 hour, and further dried at 180 ° C. for 2 hours to obtain a film D having a thickness of 100 μm. The softening point of the film D is 240 ° C., and as shown in Table 1, it is excellent in heat resistance, transparency and low water absorption, has a high breaking strength, but has a small elongation, and is a break that is an index of the toughness of the film. Since the energy was small, the film was fragile and the copolymer was difficult to be melt-molded.

[Comparative Example 2]
In a 1.4 L stainless steel reactor under a nitrogen atmosphere, 600 g of toluene, 60 g (0.40 mol) of 5-butylbicyclo [2.2.1] hept-2-ene, 5-decylbicyclo [2
. 2.1] 140 g (0.60 mol) of hepta-2-ene was charged, and ethylene was introduced to 0.010 MPa while stirring. The temperature inside the container was raised to 30 ° C., and a toluene solution of (tricyclopentylphosphine) palladium di (acetate) was added to 3.99 × 10 ⁻³ mmo.
Polymerization was initiated by adding 3.99 × 10 ⁻³ mmol of toluene solution of l and triphenylcarbenium tetrakis (pentafluorophenyl) borate. As a result of carrying out the polymerization for a total of 12 hours, the conversion was 99% from the quantification of the unreacted monomer, and the 5-decylbicyclo [2.2.1] hept-2-ene content in the copolymer was 60 mol%. It was calculated. The reaction solution diluted with toluene was coagulated with 2 L of isopropyl alcohol, and then heat-dried under vacuum to obtain 198 g of copolymer E. Copolymer E had Mn of 73,000 and Mw of 285,000.

To 100 parts by weight of this copolymer E, pentaerythrityltetox [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and tris (2,4-di-t-butylphenyl) 0.5 parts by weight of each phosphite was mixed, and then a film E having a thickness of 100 μm was obtained using a vacuum press at 250 ° C. The softening point of the film E was 150 ° C., and as shown in Table 1, the softening point was slightly higher than that of the film A of Example 1, but both the elongation at break and break energy were inferior.

The cyclic olefin addition copolymer of the present invention can be suitably used for optical materials, electrical / electronic parts, medical equipment and the like.
Optical materials include liquid crystal display elements, organic EL elements, plasma displays, electronic paper, display color filter substrates, nanoimprint substrates, and transparent conductive films and transparent conductive films laminated with ITO or conductive resin layers, touch panels, conductive materials, and so on. Optical plate, protective film, deflection film, retardation film, near infrared cut film, light diffusion film, antireflection film, high reflection film, transflective film, ND filter, dichroic filter, electromagnetic wave shielding film, beam splitter, optical communication Can be used for optical filters and camera lenses, pickup lenses, optical lenses and prisms such as F-θ lenses, and optical recording substrates such as MD, CD and DVD.

  As electronic / electrical parts, it can be used for containers, trays, carrier tapes, separation films, insulating materials for office automation equipment, insulating layer materials for flexible printed circuit boards, and the like.

  As medical equipment, it is used for medical packaging materials, sterilization containers, syringes, pipes, tubes and ampoules.

FIG. 1 shows the ¹ H-NMR spectrum of copolymer A obtained in Example 1. FIG. 2 shows the ¹ H-NMR spectrum of copolymer B obtained in Example 2. FIG. 3 shows the ¹ H-NMR spectrum of copolymer C obtained in Example 3.

Claims (7)

A cyclic olefin-based addition copolymer comprising a structural unit (1) represented by the following formula (1) and a structural unit (2) represented by the following formula (2);

(In the formula (1), any ^one of A ¹ , A ² , A ³ and A ⁴ is an alkyl group having 6 carbon atoms, and the others are independently a hydrogen atom, a halogen atom or a methyl group. (P represents an integer of 0 to 5)

(In the formula (2), any one of B ¹ , B ² , B ³ and B ⁴ is an alkyl group having 7 to 12 carbon atoms, and the others are independently a hydrogen atom, a halogen atom or methyl. Q is an integer of 0 to 5).   The molar ratio of the structural unit (1) to the structural unit (2) (structural unit (1) / structural unit (2)) is 10/90 to 90/10, and the structural unit (1) and the structural unit (2 The cyclic olefin addition copolymer according to claim 1, wherein the total of the cyclic olefin-based addition copolymer is an amount of 80 to 100 mol% in all structural units. The cyclic olefin addition copolymer according to claim 1 or 2, wherein the structural unit (3) represented by the following formula (3) is contained in all structural units in an amount of 20 mol% or less. ;

(In formula (3), C ^{1 to} C ⁴ are each independently selected from the group consisting of an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkenylcarbonyloxy group, an acid anhydride group, an oxetanyl group, and a hydrolyzable silyl group. A hydrogen atom; a methyl group; and an atom or group selected from a halogen atom, and r represents an integer of 0 to 5.   The cyclic olefin addition copolymer according to any one of claims 1 to 3, which has a softening point of 80 to 210 ° C and a number average molecular weight of 20,000 to 200,000. Monomer (1m) represented by the following formula (1m), monomer (2m) represented by the following formula (2m), and monomer represented by the following formula (3m) as necessary (3m) and
The molar ratio of monomer (1m) to monomer (2m) (monomer (1m) / monomer (2m)) satisfies 10/90 to 90/10, and
A monomer composition in which the total of the monomer (1m) and the monomer (2m) is in an amount of 80 to 100 mol% in all monomers,
A cyclic olefin characterized by addition copolymerization in the presence of a catalyst obtained using the following (a), (b) and (d), or a catalyst obtained using the following (c) and (d): A method for producing a system addition copolymer;

(In the formula (1m), any ^one of A ¹ , A ² , A ³ and A ⁴ is an alkyl group having 6 carbon atoms, and the others are independently a hydrogen atom, a halogen atom or a methyl group. (P represents an integer of 0 to 5)

(In the formula (2m), any one of B ¹ , B ² , B ³ and B ⁴ is an alkyl group having 7 to 12 carbon atoms, and the others are independently a hydrogen atom, a halogen atom or methyl. (Q represents an integer of 0 to 5)

(In Formula (3m), C ^{1 to} C ⁴ are each independently selected from the group consisting of an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkenylcarbonyloxy group, an acid anhydride group, an oxetanyl group, and a hydrolyzable silyl group. Represents a hydrogen atom; a methyl group; and an atom or group selected from halogen atoms, r represents an integer of 0 to 5).
(A) an organic acid salt of palladium or a β-diketonate compound of palladium;
(B) a phosphine compound represented by the following formula (b);
P (R ¹ ) ₂ (R ² ) (b)
(In formula (b), R ¹ is a substituent selected from a cyclopentyl group, a cyclohexyl group or an isopropyl group, and R ² represents a hydrocarbon group having 3 to 10 carbon atoms.)
(C) a phosphine complex of divalent palladium represented by the following formula (c);
Pd [P (R ¹ ) ₂ (R ² )] _n X ₂ (c)
(In formula (c), R ¹ is a substituent selected from a cyclopentyl group, a cyclohexyl group and an isopropyl group, and R ² represents a hydrocarbon group having 3 to 10 carbon atoms. X is an organic acid anion or β-di- Ketonate anion, n is 1 or 2.]
(D) An ionic boron compound.   An optical film formed from the cyclic olefin addition copolymer according to any one of claims 1 to 4 by a solution casting method (cast method).   An optical film formed from the cyclic olefin addition copolymer according to any one of claims 1 to 4 by a melt molding method.

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