JP2003327630A - Cyclic olefin copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a cyclic olefin copolymer improved in transparency, heat resistance and water resistance (low water absorption) by resolving the problems in conventional transparent resins and further improved in low birefringence and an improved mechanical property (toughness). <P>SOLUTION: The cyclic olefin copolymer has (A) a structural unit having a cyclic olefin skeleton with a specified structure, (B) a structural unit with an electron attractive unit (excepting the structural unit (A)), and (C) at least one structural unit selected from the group consisting of a structural unit of formula (2) (wherein, R<SP>5</SP>and R<SP>6</SP>are each independently hydrogen atom or a 1-20C alkyl and at least one of R<SP>5</SP>and R<SP>6</SP>is the 1-20C alkyl) and a structural unit of formula (3) (wherein, R<SP>7</SP>and R<SP>8</SP>are each independently hydrogen atom or a 1-20C alkyl and R<SP>9</SP>is a 1-20C alkyl). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a cyclic olefin-based copolymer having excellent transparency, mechanical properties, heat resistance and water resistance, as well as low birefringence and mechanical properties (toughness).

[0002]

2. Description of the Related Art Conventionally, transparent resins have been used for automobile parts,
It has been used as a material for a molded body that requires transparency in the fields of lighting equipment, electric parts, and the like. Recently, as a material for optical parts such as optical lenses and prisms that require higher optical properties, transparent resins have come to be used as a substitute material for glass. The demand for is becoming severe. That is, in addition to high transparency, it is required to meet high-level requirements for heat resistance, mechanical strength (mechanical properties), water resistance (low water absorption), and low birefringence. Is coming. Conventionally, acrylic resins and polycarbonate resins have been generally known as transparent resins. However, acrylic resin is excellent in transparency,
It has drawbacks such as insufficient heat resistance, high water absorption and poor water resistance. In order to improve such a drawback of the acrylic resin, a terpolymer (contains a monomer having a (meth) acrylic acid ester, a monomer having a norbornene skeleton, and maleic anhydride) as a constituent component Kaihei 4-6
No. 3810), or a binary copolymer of methyl methacrylate and a monomer having a norbornene skeleton (JP-A-7-24).
No. 2711), a molded product obtained from these copolymers is extremely brittle, has insufficient toughness, and has a serious problem that it may crack when the molded product is taken out. On the other hand, the polycarbonate resin is superior to the acrylic resin in heat resistance, toughness and water resistance, but has a problem that it has a high birefringence and is inferior in transparency to the acrylic resin.

In order to solve the above problems of conventional transparent resins, in recent years, cyclic olefin resins having high transparency, water resistance (low water absorption), heat resistance, low birefringence and the like have been developed. Developed and used as an optical material to replace glass for advanced optical components. However,
Even with these cyclic olefin resins, there is a problem that the birefringence is not always sufficiently reduced and the toughness is not sufficient for use in recent lenses and optical disks, and therefore, it is more excellent. Development of a transparent resin having birefringence and improved toughness is desired.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems of the conventional transparent resin, to provide excellent transparency, heat resistance and water resistance (low water absorption), as well as low birefringence. It is to provide a novel cyclic olefin-based copolymer which is also excellent in mechanical properties (toughness).

[0005]

Means for Solving the Problems In order to achieve the above object, the present inventors have (A) a structural unit having a cyclic olefin skeleton represented by the following general formula (1), and (B) an electron-withdrawing group. And (C) a structural unit represented by the following general formula (2) and a structural unit represented by the following general formula (3). Provided is a cyclic olefin-based copolymer having at least one structural unit selected from the group.

[0006]

[Chemical 6] [In the formula, m and n are each independently an integer of 0 to 2,
R ¹ , R ² , R ³ and R ⁴ are independently a hydrogen atom; a halogen atom to the ring structure; a substituted or unsubstituted carbon atom which may have a linking group containing oxygen, nitrogen, sulfur or silicon. Represents a hydrocarbon group of the number 1 to 20; or a polar group. ]

[0007]

[Chemical 7] [In the formula, R ⁵ and R ⁶ are independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and at least one of R ⁵ and R ⁶ is an alkyl group having 1 to 20 carbon atoms. ]

[0008]

[Chemical 8] [Wherein R ⁷ and R ⁸ are independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ⁹ is 1 to 1 carbon atom.
20 alkyl groups. ]

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The cyclic olefin-based copolymer of the present invention contains a monomer represented by the following general formula (6) (hereinafter referred to as "specific monomer (A)") in the molecule. A monomer having one olefinically unsaturated bond and at least one electron-withdrawing group at the same time (however, a monomer represented by the following general formula (6) is excluded. Body (B) "
Say. ), And at least one monomer selected from the group consisting of a monomer represented by the following general formula (7) and a monomer represented by the following general formula (8) (hereinafter, referred to as “specific It can be obtained by copolymerizing with a monomer (C) ”by a radical reaction. <Specific monomer (A)>

[0010]

[Chemical 9] [In the formula, R ^{1 to} R ⁴ , m and n are as defined for the general formula (1) (provided that in the case of n = 0 and m = 1, one more non-polymerizable endocyclic ring It may have a saturated bond). ]

The above R ^{1 to} R ⁴ will be described. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and isobutyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; phenyl group Aryl groups such as naphthyl group and anthracenyl group; alkaryl groups such as methylphenyl group, ethylphenyl group and isopropylphenyl group; benzyl group
And an aralkyl group such as a phenethyl group; and the like. The hydrogen atom of these hydrocarbon groups may be substituted, and examples of the substituent include a halogen atom such as fluorine, chlorine and bromine, a cyano group and a phenylsulfonyl group.

The above-mentioned substituted or unsubstituted hydrocarbon group may be directly bonded to a ring structure, or a linking group (linkag) containing oxygen, nitrogen, sulfur or silicon.
It may be attached to the ring structure via e). Examples of the linking group include a carbonyl group (-C (= O)-), a carbonyloxy group (-C (= O) O-), an oxycarbonyl group (-OC (= O)-), a sulfonyl group ( -SO ₂
-), Ether bond (-O-), thioether bond (-)
S-), imino group (-NH-), amide bond (-NHC)
O-, -CONH-), siloxane bond (-OSi (R
₂ )-) (wherein R is an alkyl group such as methyl or ethyl)
And the like, and may be a linking group containing a plurality of these. More specifically, the linking group is an ether bond (-
When it is O-), the substituent on the ring structure is, for example, methoxy group, ethoxy group, n-propoxy group, i-
Examples thereof include alkoxyl groups such as propoxy group, n-butoxy group and t-butoxy group, and halogen-substituted alkoxyl groups such as pentafluoropropoxy group and heptafluoropropoxy group. The linking group is a carbonyloxy group (-
When C (= O) O-), the substituent on the ring structure may, for example, be an acetoxy group, a propionyloxy group or a benzoyloxy group. When the linking group is an oxycarbonyl group (-OC (= O)-), examples of the substituent for the ring structure include a methoxycarbonyl group,
Alkyloxycarbonyl groups such as ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, trifluoroethoxycarbonyl group; and, for example, phenoxycarbonyl group, naphthyloxycarbonyl group, fluorenyloxycarbonyl group, biphenylyl An oxycarbonyl group and the like can be mentioned. The linking group is a siloxane bond (—OSi (R ₂ ) —)
When R is an alkyl group such as methyl and ethyl in the formula, examples of the substituent for the ring structure include a trimethylsiloxy group and a triethylsiloxy group. Examples of the polar group include a hydroxyl group, a cyano group (—CN), an amide group (—CONH ₂ ), an amino group (—NH ₂ ), a carboxyl group, an imide ring-containing group; a triorgano group such as a trimethylsilyl group and a triethylsilyl group. Silyl group: Trimethoxysilyl group, trialkoxysilyl group such as triethoxysilyl group and the like can be mentioned.

The structural unit represented by the above general formula (1) is given.
Specific examples of the specific monomer (A) to be obtained include, for example,
However, the present invention is not limited to these.
It is not limited to the example. Bicyclo [2.2.1] hept-2-ene, Tricyclo [5.2.1.0]^2,6 ] -8-decene, 1-Methyltricyclo [5.2.1.0^2,6 ] -8-de
Sen, Tetracyclo [4.4.0.1^2,5 ． 1^7,10] -3-D
Decene, 10-methyltricyclo [4.4.0.1^2,5 ] -3-
Undecen, 5-methylbicyclo [2.2.1] hept-2-ene, 5,6-Dimethylbicyclo [2.2.1] hept-2-
EN, 1-methylbicyclo [2.2.1] hept-2-ene, 7-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-n-propylbicyclo [2.2.1] hept-2-
EN, 5-Isopropylbicyclo [2.2.1] hept-2-
EN, 5-n-butylbicyclo [2.2.1] hept-2-e
The 5-isobutylbicyclo [2.2.1] hept-2-e
The 5-Methoxycarbonylbicyclo [2.2.1] hept
-2-en, 5-methyl-5-methoxycarbonylbicyclo [2.
2.1] Hept-2-ene, 5-methyl-5-ethoxycarbonylbicyclo [2.
2.1] Hept-2-ene, 5-methyl-5-n-propoxycarbonylbicyclo
[2.2.1] hept-2-ene, 5-methyl-5-isopropoxycarbonylbicyclo
[2.2.1] hept-2-ene, 5-methyl-5-n-butoxycarbonylbicyclo
[2.2.1] hept-2-ene, 5-cyanobicyclo [2.2.1] hept-2-ene, 8-methyltetracyclo [4.4.0.1^2,5 ．
1^7,10] -3-dodecene, 8-Ethyltetracyclo [4.4.0.1^2,5 ．
1^7,10] -3-dodecene, 8-Methoxycarbonyltetracyclo [4.4.0.1
^2,5 ． 1^7,10] -3-dodecene, 8-ethoxycarbonyltetracyclo [4.4.0.1
^2,5 ． 1^7,10] -3-dodecene, 8-n-propoxycarbonyltetracyclo [4.4.
0.1^2,5 ． 1^7,10] -3-dodecene, 8-isopropoxycarbonyltetracyclo [4.4.
0.1^2,5 ． 1^7,10] -3-dodecene, 8-n-butoxycarbonyltetracyclo [4.4.
0.1^2,5 ． 1^7,10] -3-dodecene, 8-methyl-8-methoxycarbonyltetracyclo
[4.4.0.1^2,5 ． 1^{7, Ten}] -3-dodecene, 8-methyl-8-ethoxycarbonyltetracyclo
[4.4.0.1^2,5 ． 1^{7, Ten}] -3-dodecene, 8-Methyl-8-n-propoxycarbonyltetracycline
B [4.4.0.1^2,5． 1^7,10] -3-dodecene, 8-methyl-8-isopropoxycarbonyltetracycline
B [4.4.0.1^2,5． 1^7,10] -3-dodecene, 8-methyl-8-n-butoxycarbonyltetracyclo
[4.4.0.1^2,5 ． 1^7,10] -3-dodecene, Heptacyclo [8.7.0.1^3,6 ． 1^10,17 ． 1
^12,15 ． 0^2,7 ． 0^11,16 ] -4-Eikosen, 5-phenylbicyclo [2.2.1] hept-2-e
The 5-Methyl-5-phenylbicyclo [2.2.1] hep
To-2-en, 5-benzylbicyclo [2.2.1] hept-2-e
The 5- (4-methylphenyl) bicyclo [2.2.1] f
Put-2-en, 5- (4-ethylphenyl) bicyclo [2.2.1]
Put-2-en, 5- (4-isopropylphenyl) bicyclo [2.2.
1] hept-2-ene, 8-phenyltetracyclo [4.4.0.1^2,5 ． 1
^7,10] -3-dodecene, 5-fluorobicyclo [2.2.1] hept-2-e
The 5-fluoromethylbicyclo [2.2.1] hept-2
-En, 5-trifluoromethylbicyclo [2.2.1] hept
-2-en, 5-pentafluoroethylbicyclo [2.2.1] hep
To-2-en, 5,5-difluorobicyclo [2.2.1] hept-2
-En, 5,6-Difluorobicyclo [2.2.1] hept-2
-En, 5,5-bis (trifluoromethyl) bicyclo [2.
2.1] Hept-2-ene, 5,6-bis (trifluoromethyl) bicyclo [2.
2.1] Hept-2-ene, 5-methyl-5-trifluoromethylbicyclo [2.
2.1] Hept-2-ene, 5,5,6-Trifluorobicyclo [2.2.1] hep
To-2-en, 5,5,6-Tris (fluoromethyl) bicyclo [2.
2.1] Hept-2-ene, 5,5,6,6-Tetrafluorobicyclo [2.2.
1] hept-2-ene, 5,5,6,6-tetrakis (trifluoromethyl) bi
Cyclo [2.2.1] hept-2-ene, 5,5-difluoro-6,6-bis (trifluoromethyi)
Ru) bicyclo [2.2.1] hept-2-ene, 5,6-difluoro-5,6-bis (trifluoromethyi)
Ru) bicyclo [2.2.1] hept-2-ene, 5,5,6-trifluoro-5-trifluoromethylbi
Cyclo [2.2.1] hept-2-ene, 5-fluoro-5-pentafluoroethyl-6,6-bi
Su (trifluoromethyl) bicyclo [2.2.1] hep
To-2-en, 5,6-difluoro-5-heptafluoroisopropyl
-6-Trifluoromethylbicyclo [2.2.1] hep
To-2-en, 5-chloro-5,6,6-trifluorobicyclo [2.
2.1] Hept-2-ene, 5,6-dichloro-5,6-bis (trifluoromethyi)
Ru) bicyclo [2.2.1] hept-2-ene, 5,5,6-trifluoro-6-trifluoromethoxy
Bicyclo [2.2.1] hept-2-ene, 5,5,6-Trifluoro-6-heptafluoropropo
Xybicyclo [2.2.1] hept-2-ene, 8-fluorotetracyclo [4.4.0.1^2,5 ． 1
^7,10] -3-dodecene, 8-fluoromethyltetracyclo [4.4.0.1
^2,5 ． 1^7,10] -3-dodecene, 8-difluoromethyltetracyclo [4.4.0.1
^2,5 ． 1^7,10] -3-dodecene, 8-trifluoromethyltetracyclo [4.4.0.1
^2,5 ． 1^7,10] -3-dodecene, 8-pentafluoroethyltetracyclo [4.4.0.
1^2,5 ． 1^7,10] -3-dodecene, 8,8-Difluorotetracyclo [4.4.0.1
^2,5 ． 1^7,10] -3-dodecene, 8,9-Difluorotetracyclo [4.4.0.1
^2,5 ． 1^7,10] -3-dodecene, 8,8-bis (trifluoromethyl) tetracyclo
[4.4.0.1^2,5 ． 1^{7, Ten}] -3-dodecene, 8,9-bis (trifluoromethyl) tetracyclo
[4.4.0.1^2,5 ． 1^{7, Ten}] -3-dodecene, 8-methyl-8-trifluoromethyltetracyclo
[4.4.0.1^2,5 ． 1^{7, Ten}] -3-dodecene, 8,8,9-Trifluorotetracyclo [4.4.0.
1^2,5 ． 1^7,10] -3-dodecene, 8,8,9-Tris (trifluoromethyl) tetrasic
B [4.4.0.1^2,5． 1^7,10] -3-dodecene, 8,8,9,9-tetrafluorotetracyclo [4.
4.0.1^2,5 ． 1^7,10] -3-dodecene, 8,8,9,9-tetrakis (trifluoromethyl) te
Tracyclo [4.4.0.1^2,5 ． 1^7,10] -3-Dode
Sen, 8,8-Difluoro-9,9-bis (trifluoromethyi)
Le) tetracyclo [4.4.0.1^2,5 ． 1^7,10] -3
-Dodecene, 8,9-Difluoro-8,9-bis (trifluoromethyi)
Le) tetracyclo [4.4.0.1^2,5 ． 1^7,10] -3
-Dodecene, 8,8,9-trifluoro-9-trifluoromethyl te
Tracyclo [4.4.0.1^2,5 ． 1^7,10] -3-Dode
Sen, 8,8,9-trifluoro-9-trifluoromethoxy
Tetracyclo [4.4.0.1^2,5 ． 1^7,10] -3-D
Decene, 8,8,9-trifluoro-9-pentafluoropropo
Xytetracyclo [4.4.0.1^2,5 ． 1^7,10] -3
-Dodecene, 8-fluoro-8-pentafluoroethyl-9,9-bi
Sus (trifluoromethyl) tetracyclo [4.4.0.
1^2,5 ． 1^7,10] -3-dodecene, 8,9-difluoro-8-heptafluoroisopropyl
-9-Trifluoromethyltetracyclo [4.4.0.
1^2,5 ． 1^7,10] -3-dodecene, 8-chloro-8,9,9-trifluorotetracyclo
[4.4.0.1^2,5 ． 1 ^7,10] -3-dodecene, 8,9-dichloro-8,9-bis (trifluoromethyi)
Le) tetracyclo [4.4.0.1^2,5 ． 1^7,10] -3
-Dodecene, 8- (2,2,2-trifluoroethoxycarbonyl)
Tetracyclo [4.4.0.1^2,5 ． 1^7,10] -3-D
Decene, 8-methyl-8- (2,2,2-trifluoroethoxy
Carbonyl) tetracyclo [4.4.0.1^2,5 ． 1
^7,10] -3-dodecene, Tricyclo [5.2.1.0]^2,6 ] Deca-3,8-die
The These may be used alone or in combination of two or more.
be able to.

Among these monomers, bicyclo [2.
2.1] Hept-2-ene, 5-ethylbicyclo [2.
2.1] Hept-2-ene, 5-methylbicyclo [2.
2.1] hept-2-ene, 5,6-dimethylbicyclo [2.2.1] hept-2-ene, 1-methylbicyclo [2.2.1] hept-2-ene, 7-methylbicyclo [2.2.1] Hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-n-propylbicyclo [2.2.1] hept-2-ene, 5 -Isopropylbicyclo [2.2.1] hept-2-ene, 5-n
-Butylbicyclo [2.2.1] hept-2-ene, 5
-Isobutylbicyclo [2.2.1] hept-2-ene, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-methoxycarbonylbicyclo [2.2.1] Hept-2-ene, 5-methyl-5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-n-propoxycarbonylbicyclo [2.2.1] hept-2- Ene, 5-methyl-5-isopropoxycarbonylbicyclo [2.
2.1] hept-2-ene, 5-methyl-5-n-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyanobicyclo [2.2.1] hept-2-ene , 5-phenylbicyclo [2.2.1] hept-2-
Ene, 5-methyl-5-phenylbicyclo [2.2.
1] hept-2-ene, 5-benzylbicyclo [2.
2.1] hept-2-ene, 5- (4-methylphenyl) bicyclo [2.2.1] hept-2-ene, 5-
(4-Ethylphenyl) bicyclo [2.2.1] hept-2-ene, 5- (isopropylphenyl) bicyclo [2.2.1] hept-2-ene, tricyclo [5.
2.1.0 ^2,6 ] -8-decene, tricyclo [5.2.
1.0 ^2,6 ] deca-3,8-diene, 1-methyltricyclo [5.2.1.0 ^2,6 ] -8-decene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8
-Methyl-8-methoxycarbonyltetracyclo [4.
4.0.1 ^2,5 . It is preferable to use ^1,7,10 ] -3-dodecene in that a high molecular weight cyclic olefin copolymer is obtained.

More preferably, bicyclo [2.2.
1] hept-2-ene, 5-ethylbicyclo [2.2.
1] hept-2-ene, tricyclo [5.2.1.0]
^2,6 ] deca-3,8-diene, tricyclo [5.2.
1.0 ^2,6 ] deca-3-ene, and particularly preferably,
Bicyclo [2.2.1] hept-2-ene and 5-ethylbicyclo [2.2.1] hept-2-ene. When these monomers are used, a high molecular weight cyclic olefin-based copolymer can be obtained, and a molded product having particularly high toughness can be obtained from the copolymer.

<Specific monomer (B)> Specific monomer (B)
Has an electron-withdrawing group together with one olefinic unsaturated bond, and examples of the electron-withdrawing group include, for example, —CO—, —CONH—, — (CF ₂ ) p— (here, p is an integer of 1 to _{10), - C (CF 3)} 2 -, -
COO -, - SO -, - SO 2 - , and the like. By using the specific monomer (B) having an electron-withdrawing group, the specific monomer (A), which does not undergo radical polymerization by itself, forms a charge transfer complex with the specific monomer (B), thereby forming a specific monomer. Copolymerization of the body (A) becomes possible. Specific examples of the specific monomer (B) include, for example, divalent carboxylic acid anhydrides such as maleic anhydride, diesters such as diethyl fumarate and dibutyl fumarate, and the following general formula (4) or (5 And a specific monomer (B) which gives the structural unit represented by the general formula (4) is referred to as a "specific monomer (B1)", Further, the specific monomer (B) which gives the structural unit represented by the general formula (5)
Is referred to as “specific monomer (B2)”).

[0017]

[Chemical 10] [In the formula, R ¹⁰ is a hydrogen atom or a methyl group, and R ¹¹ is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms. In the general formula (4), R ¹¹ is, for example, a methyl group, an ethyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, an isoamyl group, a 2-ethylhexyl group, a lauryl group, Alkyl groups such as isooctyl group, n-octyl group, isononyl group, tridecyl group, stearyl group, isostearyl group; 2-hydroxyethyl group, 2-hydroxypropyl group, 2-methoxyethyl group, 2-ethoxyethyl, 4- Methoxybutyl group,
Substituted alkyl groups such as 2-butoxyethyl group, methoxyethoxyethyl group, phenoxyethyl group and 2-dimethylaminoethyl group; alicyclic groups such as cyclohexyl group and isobornyl group, among which methyl group, ethyl group, butyl group A structural unit having a cyclohexyl group or an isobornyl group is preferable because the cyclic olefin copolymer of the present invention has a good balance between heat resistance and water resistance (low water absorption).

Specific examples of the specific monomer (B1) include those shown below, but the present invention is not limited to these examples. Methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, t-butyl acrylate, isoamyl acrylate, cyclohexyl acrylate, acrylate-2
-Ethylhexyl, isobornyl acrylate, lauryl acrylate, stearyl acrylate, isooctyl acrylate, -n-octyl acrylate, isononyl acrylate, 2-ethoxyethyl acrylate, acrylic acid-
4-methoxybutyl, benzyl acrylate, 2-dimethylaminoethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-methoxyethyl acrylate, methyl methacrylate,
Butyl methacrylate, isobutyl methacrylate, -t-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, isostearyl methacrylate, benzyl methacrylate. , 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-ethoxyethyl methacrylate, 4-methoxybutyl methacrylate, methoxydiethylene glycol methacrylate methacrylate, 2-butoxyethyl methacrylate, phenoxy methacrylate. Ethyl, etc. These can be used alone or in combination of two or more.

Of these, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, isobornyl acrylate, methyl methacrylate, butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, The use of cyclohexyl methacrylate is preferable in that the heat resistance and water resistance (low water absorption) of the obtained cyclic olefin-based copolymer are well balanced. In particular, when methyl methacrylate, butyl methacrylate, isobutyl methacrylate, -t-butyl methacrylate, and cyclohexyl methacrylate are used, the cyclic olefin copolymer obtained can have a high molecular weight and a tough copolymer can be obtained. It is preferable because it is obtained.

[0020]

[Chemical 11] [In the formula, R ¹² is a hydrocarbon group having 1 to 20 carbon atoms. In the above general formula (5), R ¹² is, for example, a methyl group, an ethyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, an isoamyl group, a 2-ethylhexyl group, a heptyl group, Octyl group, isooctyl group, nonyl group, isononyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, lauryl group,
Examples thereof include alkyl groups such as alkyl groups such as stearyl groups and isostearyl groups; alicyclic groups such as cyclohexyl groups; aryl groups such as phenyl groups and naphthyl groups; aralkyl groups such as benzyl groups and phenethyl groups. Specific examples of the specific monomer (B2) include those shown below, but the present invention is not limited to these examples. N-methyl maleimide, N-ethyl maleimide, N-propyl maleimide, N-isopropyl maleimide, N-butyl maleimide, N-isobutyl maleimide, Nt-butyl maleimide, N-pentyl maleimide, N-hexyl maleimide, N-cyclohexyl Maleimide, N-heptyl maleimide, N-octyl maleimide, N-nonyl maleimide, N-decyl maleimide, N-undecyl maleimide, N-dodecyl maleimide, N-tridecyl maleimide, N-tetradecyl maleimide, N-pentadecyl maleimide , N-hexadecylmaleimide, N-heptadecylmaleimide, N
-Octadecyl maleimide, N-nonadecyl maleimide, N-eicosyl maleimide, N-phenyl maleimide, N-benzyl maleimide and the like. These can be used alone or in combination of two or more.

Of these, N-methylmaleimide, N
-Ethyl maleimide, N-propyl maleimide, N-isopropyl maleimide, N-butyl maleimide, N-isobutyl maleimide, Nt-butyl maleimide, N-
Hexyl maleimide and N-cyclohexyl maleimide are preferable because a copolymer having excellent transparency can be obtained. In particular, N-methylmaleimide, N-ethylmaleimide, and N-cyclohexylmaleimide are highly reactive, and the reaction is completed in a short time, which is preferable for production. When this specific monomer (B2) is used, a cyclic olefin-based copolymer that does not significantly impair transparency even at 405 nm (blue laser wavelength) can be obtained. The specific monomer (B
1) and the specific monomer (B2) can be used alone or in combination.

<Specific monomer (C)> Specific monomer (C)
Is a monomer represented by the following general formula (7) that gives a structural unit represented by the above general formula (2) (hereinafter referred to as “specific monomer (C1)”) and the above general formula (3). It is at least one kind of monomer selected from the group consisting of monomers represented by the following general formula (8) (hereinafter, referred to as “specific monomer (C2)”) that gives a structural unit represented by . By using this specific monomer (C), a structural unit having excellent flexibility is contained in the copolymer, so that a tough cyclic olefin-based copolymer can be obtained.

[0023]

[Chemical 12] [Wherein R ⁵ and R ⁶ are as defined for the general formula (2). ] Examples of R ⁵ and R ⁶ which are not hydrogen atoms include, for example, methyl group, ethyl group, n-propyl group,
n-butyl group, n-pentyl group, n-hexyl group, n-
Heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n
-Alkyl groups such as hexadecyl group, n-heptadecyl group, n-octadecyl group, and n-nonadecyl group. Specific examples of the specific monomer (C1) include those shown below, but the present invention is not limited to these examples. Propylene, 1
-Butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene , 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1-hexene, 2-methyl -1-Heptene, 2-methyl-1-octene, 2-methyl-1-nonene, 2-methyl-1-decene, 2-methyl-1-undecene, 2-
Methyl-1-dodecene, 2-methyl-1-tridecene,
2-methyl-1-tetradecene, 2-methyl-1-pentadecene, 2-methyl-1-hexadecene, 2-methyl-1-heptadecene, 2-methyl-1-octadecene,
2-methyl-1-nonadecene, 2-methyl-1-eicosene, 2-methyl-1-heneicosene, 2-methyl-
1-dodecene, 2-ethyl-1-butene, 2-ethyl-
1-pentene, 2-ethyl-1-hexene, 2-ethyl-1-heptene, 2-ethyl-1-octene, 2-ethyl-1-nonene, 2-ethyl-1-decene, 2-ethyl-1- Undecene, 2-ethyl-1-dodecene, 2-ethyl-1-tridecene, 2-ethyl-1-tetradecene, 2-ethyl-1-pentadecene, 2-ethyl-1-
Hexadecene, 2-ethyl-1-heptadecene, 2-ethyl-1-octadecene, 2-ethyl-1-nonadecene, 2-ethyl-1-eicosene, 2-ethyl-1-heneicosene, 2-ethyl-1-dodecene, 2-propyl-1-pentene, 2-propyl-1-hexene, 2-
Propyl-1-heptene, 2-propyl-1-octene, 2-propyl-1-nonene, 2-propyl-1-decene, 2-propyl-1-undecene, 2-propyl-
1-dodecene, 2-propyl-1-tridecene, 2-propyl-1-tetradecene, 2-propyl-1-pentadecene, 2-propyl-1-hexadecene, 2-propyl-1-heptadecene, 2-propyl-1- Octadecene, 2-propyl-1-nonadecene, 2-propyl-1
-Eicosene, 2-propyl-1-heneicosene, 2
-Propyl-1-dodecene and the like. These are 1 alone or 2
A combination of two or more species can also be used.

Of these, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1. -Hexene, 2-methyl-1-
Heptene, 2-methyl-1-octene, 2-ethyl-1
-Butene, 2-ethyl-1-pentene, 2-ethyl-1
-Hexene, 2-ethyl-1-heptene, 2-ethyl-
1-octene, 2-propyl-1-pentene, 2-propyl-1-hexene, 2-propyl-1-heptene, 2
Since -propyl-1-octene contains a structural unit having excellent flexibility in the copolymer, a copolymer having excellent toughness can be obtained, which is preferable. Especially, 1-butene, 1-pentene, 1-hexene, isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1-hexene, 2-ethyl-1-butene, 2- Ethyl-1-pentene, 2-ethyl-1-hexene, 2-propyl-1-
Pentene and 2-propyl-1-hexene are preferable because a copolymer having excellent toughness can be obtained without lowering the heat resistance. In particular, a monomer having a double bond α-position methylene hydrogen (aryl-position hydrogen) has high chain group mobility,
It is difficult to obtain a high molecular weight copolymer. It is preferable to use isobutene which does not have hydrogen at the aryl position because a copolymer having excellent heat resistance and toughness can be obtained.

[0025]

[Chemical 13] [In formula, R < ⁷ > -R < ⁹ > is as a definition regarding general formula (3). ]

Examples of R ⁷ and R ⁸ which are not hydrogen atoms and R ⁹ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group and n. -Hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n
-Undecyl group, n-dodecyl group, n-tridecyl group,
n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group,
Examples thereof include alkyl groups such as n-nonadecyl group and n-eicosyl group. Specific examples of the specific monomer (C2) include those shown below, but the present invention is not limited to these examples.

Methoxyethylene, ethoxyethylene, propoxyethylene, isopropoxyethylene, butyroxyethylene, isobutyroxyethylene, pentyloxyethylene, hexyloxyethylene, heptoxyethylene, octyloxyethylene, nonyloxyethylene, decyloxyethylene, Undecyloxyethylene, dodecyloxyethylene, tridecyloxyethylene, tetradecyloxyethylene, pentadecyloxyethylene, hexadecyloxyethylene, heptadecyloxyethylene, octadecyloxyethylene, nonadecyloxyethylene, eicosiloxyethylene, 2-methoxy Propylene, 2-ethoxypropylene, 2-propoxypropylene, 2-isopropoxypropylene, 2-butyroxypropylene, 2-isobutyroxypropyl 2-pentyloxypropylene, 2-hexyloxypropylene, 2-heptyloxypropylene, 2-octyloxypropylene, 2-nonyloxypropylene, 2-decyloxypropylene, 2-undecyloxypropylene, 2-dodecyloxy. Propylene, 2
-Tridecyloxypropylene, 2-tetradecyloxypropylene, 2-pentadecyloxypropylene, 2-hexadecyloxypropylene, 2-heptadecyloxypropylene, 2-octadecyloxypropylene, 2-nonadecyloxypropylene, 2-eico Siloxypropylene, 2
-Methoxy-1-butene, 2-ethoxy-1-butene,
2-propoxy-1-butene, 2-isopropoxy-1
-Butene, 2-butyroxy-1-butene, 2-isobutyroxy-1-butene, 2-pentyloxy-1-butene,
2-hexyloxy-1-butene, 2-heptyloxy-1
-Butene, 2-octyloxy-1-butene, 2-nonyloxy-1-butene, 2-decyloxy-1-butene, 2-
Undecyloxy-1-butene, 2-dodecyloxy-1-
Butene, 2-tridecyloxy-1-butene, 2-tetradecyloxy-1-butene, 2-pentadecyloxy-1-
Butene, 2-hexadecyloxy-1-butene, 2-heptadecyloxy-1-butene, 2-octadecyloxy-1
-Butene, 2-nonadecyloxy-1-butene, 2-eicosyloxy-1-butene, 2-methoxy-2-butene,
2-ethoxy-2-butene, 2-propoxy-2-butene, 2-isopropoxy-2-butene, 2-butyroxy-2-butene, 2-isobutyroxy-2-butene, 2-
Pentyloxy-2-butene, 2-hexyloxy-2-butene, 2-heptyloxy-2-butene, 2-octyloxy-2-butene, 2-nonyloxy-2-butene, 2-decyloxy-2-butene, 2-undecyloxy. -2-butene, 2-dodecyloxy-2-butene, 2-tridecyloxy-2-butene, 2-tetradecyloxy-2-butene,
2-pentadecyloxy-2-butene, 2-hexadecyloxy-2-butene, 2-heptadecyloxy-2-butene, 2-octadecyloxy-2-butene, 2-nonadecyloxy-2-butene, 2-eicosiloxy -2-butene etc. These can be used alone or in combination of two or more.

Of these, methoxyethylene, ethoxyethylene, propoxyethylene, isopropoxyethylene, butyroxyethylene, isobutoxyethylene,
2-methoxypropylene, 2-ethoxypropylene, 2
-Propoxypropylene, 2-isopropoxypropylene, 2-butyroxypropylene, 2-isobutyroxypropylene, 2-methoxy-2-butene, 2-ethoxy-
2-butene, 2-propoxy-2-butene, 2-isopropoxy-2-butene, 2-butoxy-2-butene,
2-Isobutyroxy-2-butene is preferable because it can contain a structural unit having excellent flexibility in the copolymer. In particular, methoxyethylene, ethoxyethylene, propoxyethylene, and structural units having excellent flexibility can be contained in the copolymer without lowering the heat resistance, which are preferable. The specific monomer (C1) and the specific monomer (C2) can be used alone or in combination.

The ratio of the structural units in the cyclic olefin copolymer of the present invention is (A): 1 to 45 mol% of the structural units represented by the general formula (1), and (B):
50 to 95 mol% of the structural unit having an electron-withdrawing property, and (C): at least one structural unit selected from the group consisting of structural units represented by the general formulas (2) and (3). 5 to 49 mol%, preferably (A) 3 to 30 mol%, (B) 55 to 90 mol%, and (C) 20 to 47 mol% (the above (A) to
The total proportion of (C) is 100 mol%).

In synthesizing the cyclic olefin copolymer of the present invention, a copolymerizable monomer other than the specific monomers (A) to (C) described above may be used in combination. Examples of the copolymerizable monomer include styrene, α-methylstyrene, β-methylstyrene, stilbene, butadiene, isoprene, ethyl vinyl sulfide and phenyl vinyl sulfide. When these are used, the amount used is about 5 to 10 mol% with respect to the total amount of the specific monomers (A) to (C).

If necessary, in addition to the specific monomers (A) to (C) described above, a cross-linking agent having at least two radically polymerizable groups in one molecule is used in combination, A cyclic olefin-based copolymer having high toughness and high molecular weight can be obtained. Specific examples of this cross-linking agent include, for example, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di ( (Meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di
(Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth)
Acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, bis (hydroxymethyl) tricyclodecane di (meth) acrylate, ethylene oxide of bisphenol A Or diol di (meth) acrylate which is an adduct of propylene oxide, ethylene oxide of hydrogenated bisphenol A or di (meth) acrylate of diol which is an adduct of propylene oxide, and diglycidyl ether of bisphenol A with hydroxy (meth) Epoxy (meth) acrylate to which hydroxyalkyl (meth) acrylate such as acrylate is added, di (meth) acrylate of polyoxyalkylenated bisphenol A, p- or m-divinylbenzene, triethylene group Call divinyl ether, N, N'-1,6-hexane di-maleimide, N,
N'-1,3-benzenedimaleimide, N, N'-
1,4-benzenedimaleimide and the like can be mentioned.

Commercially available products of the cross-linking agent include, for example, K
AYARAD-DPHA, KAYARAD R-60
4, DPCA-20, -30, -60, -120, HX
-620, D-310, D-330 (Nippon Kayaku Co., Ltd. product) Iupimer UV SA1002, SA2007
(Made by Mitsubishi Chemical Corporation), Viscoat # 195,
# 230, # 215, # 260, # 335HP, # 29
5, # 300, # 700 (Osaka Organic Chemical Industry Co., Ltd.)
Made), light acrylate 4EG-A, 9EG-A,
NP-A, DCP-A, BP-4EA, BP-4PA,
PE-3A, PE-4A, DPE-6A (all manufactured by Kyoeisha Chemical Co., Ltd.), Aronix M-208, M-21
0, M-215, M-220, M-240, M-30
5, M-309, M-315, M-325 (all manufactured by Toagosei Co., Ltd.) and the like. These crosslinkers are 1
They can be used alone or in combination of two or more.

The amount of the crosslinking agent used is 10 mol% or less, preferably 5 mol% or less, based on all the monomers. When the amount of the cross-linking agent used exceeds 10 mol%, when the polymerization reaction is carried out by solution polymerization, it becomes insoluble in the solvent, which causes problems in production such that stirring cannot be performed.

In the synthesis of the cyclic olefin copolymer of the present invention, known free radical-generating organic peroxides and azobis radical polymerization initiators can be used. Specific examples of the organic peroxide include dibenzoyl peroxide, diisobutyroyl peroxide, bis (2,4-dichlorobenzoyl) peroxide, (3,5,5-
Diacyl peroxides such as trimethylhexanoyl) peroxide, dioctanoyl peroxide, dilauroyl peroxide, distearoyl peroxide, etc .;

Ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, acetylacetone peroxide; hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, diisopropyl Hydroperoxides such as benzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide and t-hexyl hydroperoxide; di-t-butyl peroxide, dicumyl peroxide, dilauryl peroxide , Α, α'-bis (t-butylperoxy) diisopropylben, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylcumyl peroxide, 2,5-dimethyl- 2,5-bis (t-butylpa -Oxy) hexyne-3 and other dialkyl peroxides;

T-butyl peroxyacetate, t-butyl peroxypivalate, t-hexyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, 2,5- Dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, t-butyl Peroxy 2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleate, t-butylperoxy 3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-Dimethyl-2,5-bis (m-toluoylperoxy) hexane, α, α'-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxy neodecanoate, 1,1,3 , 3-tetramethyl Chill peroxyneodecanoate, 1-cyclohexyl-1-
Methyl ethyl peroxy neodecanoate, t-hexyl peroxy neodecanoate, t-butyl peroxy neododecanoate, t-butyl peroxybenzoate, t-
Hexylperoxybenzoate, bis (t-butylperoxy) isophthalate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxy m-toluoylbenzoate, 3,3 ', Peroxyesters such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone;

1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy)
3,3,5-Trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2,2-bis (t-butylperoxy)
Peroxyketals such as butane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane; t-hexylper Oxyisopropyl carbonate, t-butyl peroxy isopropyl carbonate, t-butyl peroxy-2-ethylhexyl carbonate, t-butyl peroxyallyl carbonate, di-n-propyl peroxy carbonate, disopropyl peroxy carbonate, bis (4- t-butylcyclohexyl) peroxycarbonate, di-2-ethoxyethylperoxycarbonate, di-2-ethylhexylperoxycarbonate, di-
Examples thereof include peroxycarbonates such as 2-methoxybutylperoxycarbonate and di (3-methyl-3-methoxybutyl) peroxycarbonate, and t-butyltrimethylsilylperoxide.

Specific examples of the azobis radical polymerization initiator include azobisisobutyronitrile, azobisisovaleronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2, 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) Isobutyronitrile, 2,2'-
Azobis [2-methyl-N- {1,1-bis (hydroxymethyl) -2-
Hydroxyethyl} propionamide], 2,2'-azobis
[2-Methyl-N- {2- (1-hydroxybutyl)} propionamide], 2,2'-azobis [2-methyl-N- (2-hydroxyethyl)]
-Propionamide], 2,2'-azobis [N- (2-propenyl)]
-2-Methylpropionamide], 2,2'-azobis (N-butyl
-2-methylpropionamide), 2,2'-azobis (N-cyclohexyl-2-methylpropionamide), 2,2'-azobis
[2- (5-Methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazoline-2-
Ile) propane] dihydrochloride, 2,2'-azobis
[2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 2,2′-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- {1- (2-hydroxyethyl) -2-imidazolin-2-yl} propane] dihydrochloride,
2,2'-azobis [2- (2-imidazolin-2-yl) propane],
2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis [N- (2-carboxyethyl)
-2-Methyl-propionamidine], 2,2'-azobis (2-methylpropionamidoxime), dimethyl 2,2'-azobisbutyrate, 4,4'-azobis (4-cyanopentanoic acid), 2,2′-azobis (2,4,4-trimethylpentane) and the like can be mentioned.

Further, persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate can also be used as the radical polymerization initiator. These radical polymerization initiators may be used either individually or in combination of two or more. The amount of the radical polymerization initiator used is 0.01 to 10 mol, based on 100 mol of the total amount of all the monomers,
Preferably 0.01-3 mol, more preferably 0.05
~ 2 moles. If the amount of the initiator is less than 0.01 mol, the reaction rate of the monomer becomes low, which is not preferable in production. Also, 10
If it exceeds the molar amount, the molecular weight of the obtained cyclic olefin-based copolymer will be small, and the toughness of the obtained molded article will be decreased, such being undesirable.

When the cyclic cycloolefin copolymer of the present invention is synthesized by using the specific monomer (B1) in an amount of 31 mol% or more based on all the monomers, the reaction rate is improved by using a Lewis acid. It is high and preferable in production. By using a Lewis acid, the electron-withdrawing property of the specific monomer (B1) is enhanced, so that the production of a homopolymer of the specific monomer (B1) can be suppressed, and the specific monomer (A ), The content of the structural unit represented by the general formula (1) in the copolymer is increased, and the strength (toughness), water resistance (low water absorption) and heat resistance are improved. An excellent cyclic olefin-based copolymer can be obtained. Further, since the rate of the copolymerization reaction is improved, the reaction time can be shortened, which is preferable in terms of productivity.

Examples of the Lewis acid to be used include aluminum trichloride, ethyl aluminum dichloride, ethyl aluminum sesquichloride, ethyl aluminum chloride, ethoxy aluminum dichloride, triethyl aluminum, aluminum triiodide, aluminum tribromide, antimony pentachloride, and the like. Examples include tin tetrachloride, antimony trichloride, iron trichloride, titanium tetrachloride, zinc dichloride, mercury dichloride, cadmium dichloride, boron trifluoride, boron trichloride, boron tribromide, boron triiodide, etc. . These can be used alone or in combination of two or more.

Of these Lewis acids, the use of ethylaluminum dichloride is preferable since the rate of the polymerization reaction is high and a high molecular weight cyclic cycloolefin copolymer is obtained.

The amount of the Lewis acid used is the above-mentioned specific monomer (B
1) It is 1 to 100 mol, preferably 1 to 50 mol, and more preferably 10 to 30 mol, relative to 100 mol. If the amount of the Lewis acid used is less than 1 mol, a homopolymer of the above-mentioned specific monomer (B1) is by-produced, and the resulting molded product of the cyclic olefin copolymer becomes cloudy or optically nonuniform. It is not preferable because it may cause defects such as If the amount of Lewis acid used exceeds 100 moles, the Lewis acid removal step becomes difficult, which is not preferable.

In order to produce the cyclic olefin-based copolymer of the present invention, any of the known bulk polymerization method, solution polymerization method, emulsion polymerization method, or suspension polymerization method can be adopted, but a specific polymerization method is used. When maleic anhydride is used as the monomer (B), or when a combination of the specific monomer (B1) and a Lewis acid is used, maleic anhydride or Lewis acid may be hydrolyzed. It is preferable to employ a bulk polymerization method or a solution polymerization method.

As the solvent used in the solution polymerization method, methanol, isopropyl alcohol, butyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate,
Examples thereof include ethyl lactate, ethyl lactate, tetrahydrofuran, dioxane, butyl cellosolve, dimethylformamide, dimethyl sulfoxide, benzene, toluene, xylene, ethylbenzene and acetonitrile. These solvents may be used alone or in combination of two or more. When the solution polymerization method is adopted, the amount of the solvent used is 500 parts by weight or less, preferably 300 parts by weight or less, particularly preferably 50 parts by weight, based on 100 parts by weight of all monomers.
It is less than or equal to parts by weight. If it exceeds 500 parts by weight, a high molecular weight cyclic olefin-based copolymer may not be obtained, which is not preferable.

When the copolymer of the present invention is produced by emulsion polymerization, emulsifiers that can be used include anionic surfactants, nonionic surfactants, and amphoteric surfactants. Examples of the anionic surfactant include sulfuric acid esters of higher alcohols, alkylbenzene sulfonates, fatty acid sulfonates, and phosphoric acid-based agents. As the nonionic surfactant, an alkyl ester type of polyethylene glycol, an alkyl ether type, an alkylphenol type, etc. are usually used. Further, examples of the amphoteric surfactant include those having a carboxylate salt, a sulfate ester salt, a sulfonate salt, and a phosphoric acid ester salt as an anion part and an amine salt, a quaternary ammonium salt, etc. as a cation part. Specific examples of the amphoteric surfactant include betaines such as lauryl betaine and stearyl betaine, amino acid type ones such as lauryl-β-alanine, lauryl di (aminoethyl) glycine, and octyl di (aminoethyl) glycine. . These emulsifiers can be used alone or in combination of two or more. The amount of the emulsifier used is usually about 0.1 to 5 parts by weight, based on 100 parts by weight of all the monomers.

In producing the cyclic cycloolefin copolymer of the present invention, a chain transfer agent can be used to adjust the molecular weight. Specific examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan, tetraethyl thiuram sulfide, and tetrachloride tetrachloride. Hydrocarbons such as carbon, ethylene bromide and pentanephenylethane, or acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycol, α-methylstyrene dimer and the like can be mentioned. These chain transfer agents may be used either individually or in combination of two or more. The amount of chain transfer agent used is 100 parts by weight of all monomers,
It is 5 parts by weight or less, preferably 1 part by weight or less, and particularly preferably 0. If the chain transfer agent is used in an amount of more than 5 parts by weight, a high molecular weight cyclic olefin-based copolymer may not be obtained, which is not preferable.

In the polymerization, it is appropriate to remove dissolved oxygen outside the system by vacuum deaeration or nitrogen substitution. The polymerization temperature employed is in the range of −50 to 200 ° C., and the polymerization time is preferably in the range of 1 to 100 hours. From the aspects of preventing runaway of polymerization and productivity, the polymerization temperature is in the range of 40 to 150 ° C., The polymerization time is more preferably in the range of 1 to 50 hours. Further, the temperature may be raised during the polymerization, if necessary. When synthesizing the cyclic cycloolefin copolymer of the present invention using the specific monomer (B1) and the Lewis acid, the polymerization temperature is 0 to 70 ° C., preferably 20 to 5
When synthesized at 0 ° C., a cyclic cycloolefin-based copolymer which has a large molecular weight and gives a tough molded product is obtained.

As the specific monomer (A), a monomer having a non-polymerizable cyclic unsaturated bond such as tricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene is used. In some cases, it is necessary to hydrogenate such unsaturated bonds with a hydrogenation catalyst. Even if not in the above case, when the olefinic unsaturated bond remains in the structural unit of the cyclic olefin-based copolymer of the present invention, such an unsaturated bond may be formed by using a hydrogenation catalyst depending on the necessity. It can be hydrogenated. The hydrogenation reaction is carried out by an ordinary method, that is, a hydrogenation catalyst is added to a solution of a cyclic olefin-based copolymer having an olefinic unsaturated bond, and hydrogen is added thereto under normal pressure to 300 atm, preferably 3 to 200 atm. Gas 0-200
It is carried out by operating at 0 ° C, preferably 20 to 180 ° C. As the hydrogenation catalyst, those used in ordinary hydrogenation reactions of olefinic compounds can be used. Heterogeneous catalysts and homogeneous catalysts are known as the hydrogenation catalyst.

Examples of the heterogeneous catalyst include solid catalysts in which a noble metal catalyst substance such as palladium, platinum, nickel, rhodium and ruthenium is supported on a carrier such as carbon, silica, alumina and titania. Further, as a homogeneous catalyst, nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium. , Dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium, and the like. The catalyst may be in the form of powder or particles. However, in the hydrogenation of the copolymer of the present invention, hydrogenation catalysts and conditions in which the aromatic ring is nucleus-hydrogenated cannot be used.

In these hydrogenation catalysts, the cyclic cycloolefin copolymer: hydrogenation catalyst (weight ratio) is 1: 1.
It is used at a ratio of × 10 ^-6 to 1: 2. As described above, the hydrogenated polymer obtained by hydrogenation has excellent thermal stability, and its characteristics are not deteriorated by heating during molding or use as a product. Here, the hydrogenation rate is usually 50% or more, preferably 80% or more, and more preferably 95% or more.

The cyclic olefin copolymer of the present invention is isolated from the reaction system by removing the residual monomer and solvent by a known method. As the metal compound such as Lewis acid used, inorganic acid such as hydrogen chloride, sulfuric acid and phosphoric acid, and organic acid such as lactic acid, acetic acid, p-toluenesulfonic acid and phosphoric acid ester may be used, if necessary. To be removed. The cyclic olefin-based copolymer of the present invention may further contain a suitable plasticizer, heat stabilizer, colorant, ultraviolet absorber, release agent, antioxidant and the like.

The glass transition temperature (Tg) of the cyclic olefin copolymer of the present invention is 80 to 300 ° C, preferably 90 to 200 ° C. If the Tg is less than 90 ° C, the heat resistance is insufficient, and if the obtained molded product is used in a part that easily accumulates heat in electronic products, automobile parts, etc., it will be thermally deformed, and when used as an optical lens, There is a problem that the beam diameter shifts, which is not preferable. Also, Tg is 30
If it exceeds 0 ° C, problems such as difficulty in molding occur, which is not preferable.

The total light transmittance of the cyclic olefin copolymer of the present invention is preferably 80% or more (optical path length: 3 mm). When the total light transmittance is less than 80%, the loss of light is large and the use as an optical material may be limited, which is not preferable.

The cyclic olefin copolymer of the present invention has a polystyrene-reduced number average molecular weight of 5,000 to 1,0 measured by gel permeation chromatography.
It is preferably 10,000. Number average molecular weight is 5
When it is less than 000, the toughness of the obtained molded product is insufficient, which may cause a problem in strength. Further, if the number average molecular weight exceeds 1,000,000, the melt viscosity becomes high and molding may become difficult.

The cyclic olefin-based copolymer of the present invention preferably has an absolute value of stress optical coefficient (C _R ) in the rubber state of 1000 or less, more preferably 800 or less,
It is particularly preferably 500 or less. C _R and the birefringence of the molded product have a good correlation, and if C _R exceeds 1000, the optical properties may be deteriorated due to the birefringence in optical applications such as lenses and optical disks. There is not preferable.

[0057]

EXAMPLES The method of the present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples. The copolymers obtained in Examples and Comparative Examples and the molded products thereof were evaluated by the following methods.

Number average molecular weight (Mn), weight average molecular weight
Measurement of (Mw): Measured by gel permeation chromatography (manufactured by Tosoh Corporation) HLC8220 (converted to polystyrene). Glass transition temperature (Tg): Measured at a temperature rising rate of 20 ° C./min using a differential scanning calorimeter (manufactured by Seiko Instruments Inc.) DSC6200. Copolymer composition: ¹³ C--N in deuterated chloroform
MR (manufactured by Bruker, AVANCE500, 500
MHz) inverted-decouplin
After measurement by the g method, flip angle of 30 degrees, and pulse interval of 1.6 seconds, the copolymerization composition was determined by the integral ratio of structural units derived from each monomer. For the measurement, a solution prepared by dissolving 300 mg of the copolymer and 100 mg of chromium acetylacetonate in 3.3 g of deuterated chloroform was used.

Stress optical coefficient ( _CR ): publicly known method (Po
Lymer Journal, Vol.27, No.9, pp943-950 (1995)). That is, the cyclic cycloolefin-based copolymer obtained in the present invention was press-molded to 0.5 mm × 5
Create four test pieces molded to a size of about 50 mm x 50 mm, apply different loads in the range of 10 to 300 g to each test piece, put them in a heating furnace at Tg + 20 ° C and leave for about 30 minutes. And stretched. afterwards,
The heating furnace was gradually cooled to room temperature with a load applied, and the retardation of each stretched test piece was measured. Phase difference is KOB
It measured using RA-21ADH (made by Oji Scientific Instruments). According to the following formula, stress (σ) and birefringence (ΔN) were calculated for each test piece, and C _R was calculated from the slope of the straight line of the σ-ΔN plot. Formula: σ = F / (d · w) (F: load, d: thickness of test piece after stretching, w: width of test specimen after stretching) Formula: ΔN = Re / d (Re: retardation, d: stretching Later test piece thickness) Formula: C _R = ΔN / σ (unit: Br = 10 ^-12 Pa ^-1 )

Transparency (measurement of total light transmittance): A test piece (thickness 3 for evaluating transparency by an injection molding machine.
mm) was prepared and the total light transmittance was measured according to ASTM D1003. -Water resistance (measurement of water absorption): A test piece (3 mm x 40 mm x 80 m ) for evaluating water resistance by an injection molding machine.
m) was prepared. The weight of this test piece: W ₀ was measured and 2
The weight after being immersed in water at 3 ° C. for 24 hours: W ₁ was measured, and the water absorption rate was calculated by the following mathematical formula. Formula: Water absorption rate (%) = [(W ₁ −W ₀ ) / W ₀ ] × 100 Bending characteristics (bending strength, bending elastic modulus) ASTM D79
It measured according to 0.

Example 1 A 3 L autoclave purged with nitrogen was placed under a nitrogen stream to remove dehydrated methyl methacrylate (MM).
A) 500.6 g (5 mol), dehydrated toluene 163 g,
Dehydrated toluene solution of ethylaluminum dichloride (EADC) (concentration: 24.7% by weight) 257.5 g (0.
5 mol) in that order, and the mixture was stirred at room temperature for 30 minutes. Then, a dehydrated toluene solution of bicyclo [2.2.1] hept-2-ene (NB) was added to this solution (concentration: 75% by weight).
64.9 g (4.5 mol), isobutene (IB) 28.
05 g (0.5 mol), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (trade name: V
-70, 7.71 g (0.025 mol) of Wako Pure Chemical Industries, Ltd. was added, and the mixture was stirred at 30 ° C for 10 hours. Further, 7.71 g (0.025 mol) of V-70 was added and the reaction was carried out for 10 hours (total monomer weight of reaction solution in polymerization reaction / toluene weight = 0.5). After the reaction, toluene 14
30 g was added and diluted to a uniform polymer solution (total monomer weight of diluted solution / toluene amount = 2). In order to remove EADC from the obtained reaction mixture, 54 g (0.6 mol) of lactic acid 1.2 times the molar amount of EADC was added, and the mixture was stirred at 60 ° C. for 1 hour. Then, 545 g of methanol was added to this solution (toluene weight / methanol weight ratio = 3.5), and 60
After stirring at ℃ for 1 hour, the reaction solution was taken out into a separating funnel. After standing for 6 hours, the reaction mixture separated into two layers. The upper layer was collected, 54 g (0.6 mol) of lactic acid was added, and 60
After stirring at 0 ° C for 1 hour, 545 g of methanol and 109 g of water were added, and the mixture was stirred at 60 ° C for 1 hour. After standing for 6 hours, the lower layer of the solution separated into two layers was collected and purified by reprecipitation with n-hexane. The purified product was separated and vacuum dried at 70 ° C. to obtain 676 g of a white powdery copolymer (yield = 71%).

A GPC chart of the obtained cyclic cycloolefin copolymer is shown in FIG. Polystyrene-equivalent weight average molecular weight (Mw) = 97,700, number average obtained molecular weight (Mn) = 42,000, molecular weight distribution (Mw / Mn) =
It was 2.31. The molecular weight distribution observed from the GPC chart was monomodal, and the bimodal molecular weight distribution observed when the PMMA homocopolymer was by-produced was not observed. D of the obtained cyclic cycloolefin-based copolymer
The SC chart is shown in FIG. Clear glass transition temperature (T
g) was observed only at 121 ° C., and no peak was observed at 100 ° C., which is the Tg derived from PMMA. The ¹³ C-NMR spectrum of the obtained cyclic cycloolefin copolymer is shown in FIG. Also, FIG.
The putative structural formula of the obtained copolymer is shown in the figure with the structural sites being numbered. Calculated from the NMR integrated value,
The composition of the structural units of the polymer is NB unit / IB unit / M
MA unit = 10.0 / 6.2 / 83.8 (mol%). The infrared spectroscopic spectrum (IR) of the obtained cyclic cycloolefin-based copolymer is shown in FIG. The following absorption peaks were observed on the IR chart (identification of absorption peaks is for reference only). 2994,2840cm ^-1: stretching vibration of C-H methylene group attribution 2951,2883cm ^-1: stretching vibration of C-H of the methyl groups attributed 1743,1723cm ^-1: stretching vibration attributable 1489cm of C = O of aliphatic ester ^-1 : paraffin C-H symmetric bending vibration attribution 1449 cm ^-1 : methyl group anti-symmetric bending vibration attribution 1387 cm ^-1 : hydrocarbon C-CH ₃ symmetric bending vibration attribution 1198, 1161 cm ^-1 : methyl ester Group C-O
Stretching vibration of -C 989 cm ⁻¹ : C—H out-of-plane bending vibration assignment of cyclohexane ring 964 cm ⁻¹ : Cyclohexane ring ring vibration assignment 915 cm ⁻¹ : Ring vibration assignment 739 cm ⁻¹ : Methylene group skeletal vibration assignment

The characteristics of the obtained copolymer are C _R = 28
Br, total light transmittance: 91%, water absorption: 0.55%, bending strength: 78 MPa, bending elastic modulus: 3970, yield point displacement: 9.35 mm. Also, the obtained test piece,
It did not break in the bending test, and the toughness was extremely excellent.

[Second Embodiment] In the first embodiment, the IB
(0.5 mol) of 1-hexene (Hx) 42.1 g
Copolymer 72 in the form of a white powder was obtained by polymerization, purification and drying in the same manner as in Example 1 except that the amount was changed to (0.5 mol).
5 g was obtained (yield = 75%). A GPC chart of the obtained cyclic cycloolefin-based copolymer is shown in FIG. Polystyrene-equivalent Mw = 94,600, Mn = 41,20
0, molecular weight distribution (Mw / Mn) = 2.29. G
The molecular weight distribution observed from the PC chart was unimodal, and the bimodal molecular weight distribution observed when the PMMA homocopolymer was by-produced was not observed. FIG. 6 shows a DSC chart of the obtained cyclic cycloolefin copolymer.
Shown in. Only one clear glass transition temperature (Tg) was observed at 122 ° C., which is a Tg derived from PMMA 10.
No peak was observed at 0 ° C. The ¹³ C-NMR spectrum of the obtained cyclic cycloolefin-based copolymer is shown in FIG. 7. The composition of the structural unit of the polymer calculated from the NMR integrated value is NB unit / Hx unit / MMA
The unit was 11.1 / 2.22 / 86.7 (mol%). The infrared spectroscopic spectrum (IR) of the obtained cyclic cycloolefin-based copolymer is shown in FIG. The following absorption peaks were observed on the IR chart (identification of absorption peaks is for reference only). 2994,2840cm ^-1: stretching vibration of C-H methylene group attribution 2952,2883cm ^-1: stretching vibration of C-H of the methyl groups attributed 1743,1711cm ^-1: stretching vibration attributable 1476cm of C = O of aliphatic ester ^-1 : C-H symmetric bending vibration attribution of paraffin 1451 cm ^-1 : Inverse symmetric bending vibration attribution of methyl group 1387 cm ^-1 : C-CH ₃ symmetry bending vibration attribution of hydrocarbon 1199, 1161 cm ^-1 : methyl ester Group C-O
-C stretching vibration 988cm ^-1: C-H out-of-plane of the cyclohexane ring deformation vibration attributed 964cm ^-1: cyclohexane ring in the vibration attributed 915 cm ^-1: ring vibration attributable 736cm ^-1: obtained Attribution skeleton vibration of methylene group The physical properties of the copolymer are shown below. C _R = 8.6
Br, total light transmittance: 93%, water absorption rate: 0.58%, bending strength: 76 MPa, bending elastic modulus: 4020, yield point displacement: 10.03 mm. Further, the obtained test piece did not break in the bending test, and the toughness was extremely excellent.

Example 3 In Example 1, the monomer charging composition was changed to IB 140.25 g (2.5 mol),
NB 235 g (2.5 mol), N-cyclohexylmaleimide (CHMI) 448 g (2.5 mol), butyl methacrylate (BMA) 355 g (2.5 mol) were used as the polymerization initiator, 1,1′-azobis (cyclohexane). -1-carbonitrile) (trade name: V-40, manufactured by Wako Pure Chemical Industries, Ltd.) 6.108 g (0.025 mol) was used,
The reaction was carried out at 90 ° C. for 5 hours without using EADC. Reprecipitation, purification and drying were carried out in the same manner as in Example 1 except that the EADC removal operation was not carried out to obtain 884 g of a white solid (yield = 75%). The composition of the structural unit of the polymer, which is targeted by NMR and IR analysis in the same manner as in Example 1, is NB unit / IB unit / BMA unit / CHMI unit =
It was found to be a quaternary copolymer with 15.9 / 20.3 / 25.0 / 38.8 (mol%). The physical properties of the obtained copolymer are shown below. Mw: 122,000, M
n: 57,000, molecular weight distribution (Mw / Mn) = 2.1
4, Tg: 125 ° C., C _R = 390Br, total light transmittance: 94%, water absorption rate: 0.38%, bending strength: 81MP
a, bending elastic modulus: 4210, yield point displacement: 9.02 m
m. Further, the obtained test piece did not break in the bending test, and the toughness was extremely excellent.

Comparative Example 1 MMA unit / NB unit = 6 in the same manner as in Example 1 except that IB is not used.
A 3/73 (mol%) binary copolymer was obtained. The physical properties of the obtained copolymer are shown below. Tg: 183 ° C., Mw =
49,900, Mn = 18,600, molecular weight distribution (Mw
/Mn)=2.68, _{C R} = 220Br, total light transmittance: 90%, water absorption rate: 0.97%, bending strength: 42MP
a, bending elastic modulus: 2530, yield point displacement: 3.25 m
m. Also, the obtained test piece was broken in the bending test,
It was a very brittle material. Moreover, when the molded body is taken out of the mold when the molded body is formed, the molded body is broken into pieces,
I could not take it out as a product.

[Comparative Example 2] Without using MMA and EADC, the monomer charging composition was changed to 627 g (5 mol) of a 75% toluene solution of NB and 280.6 g (5 of IB).
Polymerization reaction was carried out in the same manner as in Example 5 except that the amount was set to mol. After the reaction, a reprecipitation operation was performed, but no copolymer was obtained (yield = 0 g, yield = 0%).

[Comparative Example 3] In the same manner as in Example 1 except that NB was not used, the IB unit / MMA unit = 28.6 / 71.4 (mol%) of the binary combination was used. A polymer was synthesized. The physical properties of the obtained copolymer are shown below. Tg: 75 ° C., Mw = 136,000, Mn = 2
9,300, molecular weight distribution (Mw / Mn) = 4.64, C
_R = 404Br, total light transmittance: 90%, water absorption: 1.
22%, bending strength: 82 MPa, bending elastic modulus: 381
0, yield point displacement: 10.03 mm. Further, the obtained test piece did not break in the bending test and had excellent toughness, but when applied to an optical component or the like which has a low Tg and requires heat resistance of 80 ° C. or higher, the molded body is It cannot be used because it deforms.

[Comparative Example 4] NB / M synthesized in Comparative Example 2
Binary copolymer with MA and IB / MM synthesized in Comparative Example 3
The copolymer solution before reprecipitation purification of the binary copolymer with A was blended at 1: 1 in terms of solid content, reprecipitation purification was performed, and drying was performed to obtain a white powder blend. Two Tg's derived from each binary copolymer were confirmed: 75 ° C and 183 ° C. Further, a bimodal peak derived from each of the binary copolymers was also observed in the GPC analysis. It had a very low total light transmittance of 6% and was opaque. This indicates that the respective binary copolymers are incompatible with each other.

[0070]

The novel cyclic olefin-based copolymer obtained by the present invention is obtained by adopting a radical copolymerization method which can set various reaction conditions and is highly convenient. The cyclic olefin-based resin retains good properties (transparency, water resistance (low water absorption), heat resistance) and excellent low birefringence. It has higher toughness than a polymer and has the characteristic that a molded product can be obtained without any hindrance to the molding operation, and its industrial value is immeasurable.

[Brief description of drawings]

FIG. 1 is a GPC chart of the cyclic cycloolefin-based copolymer obtained in Example 1.

FIG. 2 is a DSC chart of the cyclic cycloolefin-based copolymer obtained in Example 1.

FIG. 3 is a ¹³ C-NMR spectrum of the cyclic cycloolefin-based copolymer obtained in Example 1.

4 is an infrared spectroscopy spectrum of the cyclic cycloolefin-based copolymer obtained in Example 1. FIG.

5 is a GPC chart of the cyclic cycloolefin-based copolymer obtained in Example 2. FIG.

FIG. 6 is a DSC chart of the cyclic cycloolefin-based copolymer obtained in Example 2.

FIG. 7 is a ¹³ C-NMR spectrum of the cyclic cycloolefin-based copolymer obtained in Example 2.

FIG. 8 is an infrared spectroscopic spectrum of the cyclic cycloolefin-based copolymer obtained in Example 2.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Seiji Fukuhara             2-11-21 Tsukiji, Chuo-ku, Tokyo J             Within SRL Co., Ltd. (72) Inventor Yuichi Hashiguchi             2-11-21 Tsukiji, Chuo-ku, Tokyo J             Within SRL Co., Ltd. F-term (reference) 4J100 AA03Q AA04Q AA06Q AA07Q                       AA08Q AA15Q AA16Q AA19Q                       AC25P AC26P AE02Q AE03Q                       AE04Q AE05Q AE21Q AK32P                       AL03P AL04P AL05P AL08P                       AL09P AL34P AM45P AM47P                       AM48P AR09R AR11R BA04P                       BA04R BA10R BA14P BA14R                       BA20P BA20R BA30R BA31P                       BA34R BA35P BA40R BA53R                       BA55P BA58P BA58R BA71R                       BB01R BB03R BB07R BB17R                       BB18R BC03R BC04P BC04R                       BC08P BC43P BC43R BC48R                       BC49P BC49R CA05 DA01                       DA25 DA66 JA32 JA34 JA36

Claims (5)

[Claims] 1. (A) a structural unit having a cyclic olefin skeleton represented by the following general formula (1), (B) a structural unit having an electron-withdrawing group (however, the structural unit of the above (A) is excluded) And (C) at least one structural unit selected from the group consisting of structural units represented by the following general formula (2) and structural units represented by the following general formula (3). Cyclic olefin copolymer. [Chemical 1] [In the formula, m and n are each independently an integer of 0 to 2,
R ¹ , R ² , R ³ and R ⁴ are independently a hydrogen atom; a halogen atom; a substituted or unsubstituted carbon atom which may have a linking group containing oxygen, nitrogen, sulfur or silicon to the ring structure. Represents a hydrocarbon group of the number 1 to 20; or a polar group. ] [Chemical 2] [In the formula, R ⁵ and R ⁶ are independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and at least one of R ⁵ and R ⁶ is an alkyl group having 1 to 20 carbon atoms. ] [Chemical 3] [Wherein R ⁷ and R ⁸ are independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ⁹ is 1 to 1 carbon atom.
20 alkyl groups. ] 2. The structural unit having an electron-withdrawing group (B) is selected from the group consisting of structural units represented by the following general formula (4) and structural units represented by the following general formula (5). The cyclic olefin-based copolymer according to claim 1, which is at least one type of structural unit. [Chemical 4] [In the formula, R ¹⁰ is a hydrogen atom or a methyl group, and R ¹¹ is an alkyl group having 1 to 30 carbon atoms. ] [Chemical 5] [In the formula, R ¹² is a hydrocarbon group having 1 to 20 carbon atoms. ] 3. A glass transition temperature (Tg) of 80 to 300 ° C.
The cyclic olefin-based copolymer according to claim 1 or 2, wherein 4. A polystyrene-equivalent number average molecular weight of 50 as measured by gel permeation chromatography.
The cyclic olefin-based copolymer according to claim 1, wherein the cyclic olefin-based copolymer is from 0 to 1,000,000. 5. The cyclic olefin-based copolymer according to any one of claims 1 to 4, wherein the absolute value of the stress optical coefficient is 1000 or less.