JP2003082074A - Norbornene ring-opened (co)polymer and hydrogenated product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a norbornene polymer having excellent optical properties, heat resistance, and the affinity and adhesiveness with another material, having excellent chemical resistance and solvent resistance, and capable of being crosslinked without having the discoloring and deterioration of the resin, and a hydrogenated product of the same. SOLUTION: The norbornene ring-opened (co)polymer obtained by subjecting a specific silyl-having norbornene monomer 1 such as 5-(triethoxysilyl) bicyclo[2.2.1]hept-2-ene and another norbornene monomer 2 such as 8-methyl-8- methoxycarbonyltetracyclo[4.4.0.1<2> ,<5> .1<7> ,<10> ]-3-dodecene at a molar ratio of 100/0 to 1/99 to ring-opening polymerization, and having a weight-average molecular weight of 3,000-2,000,000 in terms of polystyrene. A hydrogenated product of the same.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a norbornene ring-opening ring (which is excellent in optical properties, heat resistance, affinity / adhesion with other materials, chemical resistance / solvent property, and can be crosslinked if necessary). Co) polymers (hereinafter referred to as "norbornene-based polymers") and hydrogenated products thereof.

[0002]

2. Description of the Related Art Conventionally, transparent resins such as acrylic resin and polycarbonate resin are used for automobile parts, lighting equipment parts,
It has been used as a material for molded products such as electric parts that require transparency. However, for applications in which heat resistance and higher optical properties are important, these conventional transparent resins often have insufficient properties. Therefore, recently, a cyclic polyolefin resin having transparency, water resistance (low water absorption), low birefringence, heat resistance and the like has been used as a transparent resin for optical materials. However, conventionally known cyclic polyolefin-based resins are not always sufficient in adhesiveness and adhesiveness to other materials, for example, organic materials such as ink and adhesives, and inorganic materials such as glass and metal. Also in terms of heat resistance, it is possible to raise the glass transition temperature (Tg) of the resin to improve the heat resistance of the resin itself, but if Tg becomes too high, injection molding, melt extrusion molding, etc. Processing becomes extremely difficult with the processing means used for ordinary molding, and there is a limit to practical improvement of heat resistance.

Therefore, attempts have been made to introduce a polar group into the molecular structure in order to improve the adhesion and adhesion with other materials. However, for example, Japanese Patent Laid-Open No. 1-1326
Japanese Unexamined Patent Publication No. 26 discloses a hydrogenated product of a norbornene ring-opening polymer having a polar group such as an ester group, a hydroxyl group, an amide group, or an imide group introduced therein. May be insufficient. In addition, in order to improve practical heat resistance, attempts have been made to introduce an unsaturated bond or an epoxy group into a side chain and use these to crosslink. However, as shown in JP-A-03-205408 and International Patent Publication WO-96 / 37526, in carrying out a crosslinking reaction of a compound having a vinyl, ethylidene, or epoxy group in a side chain, a radical or high temperature is used. The reaction conditions are required and the resin may be colored or deteriorated, and it is not preferable to use the crosslinking as an optical / electrical / electronic material.

[0004]

SUMMARY OF THE INVENTION The present invention has been made based on the above circumstances, and its purpose is to provide optical characteristics, heat resistance, affinity with other materials, adhesion, and chemical resistance. It is an object of the present invention to provide a norbornene-based polymer and a hydrogenated product thereof which have excellent solvent properties and can be crosslinked without causing coloring or deterioration of the resin.

[0005]

The norbornene-based polymer of the present invention and its hydrogenated product are norbornene derivatives represented by the following general formula (1) (hereinafter referred to as "monomer 1").
100-1 mol% and a norbornene derivative represented by the following general formula (5) (hereinafter referred to as "monomer 2".
"Monomer 1" and "monomer 2" are collectively referred to as "specific monomer"
Say. ) A (co) polymer (hereinafter referred to as "polymer") obtained by ring-opening polymerization of 0 to 99 mol% and a hydrogenated product obtained by hydrogenating the same.

[0006]

[Chemical 4]

[In the general formula (1), at least one of R ^{1 to} R ⁴ is a group having Si (silyl) represented by the following general formula (2), and the others are independently a hydrogen atom or a halogen. Atoms, aliphatic hydrocarbon groups having 1 to 10 carbon atoms, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, or alkoxy groups, hydroxyl groups, ester groups, cyano groups, amide groups, imide groups, sulfonyl groups, ketone groups Shows a polar group selected from the group consisting of an amino group, a sulfide group, an ether group and a thiol group, or an atom or group selected from the group consisting of a halogen atom and / or a group substituted with the above polar group,
They may be the same or different. Further, an alkylidenyl group formed by R ¹ and R ² or R ³ and R ⁴ , or a cycloalkylene group containing R ¹ and R ³ , R ¹ and R ⁴ , R ² and R ³ or R ² and R ^4. , Cycloalkenyl groups, heterocyclic groups or halogen atoms and / or
Alternatively, it may be a group substituted with the above polar group. m is 0 or a positive integer, and n is 0 or 1. However, when m is 0, n is also 0. ]

[0008]

[Chemical 5]

[In the general formula (2), R ^{5 to} R ⁷ are independently
A polar group selected from the group of hydrogen atom, halogen atom, aliphatic hydrocarbon group having 1 to 10 carbon atoms, alicyclic hydrocarbon group, aromatic hydrocarbon group, alkoxy group, and hydroxyl group, and halogen atom and / Alternatively, it represents an atom or a group selected from the group consisting of the groups substituted by the polar groups, which may be the same or different. Also,
R ^{5 to} R ⁷ are 2 represented by the following general formula (3) or (4).
They may be bonded to each other via a valent or trivalent group.
R ⁸ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, an ether group, a carbonyl group,
Alternatively, it represents a carboxyl group. Further, l represents 0 or 1. ] ^{_{- (O) p -R 9 -}} (O) q - (3) [In the general formula (3), R ⁹ is an alkylene group having 1 to 5 carbon _{atoms, - (C 2 H 4 O} ) s -, - (C ₃ H ₆ O) _t −, − (C ₄
H ₈ O) _u - indicates a group selected from, s, t and u are 1
Indicates an integer of ˜5. Further, p and q each independently represent 0 or 1. ]

[0010]

[In the general formula (4), R ⁹ and R ¹⁰ are independently an alkylene group having 1 to 5 carbon atoms,-(C ₂ H ₄ O) _s- ,
_{- (C 3 H 6 O)} t -, - (C 4 H 8 O) u - indicates a group selected from, R ¹¹ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms, alicyclic A hydrocarbon group and an aromatic hydrocarbon group are shown, and s, t, and u show the integer of 1-5. Also, p,
q and r independently represent 0 or 1. ]

[0012]

[Chemical 6]

[In the general formula (5), a to d are each a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms, or an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amide group or an imide group. , A sulfonyl group, a ketone group, an amino group, a sulfide group, an ether group, and a polar group selected from a thiol group, and a halogen atom and /
Or represents an atom or group selected from the group consisting of the above-mentioned polar hydrocarbon groups substituted with a polar group. Or
It is another monovalent organic group and may be the same or different. a and b or c and d may be integrated to form a divalent hydrocarbon group, and a or b and c or d may be bonded to each other to form a monocyclic or polycyclic structure. . Further, x is 0 or a positive integer, and y is 0 or 1. However, when x is 0, y is also 0. ]

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. Specific examples of the monomer 1 used in the present invention include 5-triethoxysilylbicyclo [2.2.1] hept-2-ene and 5-diethoxysilylbicyclo [2.
2.1] hept-2-ene, 5-ethoxysilylbicyclo [2.2.1] hept-2-ene, 5-dimethylchlorosilylbicyclo [2.2.1] hept-2-ene, 5
-Trichlorosilylbicyclo [2.2.1] hept-2
-Ene, 5-trimethoxysilylbicyclo [2.2.
1] hept-2-ene, 5-tripropoxysilylbicyclo [2.2.1] hept-2-ene, 5-tributoxysilylbicyclo [2.2.1] hept-2-ene, 5
-Triphenoxysilylbicyclo [2.2.1] hept-2-ene, 5-trimethylsilylbicyclo [2.2.
1] hept-2-ene, 5-dimethylsilylbicyclo [2.2.1] hept-2-ene, 5-triethoxysilylbicyclo [2.2.1] hept-2-ene, 8-triethoxysilyl Tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-Dodecene, 8-trimethoxysilyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 8-triisopropoxysilyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 8-tributoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]-
3-dodecene, 8-triphenoxysilyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
Trichlorotetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-Dodecene, 8-dimethylchlorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
5-diphenoxymethylsilyl-2-norbornene, 5
-Trimethoxysilylmethyl-2-norbornene, 5-
(2-Trimethoxysilyl) ethyl-2-norbornene, 5- (2-dimethoxychlorosilyl) ethyl-2-
Norbornene, 5- (1-trimethoxysilyl) ethyl-2-norbornene, 5- (2-trimethoxysilyl)
Propyl-2-norbornene, 5- (1-trimethoxysilyl) propyl-2-norbornene, 5-triethoxysilylethyl-2-norbornene, 5-dimethoxymethylsilylmethyl-2-norbornene, 5-trimethoxypropylsilyl- 2-norbornene, 5-norbornene-2-carboxylic acid trimethoxysilylpropyl, 5-
Triethoxysilylpropyl norbornene-2-carboxylic acid, dimethoxy 5-norbornene-2-carboxylic acid,
Methylsilylpropyl, 2-methoxy-5-norbornene-2-carboxylic acid trimethoxysilylpropyl, 2-methyl-5-norbornene-2-carboxylic acid dimethoxy,
Methylpropyl, 2-methyl-5-norbornene-2-
Examples thereof include triethoxysilylpropyl carboxylate. These monomers 1 can be used alone or in combination of two or more.

As a specific example of the monomer 2 used in the present invention,
Is bicyclo [2.2.1] hept-2-ene, tri
Cyclo [5.2.1.0^2,6] -8-decene, tetracy
Black [4.4.0.1^2,5． 1^7,10] -3-dodecene,
Pentacyclo [6.5.1.1^3,6． 0^2,7． 0^9,13]
-4-Pentadecene, Pentacyclo [7.4.0.1
^2,5． 1^9,12． 0^8,13] -3-Pentadecene, Trisic
B [4.4.0.1^2,5] -3-Undecene, 5-meth
Rubicyclo [2.2.1] hept-2-ene, 5-eth
Rubicyclo [2.2.1] hept-2-ene, 5-meth
Xycarbonylbicyclo [2.2.1] hept-2-e
5-methyl-5-methoxycarbonylbicyclo
[2.2.1] Hept-2-ene, 5-cyanobicyclo
[2.2.1] hept-2-ene, 8-methoxycarbo
Nyltetracyclo [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-isopropoxy
Carbonyl tetracyclo [4.4.0.1^2,5．
1^7,10] -3-Dodecene, 8-n-butoxycarbonyl
Tetracyclo [4.4.0.1^2,5． 1^7,10] -3-D
Decene, 8-phenoxycarbonyltetracyclo [4.
4.0.1^2,5． 1^7,10] -3-Dodecene, 8- (1-
Naphthoxy) carbonyltetracyclo [4.4.0.1
^2,5． 1^7,10] -3-Dodecene, 8- (2-naphthoyl
Si) Carbonyl tetracyclo [4.4.0.1^2,5． 1
^7,10] -3-Dodecene, 8- <4-phenylphenoxy
Si> carbonyltetracyclo [4.4.0.1^2,5． 1
^7,10] -3-Dodecene, 8-methyl-8-methoxycal
Bonyltetracyclo [4.4.0.1^2,5． 1^{7, Ten}]-
3-dodecene, 8-methyl-8-ethoxycarbonylthene
Tracyclo [4.4.0.1^2,5． 1^{7, Ten}] -3-Dode
Sen, 8-methyl-8-n-propoxycarbonyl tet
Lacyclo [4.4.0.1^2,5． 1^7,10] -3-Dodese
8-methyl-8-isopropoxycarbonyltetra
Cyclo [4.4.0.1^2,5． 1^7,10] -3-Dodese
8-methyl-8-n-butoxycarbonyltetrasilane
Black [4.4.0.1^2,5． 1^7,10] -3-dodecene,
8-methyl-8-phenoxycarbonyltetracyclo
[4.4.0.1^2,5． 1 ^7,10] -3-Dodecene, 8-
Methyl-8- (1-naphthoxy) carbonyltetracycle
B [4.4.0.1^{2 ,Five}． 1^7,10] -3-Dodecene, 8
-Methyl-8- (2-naphthoxy) carbonyltetrasi
Black [4.4.0.1 ^2,5． 1^7,10] -3-dodecene,
8-Methyl-8- <4-phenylphenoxy> carboni
Rutetracyclo [4.4.0.1^2,5． 1^7,10] -3-
Dodecene, Dimethanooctahydronaphthalene, Methanote
Trahydrofluorene, ethyltetracyclododecene,
6-ethylidene-2-tetracyclododecene, trimeta
Nooctahydronaphthalene, pentacyclo [8.4.
0.1^2,5． 1^9,12． 0^8,13] -3-Hexadecene, F
Putacyclo [8.7.0.1^3,6． 1^10,17．
1^12,15． 0^2,7． 0^11,16] -4-Eikosen, Hep
Tacyclo [8.8.0.1^4,7． 1^11,18． 1^13,16．
0^3,8． 0^12,17] -5-Hen Eicosene, 5-Echiri
Denbicyclo [2.2.1] hept-2-ene, 8-E
Tylidene tetracyclo [4.4.0.1^2,5． 1^7,10]
-3-Dodecene, 5-phenylbicyclo [2.2.1]
Hept-2-ene, 8-phenyltetracyclo [4.
4.0.1^2,5． 1^7,10] -3-Dodecene, 5-Ethyl
Denbicyclo [2.2.1] hept-2-ene, 5-E
Cylbicyclo [2.2.1] hept-2-ene, 5-n-
Butylbicyclo [2.2.1] hept-2-ene, 5-
n-hexylbicyclo [2.2.1] hept-2-ene,
5-Cyclohexylbicyclo [2.2.1] hept-2
-Ene, 5-n-octylbicyclo [2.2.1] hept
-2-ene, 5-n-decylbicyclo [2.2.1] hep
To-2-ene, 5-isopropylbicyclo [2.2.
1] hept-2-ene, 5-phenylbicyclo [2.
2.1] Hept-2-ene, 5-naphthylbicyclo
[2.2.1] Hept-2-ene, 5-biphenylbic
Black [2.2.1] hept-2-ene, 5-cyanobicy
Chloro [2.2.1] hept-2-ene, 5-chloromethyi
Rubicyclo [2.2.1] hept-2-ene, 5-siku
Rohesenyl bicyclo [2.2.1] hept-2-ene,
5-fluorobicyclo [2.2.1] hept-2-e
5-fluoromethylbicyclo [2.2.1] heptone
-2-ene, 5-trifluoromethylbicyclo [2.
2.1] Hept-2-ene, 5-pentafluoroethyl
Bicyclo [2.2.1] hept-2-ene, 5,5-di
Fluorobicyclo [2.2.1] hept-2-ene,
5,6-Difluorobicyclo [2.2.1] hept-2
-Ene, 5,5-bis (trifluoromethyl) bicyclo
[2.2.1] Hept-2-ene, 5,6-bis (tri
Fluoromethyl) bicyclo [2.2.1] hept-2-
Ene, 5-methyl-5-trifluoromethylbicyclo
[2.2.1] Hept-2-ene, 5,5,6-trif
Luorobicyclo [2.2.1] hept-2-ene, 5,
5,6-Tris (fluoromethyl) bicyclo [2.2.
1] hept-2-ene, 5,5,6,6-tetrafluor
Robicyclo [2.2.1] hept-2-ene, 5,5
6,6-Tetrakis (trifluoromethyl) bicyclo
[2.2.1] Hept-2-ene, 5,5-difluoro
-6,6-bis (trifluoromethyl) bicyclo [2.
2.1] Hept-2-ene, 5,6-difluoro-5,
6-bis (trifluoromethyl) bicyclo [2.2.
1] hept-2-ene, 5,5,6-trifluoro-5
-Trifluoromethylbicyclo [2.2.1] hept-
2-ene, 5-fluoro-5-pentafluoroethyl-
6,6-bis (trifluoromethyl) bicyclo [2.
2.1] Hept-2-ene, 5,6-difluoro-5-
Heptafluoro-iso-propyl-6-trifluoro
Methylbicyclo [2.2.1] hept-2-ene, 5-
Chloro-5,6,6-trifluorobicyclo [2.2.
1] hept-2-ene, 5,6-dichloro-5,6-bi
Su (trifluoromethyl) bicyclo [2.2.1] hep
To-2-ene, 5,5,6-trifluoro-6-trif
Luoromethoxybicyclo [2.2.1] hept-2-e
5,5,6-trifluoro-6-heptafluorop
Ropoxybicyclo [2.2.1] hept-2-ene, 8
-Fluorotetracyclo [4.4.0.1^2,5．
1^7,10] -3-Dodecene, 8-fluoromethyltetracy
Black [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-trifluoromethyi
Rutetracyclo [4.4.0.1^2,5． 1^7,10] -3-
Dodecene, 8-pentafluoroethyl tetracyclo
[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-difluorotetrasic
B [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-trif
Luorotetracyclo [4.4.0.1^2,5． 1^7,10]-
3-dodecene, 8,8,9-tris (trifluoromethyi)
Le) tetracyclo [4.4.0.1^2,5． 1^7,10] -3
-Dodecene, 8,8,9,9-tetrafluorotetrasi
Black [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 (trifluor
(Methyl) tetracyclo [4.4.0.1^2,5．
1^7,10] -3-Dodecene, 8,9-difluoro-8,9
-Bis (trifluoromethyl) tetracyclo [4.4.
0.1^2,5． 1^7,10] -3-Dodecene, 8,8,9-to
Lifluoro-9-trifluoromethyltetracyclo
[4.4.0.1^2,5． 1^7,10] -3-Dodecene, 8,
8,9-trifluoro-9-trifluoromethoxytet
Lacyclo [4.4.0.1^2,5． 1^7,10] -3-Dodese
, 8,8,9-trifluoro-9-pentafluoro
Ropoxytetracyclo [4.4.0.1^2,5． 1^7,10]
-3-dodecene, 8-fluoro-8-pentafluoroe
Tyl-9,9-bis (trifluoromethyl) tetrasic
B [4.4.0.1^2,5． 1^7,10] -3-dodecene,
8,9-difluoro-8-heptafluoroiso-pro
Pyr-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 (trifluoromethyl) tetracyclo
[4.4.0.1^2,5． 1^7,10] -3-Dodecene, 8-
(2,2,2-trifluoroethoxycarbonyl) teto
Lacyclo [4.4.0.1^2,5． 1^7,10] -3-Dodese
8-methyl-8- (2,2,2-trifluoroeth
Xycarbonyl) tetracyclo [4.4.0.1^2,5．
1^7,10] -3-Dodecene, 5- (2-naphthoyloxy
Ci) -5-Methylbicyclo [2.2.1] hept-2-
Ene, 5- (2-naphthoyloxy) bicyclo [2.
2.1] Hept-2-ene, 5- (4-biphenoylo
Xy) -5-methylbicyclo [2.2.1] hept-2
-Ene, 5- (4-biphenoyloxy) bicyclo
[2.2.1] Hept-2-ene, 5- (2-bipheno
Iloxy) -5-methylbicyclo [2.2.1] hep
To-2-ene, 5- (2-biphenoyloxy) bisic
B [2.2.1] hept-2-ene, 5- (3-bife
Noyloxy) -5-methylbicyclo [2.2.1] f
Put-2-ene, 5- (3-biphenoyloxy) bic
Chloro [2.2.1] hept-2-ene, 5- (9-full
Olenoyloxy) -5-methylbicyclo [2.2.
1] Hept-2-ene, 5- (9-fluorenoyloxy
Ci) Bicyclo [2.2.1] hept-2-ene, 5-a
Intracenoyloxy-5-methylbicyclo [2.2.
1] Hept-2-ene, 5-anthracenoyloxybi
Cyclo [2.2.1] hept-2-ene, 8-benzoi
Luoxy-8-methyl [4.4.0.1^2,5． 1^7,10]
-3-dodecene, 8-benzoyloxy [4.4.0.
1^2,5． 1^7,10] -3-dodecene, 8- (1-naphthoyl
Luoxy) -8-methyl [4.4.0.1^2,5．
1^7,10] -3-Dodecene, 8- (1-naphthoyloxy
Shi) [4.4.0.1^2,5． 1^7,10] -3-dodecene,
8- (2-naphthoyloxy) -8-methyl [4.4.
0.1^2,5． 1^7,10] -3-Dodecene, 8- (2-naphtho
(Toyloxy) [4.4.0.1^2,5． 1^7,10] -3-
Dodecene, 8- (4-biphenoyloxy) -8-meth
Le [4.4.0.1^2,5． 1^7,10] -3-Dodecene, 8
-(4-Biphenoyloxy) [4.4.0.1^2,5．
1^7,10] -3-Dodecene, 8- (3-biphenoyloxy
Si) -8-methyl [4.4.0.1^2,5． 1^7,10] -3
-Dodecene, 8- (3-biphenoyloxy) [4.
4.0.1^2,5． 1^7,10] -3-Dodecene, 8- (2-
Biphenoyloxy) -8-methyl [4.4.0.1
^2,5． 1^7,10] -3-Dodecene, 8- (2-Bifenoy
Luoxy) [4.4.0.1^2,5． 1^7,10] -3-Dode
Cene, 8- (9-fluorenoyloxy) -8-methyl
[4.4.0.1^2,5． 1^7,10] -3-Dodecene, 8-
(9-Fluorenoyloxy) [4.4.0.1^2,5．
1^7,10] -3-Dodecene, 8- (9-anthracenoyl
Oxy) -8-methyl [4.4.0.1^2,5． 1^{7, Ten}]
-3-dodecene, 8- (9-anthracenoyloxy)
[4.4.0.1^2,5． 1^7,10] -3-Dodecene, etc.
Is mentioned. These monomers 2 should not be used alone.
It is also possible to use in combination of two or more
It

The copolymerization ratio of the monomer 1 and the monomer 2 is a molar ratio of monomer 1 / monomer 2 = 100 to 1/0 to 99, preferably 70 to 1/30 to 99. , And more preferably 50
Is 1/50 to 99. When the amount of the monomer 1 is less than 1 mol%, the effect of improving the adhesion to an inorganic material such as a glass substrate or an aluminum substrate may be small.

In the present invention, in addition to the monomers 1 and 2, other monomers copolymerizable therewith, for example, cyclobutene, cyclopentene, cyclooctene, cyclododecene and other cyclic olefins, and 1,5-cyclooctadiene. It is also possible to copolymerize using a non-conjugated cyclic polyene such as cyclododecatriene. In this case, the amount of the other copolymerizable monomer used is 200 mol% or less, preferably 100 mol% or less, based on the total monomers.

In the present invention, the monomer 1 and the monomer are added in the presence of polybutadiene, polyisoprene, styrene-butadiene, an ethylene-non-conjugated diene polymer, a ring-opening polymerization unhydrogenated norbornene derivative, and the like. 2. If necessary, the other copolymerizable monomer may be polymerized.

<Ring-Opening Polymerization Catalyst> In the present invention, the following metathesis polymerization catalyst is used as the ring-opening polymerization catalyst. In the present invention, the polymerization and copolymerization of the norbornene-based monomer (monomer 1) represented by the above general formula (1) and the polar group-containing norbornene-based monomer (also included in the monomer 2) are performed. Since the polymerization is performed, a titanium tetrachloride-based catalyst having a very low activity with respect to the polar group-containing monomer cannot be used. The metathesis catalyst includes (a) at least one selected from compounds of W, Mo and Re, (b) an element of Group IA (eg, Li, Na, K, etc.) of the periodic table of Deming, and an element of Group IIA (eg, Mg). , Ca, etc., IIB group elements (eg Z
n, Cd, Hg, etc., III group B elements (eg, B, Al)
Etc.), IVA group element (eg Ti, Zr, etc.) or
A catalyst which is a compound of a group IVB element (for example, Si, Sn, Pb, etc.) and is formed by a combination with at least one element selected from the group having at least one element-carbon bond or the element-hydrogen bond. . Further, in this case, in order to enhance the activity of the catalyst, the below-mentioned (c) additive may be added.

Suitable W, Mo as the component (a) or
As a typical example of the compound of Re, WCl₆, MoC
l_Five, ReOCl₃ JP-A 1-240517
The compounds described in can be mentioned. (B) ingredient ingredients
As a body example, nC_FourH₉Li, (C₂H_Five)₃Al, (C
₂H_Five) ₂AlCl, (C₂H_Five)_1.5AlCl_1.5, (C₂H
_Five) AlCl₂, Methylalumoxane, LiH, etc.
The compounds described in JP-A 1-240517 may be mentioned.
it can. (C) A typical example of the additive is alcohol.
Suitable for use with compounds, aldehydes, ketones, amines, etc.
However, it is further disclosed in JP-A-1-240517.
The compounds shown in the publication can be used.

The amount of the metathesis catalyst to be used is "(a) component: specific monomer" in a molar ratio of the above component (a) to the specific monomer of usually 1: 500 to 1: 50,000. Range, preferably 1: 1,000 to 1: 10,000
The range is 0. The ratio of the component (a) to the component (b) is such that “(a) :( b)” is 1: 1 to 1: 1 in terms of metal atom ratio.
The range is 50, preferably 1: 2 to 1:30.
The molar ratio of the component (a) to the component (c) is in the range of 0.005: 1 to 15: 1, preferably 0.05: 1 to 7: 1 for "(c) :( a)". It is said that

<Molecular Weight Control Agent> The molecular weight of the ring-opening (co) polymer can be controlled by the polymerization temperature, the type of catalyst and the type of solvent. In the present invention, the molecular weight control agent is used in the reaction system. It is preferable to adjust it by coexisting with. Here, as a suitable molecular weight regulator, for example, ethylene, propene, 1-butene, 1-pentene, 1-
Hexene, 1-heptene, 1-octene, 1-nonene,
Examples thereof include α-olefins such as 1-decene and styrene, and among these, 1-butene and 1-hexene are particularly preferable. These molecular weight regulators can be used alone or in admixture of two or more. The amount of the molecular weight modifier used is 0.005 to 0.6 mol, preferably 0.02 to 0.5 mol, per 1 mol of the specific monomer used in the ring-opening polymerization reaction.

<Solvent for Ring-Opening Polymerization Reaction> Examples of the solvent used in the ring-opening polymerization reaction (solvent for dissolving the specific monomer, the metathesis catalyst and the molecular weight modifier) include pentane, hexane, heptane, octane, nonane, Alkanes such as decane; cyclohexane, cycloheptane,
Cycloalkanes such as cyclooctane, decalin and norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane,
Halogenated alkanes such as bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform, tetrachloroethylene;
Compounds such as aryl; ethyl acetate, n-butyl acetate,
Saturated carboxylic acid esters such as iso-butyl acetate, methyl propionate and dimethoxyethane; ethers such as dibutyl ether, tetrahydrofuran and dimethoxyethane can be mentioned, and these can be used alone or in combination. Of these, aromatic hydrocarbons are preferred. The amount of the solvent used is such that the "solvent: specific monomer (weight ratio)" is usually 1: 1 to 10: 1, preferably 1: 1 to 5: 1. It

<Hydrogenation Catalyst> The polymer obtained as described above can be used as it is as a molding material, but it is preferable to use a hydrogenated hydrogenated material as a molding material. The hydrogenation reaction is carried out by an ordinary method, that is, a hydrogenation catalyst is added to a solution of a ring-opening (co) polymer, and the reaction is carried out under normal pressure to 300 atm, preferably 3 to 2 atm.
Hydrogen gas at 00 atm is 0 to 200 ° C, preferably 20 to
It is carried out by operating at 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. Heterogeneous catalysts include palladium, platinum,
A solid catalyst in which a noble metal catalyst substance such as nickel, rhodium or ruthenium is supported on a carrier such as carbon, silica, alumina or titania can be mentioned. 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. In these hydrogenation catalysts, the "ring-opening (co) polymer: hydrogenation catalyst (weight ratio)" is 1: 1 × 10 ^-6 ~
Used at a ratio of 1: 2. The hydrogenation rate is usually
It is 50 to 100%, preferably 80 to 100%.

The intrinsic viscosity (ηinh) of the polymer of the present invention and the hydrogenated product thereof is chlorobenzene (0.5 g / dl) at 30 ° C. when measured with an Ubbelohde viscometer.
It is preferably in the range of 0.2 to 5, and more preferably 0.3 to 4. Moreover, in the measurement of the molecular weight by gel permeation chromatography (GPC, tetrahydrofuran solvent, polystyrene conversion), the number average molecular weight is 1 × 10 ^{3 to} 5 × 10 ⁵ , and the weight average molecular weight is 3
× 10 ^{3 to} 2 × 10 ⁶ , preferably a number average molecular weight of 3 × 10 ^{3 to} 3 × 10 ⁵ , and a weight average molecular weight of 5 × 1.
It is 0 ³ to 1 × 10 ⁶ .

The norbornene ring-opening (co) of the present invention described above
The polymer is, for example, 1,
Absorption of the adjacent double bond of the carbonyl of 730~1,740cm ^-1 (C = O), can be confirmed by such absorption of the silyl ether group represented by the general formula of 1,110cm ^-1 (2), also, Nuclear magnetic resonance spectrum ( ¹ H-NMR)
Thus, the proton peak of the carbon atom substituent of the C = C double bond at 5.0 to 5.8 ppm, 3.8 to 3.9 ppm
Peak of methylene of triethoxysilyl group of 3.6 p
The structure can be confirmed from the methyl peak of the methyl ester group of pm. Further, the proportion of repeating units derived from the monomer 1 in the copolymer was 3.6 ppm derived from methyl of the methyl ester group by ¹ H-NMR.
Can be determined from the ratio of the peak of the proton of γ and the peak of the proton of methylene of the triethoxysilyl group of 3.85 ppm. Further, in the structure of the hydrogenated product of the present invention, the peak at 5.0 to 5.8 ppm of protons at the unsaturated site (carbon atom substituent of the C = C double bond) in the (co) polymer disappears. This can be confirmed.

Various known additives can be added to the polymer obtained as described above and its hydrogenated product. Specifically, for example, 2,6-di-t-butyl-4-methylphenol, 2,2-methylenebis (4-
Ethyl-6-t-butylphenol), 2,5-di-t
-Butylhydroquinone, pentaerythrityl tetrakis
[. 3- (3,5-di-t-butyl-4-hydroxyphenyl) propiolate, 4,4-thiobis- (6-t-
Butyl-3-methylphenol), 1,1 ^, -bis (4
-Hydroxyphenyl) cyclohexane, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propiolate, and other phenolic or hydroquinone antioxidants, or tris (4-methoxy-3,
Examples thereof include phosphorus-based antioxidants such as 5-diphenyl) phosphite, tris (nonylphenyl) phosphite, and tris (2,4-di-t-butylphenyl) phosphite. Seed or 2
Addition of one or more species can improve the oxidative stability of the polymer and its hydrogenated product. Further, ultraviolet absorbers such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,
By adding 2,2, -methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-[(2H-benzotriazol-2-yl) phenol]] and the like, the polymer and the polymer thereof are added. The light resistance of the hydrogenated substance can be improved. Further, additives such as lubricants may be added for the purpose of improving processability.

The use of the polymer of the present invention and the hydrogenated product thereof is not particularly limited, but it is useful in the fields of optical and electric / electronic materials. For example, optical discs, magneto-optical discs, optical lenses (Fθ lenses, pickup lenses, laser printer lenses, camera lenses, etc.), eyeglass lenses, optical films (display films, retardation films, polarizing films, transparent conductive films, etc.) , Optical sheet, optical fiber, light guide plate, light diffusion plate, optical card, optical mirror, encapsulating material for optical semiconductors such as IC and LED, printed board material, display board (substrate for liquid crystal display element and EL display element), etc. Is mentioned.

[0029]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In addition, various measurements and evaluations in Examples and Comparative Examples were performed as follows.

(Glass transition temperature: Tg) A differential scanning calorimeter manufactured by Seiko Instruments Inc. was used to measure the temperature rising rate at 20 ° C. per minute under a nitrogen stream. (Weight average molecular weight and molecular weight distribution) Using gel permeation chromatography (GPC) in tetrahydrofuran (THF), polystyrene equivalent weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / M)
n) was measured.

(Adhesion test) The polymer was dissolved in toluene to obtain a toluene solution having a polymer concentration of 10% by weight.
A small amount of 1N hydrochloric acid was added to this and spin coating was applied to a glass substrate to a thickness of 20 μm. After that, heat-dry at normal pressure and room temperature for 3 hours and at normal pressure and 100 ° C. for 3 hours to obtain a thickness of
A dry coating film of μm was obtained. Make 1 vertical and horizontal cuts at 1 mm intervals with a cutter on the dry coating on the surface of the glass substrate 1
100 squares of 100 mm square were made, cellophane tape was firmly attached, and then peeled off vertically. After the cellophane tape was peeled off, the number of eyes that did not peel off was counted, and the ratio was shown in%.

(Total Light Transmittance) It was measured according to the ASTM D1003 test method using a direct reading base computer manufactured by Suga Test Instruments Co., Ltd.

Example 1 5- (triethoxysilyl) bicyclo [2.2.1] hept-2- as represented by the following chemical formula (I) as the monomer 1
7.68 g of ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene 1
6.70 g, molecular weight regulator 1-hexene 3.20 m
1 and 50 ml of toluene were charged into a reaction vessel purged with nitrogen and heated to 80 ° C. To this, 0.2 ml of a toluene solution of triethylaluminum (0.6 mol / L) and a methanol-modified WCl ₆ toluene solution (0.025 mol / L) of 0.
A polymer was obtained by adding 74 ml and reacting at 80 ° C. for 3 hours. Weight average molecular weight (Mw) is 14.1 x 1
A polymer having a molecular weight distribution of 0 ⁴ and a molecular weight distribution (Mw / Mn) of 4.04 was obtained. The ¹ H-NMR chart of this polymer is shown in FIG.
Here, the obtained polymer solution was put into an autoclave,
Further, 50 ml of toluene was added. RuHC which is a hydrogenation catalyst
l (CO) [P (C ₆ H ₅ )] ₃ was added in an amount of 500 ppm with respect to the charged amounts of the monomer 1 and the monomer 2, and the hydrogen gas pressure was 9 to 10 MPa,
The reaction was carried out at 160 to 165 ° C. for 3 hours. After the reaction was completed, a large amount of methanol was added to precipitate the polymer to obtain a hydrogenated product [weight average molecular weight (Mw) = 2.
0.0 × 10 ⁴ , molecular weight distribution (Mw / Mn) = 5.71, glass transition temperature (Tg) = 140.3 ° C.]. When the hydrogenation rate of the obtained hydrogenated product was measured by ¹ H-NMR (400 MHz), it was substantially 100% (99.7%). The hydrogenated product thus obtained is referred to as polymer A. The infrared absorption spectrum of this polymer A in FIG. 2, ¹ H-N
The MR chart is shown in FIG.

[0034]

[Chemical 7]

[0035]

[Chemical 8]

Comparative Example 1 As a monomer, 8-methoxycarbonyl-8-methyltetracyclo [4.4.0.
1 ^2,5 . 1 ^7,10 ] -3-dodecene was used only in 50 g,
3.6 g of 1-hexene, which is a molecular weight regulator, and 100 g of toluene were charged into a reaction vessel purged with nitrogen and heated to 80 ° C. Triethyl aluminum (0.6 mol /
L) of toluene solution 0.09 ml and methanol-modified WCl ₆ toluene solution (0.025 mol / L) 0.29 ml were added, and
A polymer was obtained by reacting at 0 ° C. for 3 hours. The hydrogenation reaction was also carried out in the same manner as in Example 1 to obtain the corresponding hydrogenated product [glass transition temperature (Tg) = 164 ° C., weight average molecular weight (Mw) = 56,000, molecular weight distribution (Mw / Mn) =
3.2]. The hydrogenation rate of the obtained hydrogenated product was determined by ¹ H-NMR.
When measured at (400 MHz), it is virtually 100%
(99.8%). The hydrogenated product thus obtained is referred to as polymer B.

Test Example 1 With respect to the polymer A, the above-mentioned adhesion test was carried out. No peeling of the eyes was observed, which was 100%. In addition, a glass substrate provided with a dry coating film is treated with water, toluene, TH
It was immersed in F and dichloromethane at room temperature for 1 day and the state of the coating film was observed. In the case of water, no abnormality was found in the coating film. In the case of toluene, THF and dichloromethane, some swelling was observed but it was not dissolved.

Test Example 2 The same evaluation as in Test Example 1 was performed except that a mirror-finished aluminum substrate whose surface was polished was used instead of the glass substrate. The adhesiveness was 100%.

Test Example 3 Polymer A was dissolved in toluene to obtain a toluene solution having a polymer concentration of 30% by weight. This solution is coated on a polyester (PET) film, then dried at 80 ° C for 4 hours at normal pressure, and further reduced pressure at 100 ° C using a vacuum dryer.
After drying at 0 ° C. for 2 hours, a film having a thickness of 100 μ was obtained.
The total light transmittance of this film was measured and found to be 93%.
It is clear that the transparency is excellent.

Comparative Test Example 1 The same evaluation as in Test Example 1 was carried out except that the polymer B was used instead of the polymer A. Adhesiveness is 40%,
In the case of water, no change in the coating film after immersion was observed,
With other solvents, the coating film dissolved.

Comparative Test Example 2 The same evaluation as in Comparative Test Example 1 was performed except that a mirror-finished aluminum substrate whose surface was polished was used instead of the glass substrate. The adhesiveness was 48%.

[0042]

INDUSTRIAL APPLICABILITY The ring-opening (co) polymer and hydrogenated product thereof of the present invention are excellent in transparency, adhesiveness, chemical resistance and solvent resistance,
It is a (co) polymer having excellent optical properties and is suitable for electronic, electrical and optical materials. For example, optical discs, magneto-optical discs, optical lenses (Fθ lenses, pickup lenses, laser printer lenses, camera lenses, etc.), eyeglass lenses, optical films (display films, retardation films, polarizing films, transparent conductive films, etc.) , Optical sheet, optical fiber, light guide plate, light diffusion plate, optical card, optical mirror, encapsulating material for optical semiconductors such as IC and LED, printed board material, display board (substrate for liquid crystal display element and EL display element), etc. Can be suitably used.

[Brief description of drawings]

[1] obtained in Example 1 polymer (hydrogenated prior to addition) ¹
It is an H-NMR chart. An unsaturated bond (double bond) is observed at around 5.0 to 5.8 ppm, and a methylene signal of the triethoxysilyl group is observed at about 3.85 ppm.
In addition, the methyl signal of the methyl ester group is 3.6 to
It can be observed at 3.7 ppm.

2 is an infrared absorption spectrum of the polymer A (hydrogenated product) obtained in Example 1. FIG. The absorption derived from the silyl ether bond of the triethoxysilyl group is 1,110 cm ^-1 , and the absorption derived from the carbonyl of the methyl ester group is 1,730 to 30.
It can be confirmed at 1,740 cm ^-1 .

FIG. 3 shows the polymer A (hydrogenated product) obtained in Example 1.
^{It is a 1} H-NMR chart. It can be seen that the signal of the unsaturated bond (double bond) around 5.0 to 5.8 ppm, which had been confirmed before hydrogenation, disappeared. 3.85ppm
A methylene signal of the triethoxysilyl group can be confirmed in the vicinity. Moreover, the methyl signal of the methyl ester group can be observed at 3.6 to 3.7 ppm.

Continued front page    (72) Inventor Toshitaka Otsuki             2-11-21 Tsukiji, Chuo-ku, Tokyo J             Within SRL Co., Ltd. F-term (reference) 4J032 CA34 CA35 CA36 CB04 CB12                       CC03 CF01 CF03

Claims (2)

[Claims] 1. A molar ratio of the norbornene-based monomer represented by the following general formula (1) and the norbornene-based monomer represented by the following general formula (5) in 100/0 to 1/99. A norbornene ring-opening (co) polymer having a polystyrene-equivalent weight average molecular weight of 3,000 to 2,000,000, which is obtained by ring-opening polymerization at a ratio of. [Chemical 1] [In the general formula (1), at least one of R ^{1 to} R ⁴ is a group having Si (silyl) represented by the following general formula (2), and the others are independently a hydrogen atom, a halogen atom, or a carbon atom. Number 1 to 1
0 aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or alkoxy group, hydroxyl group, ester group,
A polar group selected from the group consisting of a cyano group, an amide group, an imide group, a sulfonyl group, a ketone group, an amino group, a sulfide group, an ether group and a thiol group, or a group substituted with a halogen atom and / or the above polar group. It represents an atom or group selected from the group consisting of, and may be the same or different. Further, an alkylidenyl group formed by R ¹ and R ² or R ³ and R ⁴ , or a cycloalkylene group containing R ¹ and R ³ , R ¹ and R ⁴ , R ² and R ³ or R ² and R ^4. It may be a cycloalkenyl group, a heterocyclic group, or a group in which these are substituted with a halogen atom and / or the above polar group. m is 0 or a positive integer, and n is 0 or 1. However, when m is 0, n is also 0. ] [Chemical 2] [In the general formula (2), R ^{5 to} R ⁷ are independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or an alkoxy group. A group, and a polar group selected from the group of hydroxyl groups, and an atom or group selected from the group consisting of a halogen atom and / or a group substituted with the above polar group, which may be the same or different. Is also good. Further, R ^{5 to} R ⁷ are
They may be bonded to each other via a divalent or trivalent group represented by the following general formula (3) or (4). R ⁸ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, an ether group, a carbonyl group, or a carboxyl group. Further, l represents 0 or 1. ] ^{_{- (O) p -R 9 -}} (O) q - (3) [In the general formula (3), R ⁹ is an alkylene group having 1 to 5 carbon _{atoms, - (C 2 H 4 O} ) s -, - (C ₃ H ₆ O) _t −, − (C ₄
H ₈ O) _u - indicates a group selected from, s, t and u are 1
Indicates an integer of ˜5. Further, p and q each independently represent 0 or 1. ] [In the general formula (4), R ⁹ and R ¹⁰ independently have 1 to 1 carbon atoms.
5 alkylene _{group, - (C 2 H 4 O} ) s -, - (C 3 H
_{6 O) t -, - (} C 4 H 8 O) u - indicates a group selected from,
R ¹¹ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, s,
t and u show the integer of 1-5. Further, p, q and r each independently represent 0 or 1. ] [Chemical 3] [In the general formula (5), a to d are hydrogen atoms,
Halogen atom or hydrocarbon group having 1 to 10 carbon atoms, or alkoxy group, hydroxyl group, ester group, cyano group, amide group, imide group, sulfonyl group, ketone group, amino group,
A polar group selected from a sulfide group, an ether group and a thiol group, and a halogen atom and / or an atom or group selected from the group consisting of polar hydrocarbon groups substituted with the above polar groups. Alternatively, they are other monovalent organic groups, which may be the same or different. a
And b or c and d may be integrated to form a divalent hydrocarbon group, and a or b and c or d may be bonded to each other to form a monocyclic or polycyclic structure. Further, x is 0 or a positive integer, and y is 0 or 1. However, when x is 0, y is also 0. ] 2. The hydrogenated product of a norbornene ring-opening (co) polymer according to claim 1, which is obtained by hydrogenating the double bond portion in the main chain.