JP2003160620A - Cycloolefin based addition copolymer, its composition for crosslinkage, its crosslinked substance, optically transparent material, and method for manufacturing cycloolefin based addition copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a cycloolefin based addition copolymer that contains a reactive silyl group having a specific structure, has excellent optical transparency, heat resistance and adhesiveness, and can produce crosslinked substance having improved dimentional stability, solvent and chemicals resistance by crosslinking. <P>SOLUTION: The cycloolefin based addition copolymer containing the reactive silyl group that is made by addition polymerization between a cycloolefin compound having the reactive silyl group such as 5-[1',4',4'-trimethyl-2',6'-dioxa-1'- silacyclohexyl]-bicyclo[2.2.1]hepto-2-en and other cycloolefin compound such as bicyclo[2.2.1]hepto-2-en, a composition for crosslinkage made by combining with a specific crosslinking agent, the crosslinked substance made by crosslinking the composition, an optical material containing the copolymer, the composition or the crosslinked substance. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

The present invention contains a reactive silyl group having a specific structure, has excellent optical transparency, heat resistance and adhesiveness, and is crosslinked to improve dimensional stability, solvent resistance and chemical resistance. The present invention relates to a cycloolefin-based addition copolymer capable of obtaining a crosslinked product. More specifically, the present invention relates to the copolymer, a crosslinking composition containing the copolymer, a crosslinked product of the composition, uses thereof, and a method for producing the copolymer.

[0002]

2. Description of the Related Art In recent years, with the demand for lighter weight, smaller size, and higher density, optical transparency has been achieved in the field of liquid crystal display device parts such as lenses, backlights, light guide plates, substrates, etc., which have conventionally used inorganic glass. The substitution of various resins is progressing. However, in addition to optical transparency, birefringence, heat resistance, moisture absorption resistance, solvent resistance, chemical resistance, dimensional stability, adhesion / adhesion,
Further improvements in resin materials such as mechanical strength are required.

Hitherto, as materials having excellent transparency, hydrides and addition polymers of the following ring-opening polymers of cyclic olefin compounds have been proposed. (1) Hydrogenation product of ring-opening polymer of tetracyclododecene compound or norbornene compound JP-A-60-26024, Patent 3050196
JP-A No. 1-132625, JP-A No. 1-132
32626 publication, Unexamined-Japanese-Patent No. 5-214079 publication etc. (2) Addition copolymer of ethylene and norbornene-based compound or tetracyclododecene-based compound JP-A-61-292601, Makromol. Chem. Ma
cromol. Symp. Vol. 47, 83 (1991) (3) Addition Polymer of Norbornene Compounds JP-A-4-63807 and JP-A-8-198919
Publication No. 9-508649, Special Publication No. 11-
505880, (4) Addition (co) polymers AD. Of norbornene compounds containing alkoxysilyl groups. Hennis et al Am. Chem. Soc. Polymer Preprints Vo
l. 40 (2) 782 (1999), JP-A-7-196736,
International Patent Publication WO98 / 20394, International Patent Publication WO97 / 20871

The polymers (1) and (2) often have a glass transition temperature of less than 200 ° C., and are often insufficient in heat resistance. Further, since it is not crosslinked, it has a problem in solvent resistance, chemical resistance or dimensional stability. Incidentally, JP-A-5-214079 discloses a reactive silyl group-containing norbornene-based polymer obtained by hydrosilylation of a polymer of a norbornene-based monomer having an unsaturated bond in a side chain and subsequent hydrogenation. Although described, there is no description or suggestion of crosslinking using a reactive silyl group, that is, since it is uncrosslinked, there is a problem in solvent resistance, chemical resistance or dimensional stability. is there. Further, complete hydrogenation is difficult to perform, and the presence of oxygen at high temperatures often causes the polymer to be colored and deteriorated. The polymer (3) has heat resistance, but does not contain an alkoxysilyl group, so that it is difficult to crosslink and has problems in solvent resistance, chemical resistance, or dimensional stability.
The addition polymer (4) has transparency and heat resistance, and since it contains an alkoxysilyl group, it is an adhesive / adhesive polymer. However, the polymer described in JP-A No. 7-196736 has no description or suggestion of crosslinking utilizing an alkoxysilyl group, that is, since it is uncrosslinked, it has solvent resistance and chemical resistance, Or there is a problem in dimensional stability. In addition, international patent publication WO97 / 208
71 and International Patent Publication WO98 / 20394 describe a cyclic olefin-based addition copolymer containing a reactive silyl group and a crosslinked product thereof with a photoacid generator. However, in the method of crosslinking by photoirradiation using a photo-acid generator, it is difficult to obtain a uniform cross-linked structure because the cross-linking of the surface portion of a sheet or film having a large film thickness mainly progresses. In addition, when a photo-acid generator is used, crosslinking proceeds due to light, so it is necessary to block light during storage or processing, and there is also the problem of poor handleability.

[0005]

DISCLOSURE OF THE INVENTION As a result of intensive studies in view of the above problems, the present inventors have found that a cyclic olefin addition copolymer containing a reactive silyl group having a specific structure and a specific compound It was found that the use of a composition containing any of the above makes it possible to obtain a crosslinked product having excellent optical transparency, heat resistance, adhesiveness, and further improved dimensional stability, solvent resistance and chemical resistance, and the present invention Has been completed.

[0006]

The present invention is directed to a cyclic olefin-based addition copolymer containing a reactive silyl group having a specific structure described below, a crosslinking composition containing the copolymer,
The present invention provides a crosslinked product of the composition, uses thereof, and a method for producing the copolymer.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The cyclic olefin-based addition copolymer of the present invention has a repeating unit (a) represented by the following formula (1) and the following formula (4):
The repeating unit (b) represented by is included and the number average molecular weight is 10,000 to 1,000,000.

[0008]

[Chemical 5]

[In the formula (1), A ^{1 to} A ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group,
Alternatively, in the reactive silyl group represented by the following formula (2) or the following formula (3), at least one of A ^{1 to} A ⁴ represents a reactive silyl group. X is -CH ₂ -, or -O- are shown, m
Represents 0 or 1. ]

[0010]

[Chemical 6]

[In the formula (2), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 0 to 5]. In addition, Y has 2 carbon atoms
The hydrocarbon residues of aliphatic diol, alicyclic diol, or aromatic diol of 20 are shown. ]

[0012]

[Chemical 7]

[In the formula (3), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 0 to 5]. Z represents a hydrocarbon residue of an aliphatic triol, alicyclic triol or aromatic triol having 4 to 20 carbon atoms. ]

[0014]

[Chemical 8]

[In the formula (4), B ¹ , B ² , B ³ , and B ⁴ are each independently a hydrogen atom, a halogen atom, or a carbon number of 1 to 20.
Alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, halogenated hydrocarbon group, an alkoxy group, a substituent selected from aryloxy group, or - indicates a (CH _{2) k} polar group represented by the Y'. Here, Y ′ is —C (O) OR ⁴ or —OC (O) R ⁵ , and R ⁴ and R ⁵ are an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, Alternatively, a substituent selected from the group consisting of these halogen substituents, and k is an integer of 0 to 5. Also, B ¹ ~
B ⁴ is an alkenyl group formed of B ¹ and B ² or B ³ and B ^4, a cyclo group formed of B ¹ and B ³ , B ¹ and B ⁴ , B ² and B ³ or B ² and B ^4. Also included are alkylene groups and cycloalkenylene groups. p shows the integer of 0-2. ]

The structural unit (a) contained in the cyclic olefin-based addition copolymer of the present invention is a cyclic olefin compound having a reactive silyl group represented by the following formula (5) (hereinafter, referred to as
It is called "specific monomer (1)". ) Is formed by addition polymerization.

[0017]

[Chemical 9]

[In the formula (5), A ¹ , A ² , A ³ , A ⁴ , X and m are the same as those in the formula (1). Examples of such a specific monomer (1) include the following compounds, but the present invention is not limited to these specific examples.

[Specific Examples of Specific Monomer (1) Having Reactive Silyl Group Represented by Formula (2)] 5- [1'-Methyl-2 ', 5'-dioxa-1'-
Silacyclopentyl] -bicyclo [2.2.1] hept-2-ene, 5- [1'-methyl-3 ', 3', 4 ', 4'-tetraphenyl-2', 5'-dioxa- 1'-silacyclopentyl] -bicyclo [2.2.1] hept-2-ene, 5- [1 ', 3', 3 ', 4', 4'-pentamethyl-2 ', 5'-dioxa- 1'-silacyclopentyl]
-Bicyclo [2.2.1] hept-2-ene, 5- [1'-phenyl-2 ', 5'-dioxa-1'.
-Silacyclopentyl] -bicyclo [2.2.1] hept-2-ene, 5- [1'-ethyl-2 ', 5'-dioxa-1'-
Silacyclopentyl] -bicyclo [2.2.1] hept-2-ene, 5- [1'3'-dimethyl-2 ', 5'-dioxa-
1'-Silacyclopentyl] -bicyclo [2.2.1]
Hept-2-ene, 5- [1 ', 3', 4'-trimethyl-2 ', 5'-
Dioxa-1'-silacyclopentyl] -bicyclo [2.2.1] hept-2-ene, 5- [1'-methyl-2 ', 6'-dioxa-1'-
Silacyclohexyl] -bicyclo [2.2.1] hept-2-ene, 5- [1'-ethyl-2 ', 6'-dioxa-1'-
Silacyclohexyl] -bicyclo [2.2.1] hept-2-ene, 5- [1 ', 3'-dimethyl-2', 6'-dioxa-1'-silacyclohexyl] -bicyclo [2.2] ．
1] hept-2-ene, 5- [1 ', 4', 4'-trimethyl-2 ', 6'-
Dioxa-1′-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene, 5- [1 ′, 4 ′, 4′-trimethyl-2 ′, 6′-
Dioxa-1'-silacyclohexyl] methyl-bicyclo [2.2.1] hept-2-ene, 5- [1 ', 4', 4'-trimethyl-2 ', 6'-
Dioxa-1'-silacyclohexyl] ethyl-bicyclo [2.2.1] hept-2-ene, 5- [1'-phenyl-4'4'-dimethyl-2 ',
6'-dioxa-1'-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene, 5- [1'-methyl-4'-phenyl-2 ', 6'-
Dioxa-1′-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene, 5- [1′-methyl-4′-spiro-cyclohexyl-2 ′, 6′-dioxa-1′- Silacyclohexyl]
-Bicyclo [2.2.1] hept-2-ene, 5- [1'-methyl-4'-ethyl-4'-butyl-
2 ', 6'-Dioxa-1'-silacyclohexyl]-
Bicyclo [2.2.1] hept-2-ene, 5- [1 ', 3', 3'-trimethyl-5'-methylene-2 ', 6'-dioxa-1'-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene, 5- [1'-phenyl-2 ', 6'-dioxa-1'
-Silacyclohexyl] -bicyclo [2.2.1] hept-2-ene, 5- [1'-methyl-3'-phenyl-2 ', 6'-
Dioxa-1′-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene, 5- [1 ′, 4 ′, 4′-trimethyl-2 ′, 6′-
Dioxa-1′-silacyclohexyl] -7-oxa-
Bicyclo [2.2.1] hept-2-ene, 5- [1'-methyl-2 ', 6'-dioxa-1'-
Silacyclohexyl] -7-oxa-bicyclo [2.
2.1] hept-2-ene, 5- [1'-methyl-2 ', 7'-dioxa-1'-
Silacycloheptyl] -bicyclo [2.2.1] hept-2-ene, 8- [1 ', 4', 4'-trimethyl-2 ', 6'-
Dioxa-1′-silacyclohexyl] tetracyclo [4.4.0.1 ^2,5 . ^1,7,10 ] dodec-3-ene, 8- [1'-methyl-2 ', 6'-dioxa-1'-
Silacyclohexyl] tetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] dodeca-3-ene, and the like.

[Specific Examples of Specific Monomer (1) Having Reactive Silyl Group Represented by Formula (3)] 5- (2 ', 6', 7'-trioxa-1'-silabicyclo [2] .2.2] octyl) -bicyclo [2.2.
1] hept-2-ene, 5- (4'-methyl-2 ', 6', 7'-trioxa-1'-silabicyclo [2.2.2] octyl) -bicyclo [2.2.1] Hept-2-ene, 5- (4'-ethyl-2 ', 6', 7'-trioxa-1'-silabicyclo [2.2.2] octyl) -bicyclo [2.2.1] hept- 2-ene, 5- (4'-phenyl-2 ', 6', 7'-trioxa-1'-silabicyclo [2.2.2] octyl) -bicyclo [2.2.1] hept-2- Ene, 5- (4'-cyclohexyl-2 ', 6', 7'-trioxa-1'-silabicyclo [2.2.2] octyl) -bicyclo [2.2.1] hept-2-ene, And so on.

As a first method of these compounds, a halogen-containing silane compound having a terminal olefin and cyclopentadiene are subjected to a Diels-Alder reaction in advance to synthesize a silyl halide-substituted cyclic olefin compound. , A diol compound or a triol compound. For example, 5-methyl, dichlorosilyl-bicyclo [2.2.1] hept-2-ene obtained by the Diels-Alder reaction of methyl, vinyl, dichlorosilane and cyclopentadiene is converted into a tertiary amine such as triethylamine. By reacting with 1,3-propanediol in the presence of 5- [1′-methyl-
2 ', 6'-Dioxa-1'-silacyclohexyl]-
Bicyclo [2.2.1] hept-2-ene is obtained.
In addition, as a second method, a compound obtained by reacting a halogenated silane compound having a terminal olefin with a diol compound or a triol compound and cyclopentadiene are subjected to a Diels-Alder reaction in advance.
For example, 1-methyl-1-vinyl-2,6-dioxa-1-sila obtained by reacting methyl, vinyl, dichlorosilane with 1,3-propanediol in the presence of a tertiary amine such as triethylamine. By carrying out the Diels-Alder reaction of cyclohexane with cyclopentadiene,
5- [1'-methyl-2 ', 6'-dioxa-1'-silacyclohexyl] -bicyclo [2.2.1] hept-
2-ene is obtained.

Among these specific monomers (1), the monomer having a reactive silyl group represented by the formula (2) is more stable to an acid when formed into a copolymer, which is preferable. . Furthermore, Y of the reactive silyl group represented by the above formula (2) is an α, ω-diol residue having 2 to 4 carbon atoms, that is,
It is preferable that the dioxa-silacycloalkyl structure is a reactive silyl group forming a 5- to 7-membered ring from the viewpoint of the polymerization yield of the cyclic olefin-based addition copolymer of the present invention. In particular,
Propanediol in which Y is a diol having 3 carbon atoms, or a residue of a substituted propanediol, that is, dioxa-
The silacycloalkyl structure is preferably a reactive silyl group forming a 6-membered ring. The specific monomer (1)
Can be used alone or in combination of two or more.

The ratio of the structural unit (a) having a reactive silyl group in the cyclic olefin addition type polymer of the present invention is
It is preferably 0.5 to 30 mol%. When the proportion of the structural unit (a) having a reactive silyl group is less than 0.5 mol%, the crosslink density when crosslinked is small, and the improvement in solvent resistance, chemical resistance or dimensional stability becomes insufficient. There is. On the other hand, when it exceeds 30 mol%, white turbidity may occur or a problem may occur in the storage stability of the composition described below. The structural unit (a) may be randomly present in the cyclic olefin-based addition copolymer, or may be unevenly distributed in a block or taper shape.

The structural unit (b) represented by the formula (4) in the cyclic olefin-based addition copolymer of the present invention has the following formula (6).
It is formed by addition-polymerizing a cyclic olefin compound represented by (hereinafter referred to as "specific monomer (2)").

[0025]

[Chemical 10]

[In the formula (6), B ¹ , B ² , B ³ , B ⁴ and p are the same as those in the formula (4). Examples of such a specific monomer (2) include the following compounds, but the present invention is not limited to these specific examples. Bicyclo [2.2.1] hept-
2-ene, 5-methyl-bicyclo [2.2.1] hept-2-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-propyl-bicyclo [2.2. 1]
Hept-2-ene, 5-butyl-bicyclo [2.2.
1] hept-2-ene, 5-pentyl-bicyclo [2.
2.1] hept-2-ene, 5-hexyl-bicyclo [2.2.1] hept-2-ene, 5-heptyl-bicyclo [2.2.1] hept-2-ene, 5-octyl-
Bicyclo [2.2.1] hept-2-ene, 5-decyl-bicyclo [2.2.1] hept-2-ene, 5-dodecyl-bicyclo [2.2.1] hept-2-ene, 5,
6-Dimethyl-bicyclo [2.2.1] hept-2-ene, 5-methyl, 5-ethyl-bicyclo [2.2.1]
Hept-2-ene, 5-phenyl-bicyclo [2.2.
1] hept-2-ene, 5-vinyl-bicyclo [2.
2.1] hept-2-ene, 5-allyl-bicyclo [2.2.1] hept-2-ene, 5-isopropylidene-bicyclo [2.2.1] hept-2-ene, 5-ethylidene -Bicyclo [2.2.1] hept-2-ene,
5-Cyclohexyl-bicyclo [2.2.1] hept-
2-ene, 5-fluoro-bicyclo [2.2.1] hept-2-ene, 5-trifluoromethyl-5,6,6-trifluoro-bicyclo [2.2.1] hept-2-ene, 5
-Chloro-bicyclo [2.2.1] hept-2-ene,
Methyl bicyclo [2.2.1] hept-5-ene-2-carboxylate, ethyl bicyclo [2.2.1] hept-5-ene-2-carboxylate, bicyclo [2.2.1] hept- Butyl 5-ene-2-carboxylate, methyl 2-methyl-bicyclo [2.2.1] hept-5-ene-2-carboxylate, 2-methyl-bicyclo [2.2.1] hept-5- Ethyl ene-2-carboxylate, 2-methyl-bicyclo [2.2.1] hept-5-ene-2-carboxylate propyl, 2-methyl-bicyclo [2.2.1] hept-5-ene- Butyl 2-carboxylate, 2-methyl-bicyclo [2.2.1] hept-5-ene-2-carboxylate trifluoroethyl, 2-methyl-bicyclo [2.2.
1] ethyl hept-2-enyl acetate, 2-methyl-bicyclo [2.2.1] hept-5-enyl acrylate, 2-methyl-bicyclo [2.2.1] hept-5-enyl methacrylate, Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate dimethyl, bicyclo [2.
2.1] Hept- ⁵ -ene-2,3-dicarboxylate diethyl, tricyclo [4.3.0.1 ^2,5 ] dec-3-ene, tricyclo [4.3.0.1 ^2,5 ]. Deca-3,7-
Diene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
Dodeca-3-ene, 8-methyl-3-tetracyclo [4.4.0.1 ^2,5 1 ^7,10] dodeca-3-ene, 8-
Methyl-8-carboxymethyl, 3-tetracyclo [4.4.0.1 ^{2,5 17 , 10} ] dodec-3-ene, 8-
Methyl-8-carboxyethyl, 3-tetracyclo [4.4.0.1 ^{2,5 17 , 10} ] dodeca-3-ene and the like can be mentioned. These specific monomers (2) are 1
They may be used alone or in combination of two or more.

The structural unit (b) preferably contains no unsaturated group in its structure in terms of heat resistance and oxidative deterioration. Tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene, 5-vinyl-bicyclo [2.2.1] hept-2-
Ene, 5-allyl-bicyclo [2.2.1] hept-2
-Ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene and the like, the copolymer having a carbon-carbon double bond in the side chain obtained by addition polymerization is It is preferable to further hydrogenate since it can improve heat resistance, oxidation resistance and deterioration resistance. Further, in the structural unit (b), a copolymer that does not contain a polar group such as an ester group or an acid anhydride group has low water absorption and a low dielectric constant, but it is a copolymer having a low adhesiveness and adhesiveness with other materials. Alternatively, since the miscibility tends to decrease, it is preferably selected appropriately according to the purpose of use.

The repeating unit (b) of the present invention has the formula (4)
In the above, when p is 1, it indicates a 2,3 additional structural unit, but it may include a 2,7 additional structural unit. Further, in the formula (4), when p is 2,
Although 3,4 additional structural units are shown, those having a 3,11 additional structural unit or a 3,12 additional structural unit may be included.

The proportion of the structural unit (b) in the cyclic olefin-based addition copolymer of the present invention is usually 60 to 99.5 mol%, preferably 80 to 99 mol%, and more preferably 8.
It is 5 to 98 mol%. If the proportion of the structural unit (b) is less than 60 mol%, the heat resistance may be poor, whereas if it exceeds 99.5 mol%, the birefringence and the adhesiveness / adhesion may be poor.

The cyclic olefin-based addition copolymer of the present invention may further contain a structural unit (c) represented by the following formula (7). Structural unit (c) represented by formula (7)
Can be formed by addition-copolymerizing an α-olefin represented by the following general formula (8) (hereinafter, referred to as “specific α-olefin”).

—CH ₂ —CH (R ⁶ ) — ····· Formula (7) [In Formula (7), R ⁶ is a hydrogen atom, an alkyl group, a phenyl group, an alkyl-substituted phenyl group, or a trialkyl-substituted silyl group. Is a substituent selected from. ]

CH ₂ = CH (R ⁶ ) ······ Equation (8) [wherein R ⁶ is the same as the equation (7). ]

Specific examples of such a specific α-olefin include ethylene, propylene, 1-butene, 1-hexene, 1-octene, trimethylsilylethylene, triethylsilylethylene, styrene, 4-methylstyrene and 2-methyl. Examples thereof include styrene and 4-ethylstyrene. These specific α-olefins may be used alone or in combination of two or more.

The proportion of the structural unit (c) in the cyclic olefin-based addition copolymer is 0 to 40 mol%, preferably 0 to 2
0 mol% [however, structural unit (a) + (b) + (c) = 10
0 mol%]. The ratio of the structural unit (c) is 40 mol%
When it exceeds, the glass transition temperature of the cyclic olefin-based addition copolymer of the present invention becomes low, and the heat resistance is lowered.

The molecular weight of the cyclic olefin addition copolymer of the present invention is such that the polystyrene equivalent number average molecular weight (Mn) measured by gel permeation chromatography using o-dichlorobenzene as a solvent is from 10,000 to 1,
, 000,000, weight average molecular weight (Mw) is 20,000
0 to 1,500,000, preferably a number average molecular weight of 2
50,000 to 500,000, weight average molecular weight 40,
It is 000 to 1,000,000. Particularly, it is preferable that the number average molecular weight is 50,000 to 200,000 and the weight average molecular weight is 100,000 to 700,000. When the number average molecular weight is less than 10,000 and the weight average molecular weight is less than 20,000, the breaking strength and elongation when formed into a film, thin film or sheet are insufficient, and the film tends to crack. On the other hand, the number average molecular weight is 1,000,0
When the weight average molecular weight is more than 1,500,000, the molding processability of the sheet or film is lowered, the solution viscosity becomes high at the time of forming the cast film, the storage stability in the solution becomes poor, and the handling is difficult. Will be difficult.

Since the cyclic olefin-based addition copolymer of the present invention is formed by using the specific monomer (1), it is conventionally known (International Patent Publication WO97 / 20871 and International Patent Publication WO98 / 20394). Compared with the cyclic olefin compound having a reactive silyl group (see gazette, etc.), the molecular weight distribution becomes wider, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2.5 to 7. 0
The range of is relatively easy to obtain. Therefore, the cycloolefin-based addition copolymer of the present invention is excellent in terms of brittleness and cracking when formed into a thin film such as a film, sheet or coating film.

The glass transition temperature of the cyclic olefin addition copolymer of the present invention is determined by the peak temperature of Tan δ temperature dispersion measured by dynamic viscoelasticity. (Storage elastic modulus:
E ′, loss elastic modulus: E ″, Tan δ = E ″ / E ′) The glass transition temperature of the cycloolefin addition copolymer of the present invention measured as described above is usually 200 to 40.
The temperature is 0 ° C, preferably 250 to 380 ° C. When the glass transition temperature is lower than 200 ° C., problems such as thermal deformation are likely to occur when the molded product containing the cyclic olefin-based addition copolymer of the present invention is processed or used. On the other hand, when the temperature exceeds 400 ° C., the processing temperature becomes too high during processing by heat such as heat sealing, and the molded product containing the cyclic olefin addition copolymer of the present invention may be thermally deteriorated. Get higher

The cyclic olefin-based addition copolymer of the present invention is an addition polymerization of the specific monomer (1) and the specific monomer (2) and, if necessary, the "specific α-olefin". Is manufactured by. The manufacturing method will be described below.

As the polymerization catalyst, for example, the following multi-component catalyst (A) or single complex catalyst (B) is used, but the present invention is not limited thereto.

(A) The multi-component catalyst has the following 1), 2)
And 3). 1) Transition metal compound: at least one compound selected from the group of compounds listed below: organic carboxylate, organic phosphite, organic phosphate, organic sulfonate of nickel, cobalt, and palladium , A compound selected from β-diketone compounds and the like. For example, nickel acetate, nickel octoate, 2-
Nickel ethylhexanoate, nickel naphthenate, nickel oleate, nickel stearate, nickel dibutyl phosphite, nickel dibutyl phosphate, nickel dioctyl phosphate, nickel salt of dibutyl phosphate,
Nickel dodecylbenzene sulfonate, nickel p-toluenesulfonate, bis (acetylacetonate)
Nickel, bis (acetylacetate) nickel, 2-
Cobalt (II) ethylhexanoate, Cobalt (III) 2-ethylhexanoate, Cobalt (II) dodecanoate, Cobalt (II) naphthenate, Cobalt (II) versatate, Tris (acetylacetonato) cobalt (III), Palladium acetate, palladium 2-ethylhexanoate, bis (acetylacetonato) palladium and the like.・ Nickel, cobalt, and palladium organic carboxylic acid salts and superstrong acid-modified compounds such as hexafluoroantimonic acid, tetrafluoroboric acid, trifluoroacetic acid, and hexafluoroacetone, ・ Diene or triene compound is distributed on nickel Complex, for example, 1,5-cyclooctadiene complex of nickel, [(η ³ -crotyl) Ni (cyclooctadiene)] [B
_{((CF 3) 2 C 6} H 4) 4], P, N, atomic Yusuke ligand such as O coordinated to nickel complex-nickel, such as [cyclododecatriene] nickel, bis [norbornadiene] nickel Complexes such as bis (triphenylphosphine) nickel dichloride, bis (triphenylphosphine) nickel dibromide, bis (triphenylphosphine)
Cobalt dibromide, bis (tris-tolylphosphine) nickel dichloride, Bis [N- (3-tert-but
ylsalicylidene) phenylaminato] Ni, Ni [PhC (O) C
_{HPPh 2] (Ph) (PPh} 3), Ni (OC (O) (C 6 H 4) PPh 2)
(H) (PCy ₃ ), Ni [OC (O) (C ₆ H ₄ ) P Ph ₂ ] (H) (PP
h ₃ ), a reaction product of Ni (COD) ₂ and PPh ₃ = CHC (O) Ph,
_{[(ArN = CHC 6 H 3} (O) (Anth)] (Ph) (PPh 3) Ni,
_{(Wherein, Ar: 2,6- (Pr) 2} C 6 H 3, Pr: isopropy
l, Anth: 9-anthracene, Ph: phenyl, Cy: Cyclohexy
l, COD: 1,5-cyclooctadien) and other complexes

2) Organoaluminum compound Methylalumoxane, ethylalumoxane, butylalumoxane, methylalumoxane partially mixed with trialkylaluminum, trimethylaluminum, triethylaluminum, triisobutylaluminum, diisobutylaluminum hydride, diethylaluminum chloride, At least one compound selected from organic aluminum compounds such as ethyl aluminum sesquichloride and ethyl aluminum dichloride. Among these, organoaluminum containing at least methylalumoxane is preferable.

3) Compounds added for improving the polymerization activity Non-conjugated diene compounds such as 1,5-cyclooctadiene and 1,5,9-cyclododecatriene. Complexes of boron trifluoride ether, amine, phenol, etc., aluminum trifluoride ether, ein, phenol, etc., tri (pentafluorophenyl) borane, tri (3,5-
Boron and aluminum compounds exhibiting Lewis acidity such as di-trifluoromethylphenyl) borane and tri (pentafluorophenyl) aluminum. Triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (3,5-di-trifluoromethyl-phenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, N, N
-At least one compound selected from ionic boron compounds such as dimethylanilinium tetrakis (pentafluorophenyl) borate and N, N-diethylanilinium tetrakis (pentafluorophenyl) borate.

Examples of the (B) single component catalyst include the compounds shown below. B-1) a compound represented by the following formula ^{(9) [L 1 L 2} ML 3] + [A] - in ... (9) [Formula (9), M is Ni, Co, and Pd atoms Represent
L ¹ , L ² and L ³ represent M ligands, and only one ligand has a σ bond, and all the ligands have 1 to 3 π bonds. A represents a counter anion. L ¹ , L ² and L ^{3 each} represent a compound selected from cyclodiene having 6 to 12 carbon atoms, norbornadiene, cyclotriene having 10 to 20 carbon atoms, and aromatic compound having 6 to 20 carbon atoms. As the counter anion A, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₅ SO ₃ F ⁻ , AlF ₃ S
O ₃ CF ₃ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , CF ₃ CO
_{^{2 -, C 2 F 5 CO}} 2 -, CH 3 C 6 H 4 SO 3 -, B [C 6 F 5] 4
_{^{-, B [C 6 H 3}} (CF 3) 2] 4 - is preferably. ]

B-2) Ni (C ₆ F ₅ ) ₂ or A of Ni (SiCl ₃ ) ₂
RENE complex B-3) [Pd (II) (L ⁴ ) ₄ ] [A] ₂ represented by Pd
Complex [where A is the same as B-1. L ⁴ is a nitrile compound,
A tertiary amine compound and a triarylphosphine compound are shown. ]

Specific examples of these compounds include B-1) [(η ³ -crotyl) Ni (cycloocta-1,5-diene)] [B ((C
F ₃ ) ₂ C ₆ H ₄ ) ₄ ], [(η ³ -crotyl) Ni (cycloocta-1,5-di
_{ene)] [PF 6],} (PPh 3) (C 6 H 5) Ni (Ph 2 PCH =
C (O) Ph), (6-methoxy-bicyclo [2.2.1] hept
-2-ene-end-5σ, 2π) Pd (cycloocta-1,5-dien
e)] [PF ₆ ], [(6-methoxy-bicyclo [2.2.
1] hept-2-ene-end-5σ, 2π) Pd (cycloocta-1,5
-diene)] [SbF ₆ ], [(η ³ -ally) PdCl] ₂ and AgS
[(η ³ -ally) Pd] [SbF ₆ ], obtained from bF ₆ ,
Obtained from [(η ³ -ally) PdCl] ₂ and AgBF ₄ [(η ³ -a
lly) Pd] [BF ₄ ], [(η ³ -crotyl) Pd (cycloocta-1,5-
_{dien)] [PF 6],} [Ph 3 PPdCH 3] [B (CF 3) 2 C 6
_{H 4) 3], [(} clcloocta-1,5-diene) Pd (CH 3) Cl] [B
_{((CF 3) 2 C 6} H 4) 3], B-2) Toluene · Ni (C 6 F 5) 2, Xylene · Ni (C 6 F 5) 2, Mesit
_{ylene · Ni (C 6 F 5} ) 2, Toluene · Ni (SiCl 3) 2, B-3) [Pd (CH 3 CN) 4] [BF 4] 2, [Pd (C 6 H 5 CN) 4]
[BF ₄ ] ₂ , [Pd (C ₆ H ₅ CN) ₄ ] [SbF ₆ ] ₂ , [Pd
((C ₆ H ₅ ) ₃ P) ₂ ] [SbF ₆ ] ₂ , [(6-methoxy-bicycl
o [2.2.1] hept-2-ene-end-5σ, 2π) Pd (cy
cloocta-1,5-diene)] [PF ₆ ] [(6-methoxy-bicyclo [2.2.1] hept-2-ene-end
-(5σ, 2π) Pd (cycloocta-1,5-diene)] [SbF ₆ ] [(η ³ -ally) PdCl] ₂ and AgSbF ₆ [(η ³ -al
ly) Pd] [SbF ₆ ], [(η ³ -ally) PdCl] ₂ and AgBF ₄ [(η ³ -ally) Pd] [BF ₄ ], [(η ³ -crotyl) Pd
(cycloocta-1,5-dien)] [PF ₆ ], [Ph ₃ PdCH ₃ ] [B ((CF
₃ ) ₂ C ₆ H ₄ ) ₄ ] and the like.

These catalyst components are used in the use amount within the following range. A transition metal compound such as a nickel compound, a cobalt compound and a palladium compound is 0.02 to 100 mmol atom per 1 mol of the monomer, and an organoaluminum compound is 1 to 1 mol atom per transition metal compound.
The amount of the non-conjugated diene, the Lewis acid and the ionic boron compound is 5,000 mol and 0.2 to 100 mol per 1 mol atom of nickel or cobalt.

The cycloolefin-based addition copolymer of the present invention comprises a multi-component catalyst or a single catalyst comprising the components selected from the above 1), 2) and optionally 3), and cyclohexane, cyclopentane, Alicyclic hydrocarbon solvents such as methylcyclopentane, hexane, heptane, aliphatic hydrocarbon solvents such as octane, toluene, benzene, xylene, aromatic hydrocarbon solvents such as mesitylene, dichloromethane, 1,2-dichloroethylene, 1, It can be obtained by carrying out the polymerization in a solvent selected from one or more selected from halogenated hydrocarbon solvents such as 1-dichloroethylene, tetrachloroethylene, chlorobenzene and dichlorobenzene.

As a method of polymerization, a solvent and a monomer consisting of a cyclic olefin and, if necessary, a molecular weight modifier are charged into a reaction vessel in an atmosphere of nitrogen or argon, and -20
The polymerization system is set at a temperature in the range of 100 ° C to 100 ° C. Next, the above catalyst component is added and polymerization is carried out in the range of -20 ° C to 100 ° C. The solvent / monomer weight ratio is from 1 to 20.
It is done in the range of. The molecular weight can be controlled by adjusting the amount of polymerization catalyst and α
The target molecular weight is adjusted by the addition amount of the molecular weight modifier such as olefin, hydrogen, aromatic vinyl compound, cyclooctadiene, diphenyldihydrosilane, the conversion rate to the polymer and the polymerization temperature. The molecular weight regulator is preferably styrene, 3-methylstyrene, 4-
Aromatic vinyl compounds such as methylstyrene, 4-ethylstyrene, 3,5-dimethylstyrene, 1-vinylnaphthalene and divinylbenzene are used. The termination of the polymerization is carried out by a compound selected from water, alcohol, organic acid, carbon dioxide gas and the like. A water / alcohol mixture of an acid selected from lactic acid, malic acid, maleic acid, fumaric acid and oxalic acid is added to the polymer solution to separate the catalyst residue from the polymer solution. The catalyst residue can be removed by adsorption removal using an adsorbent such as diatomaceous earth, alumina, silica, activated carbon, or filtration separation using a filter. Polymer, the polymer solution is methanol, ethanol,
It is obtained by putting in alcohol selected from isopropanol, coagulating, and drying under reduced pressure. In this step, unreacted monomers remaining in the polymer solution are also removed.

The cyclic olefin-based addition copolymer having a reactive silyl group of the present invention is, for example, 3.6 to 3.8 ppm of Si-based on a nuclear magnetic resonance spectrum ( ¹ H-NMR).
O-CH ₂ - absorption by CH ₂ in the absorption derived from alicyclic hydrocarbons 0.6～3.0Ppm, and 0.2~0.6ppm
The structure can be confirmed from the absorption of Si—CH ₂ — or Si—CH ₃ of Si-alkyl of. In addition, absorption of bending vibration of C—H bond of alicyclic hydrocarbon appearing near 1,450 cm ⁻¹ by infrared absorption spectrum, 1,100
The structure can be confirmed from the absorption of the bending vibration of the Si—O bond appearing in the vicinity of cm ⁻¹ . Furthermore, when the cyclic olefin-based addition copolymer having a reactive silyl group of the present invention contains an ester group, the stretching vibration of the C═O bond appearing at 1,700 to 1,750 cm ⁻¹ in the infrared absorption spectrum. Its structure can be confirmed from the absorption of. The proportion of the repeating units resulting from the specific monomer 1 in the copolymer, ¹ H-NMR by Si-O-CH ₂ - 3.6
It can be determined from the ratio of absorption of protons at up to 3.8 ppm and absorption of protons of alicyclic hydrocarbons at 0.6 to 3.0 ppm.

The cyclic olefin-based addition copolymer of the present invention includes a conventionally known norbornene-based ring-opening (co) polymer, a hydrogenated product of the (co) polymer and addition of norbornene-based monomer and ethylene. Copolymer (for example, JP-A-61-292)
60, JP-A-60-16870, JP-A-6
0-26024, JP-A-2-51511,
JP-A-1-132625, JP-A-1-13262
6, JP-A-4-202404, JP-A-4-202404
63807, JP-A-8-198919, JP-A-9-508649 and JP-A-11-50588.
No. 0, JP-A-61-292601, etc.) to lower the melt viscosity and substantially improve heat resistance, optical properties (transparency, low birefringence, etc.), adhesion / adhesion, etc. It is also possible to improve the moldability in the case of injection molding without deteriorating. The cyclic olefin-based addition copolymer of the present invention may also be used as a thermosetting transparent resin composition by blending an alicyclic epoxy compound with a polyfunctional organic acid or acid anhydride as an auxiliary agent. You can

In such a composition, the compounding ratio of the cyclic olefin-based addition copolymer of the present invention to another polymer or a low molecular weight compound is such that the type of the polymer of the present invention and the type of the other polymer, The compatibility is appropriately selected depending on the purpose of use of the composition, but in order to obtain a polymer composition having excellent heat resistance, in the composition of the cyclic olefin-based addition copolymer of the present invention, The proportion is 5 to 95% by weight, preferably 1
It is 0 to 90% by weight, more preferably 20 to 80% by weight.

The cyclic olefin-based addition copolymer of the present invention includes known antioxidants such as 2,6-di-t-butyl, 4-methylphenol and 4,4'-thiobis- (6).
-T-butyl-3-methylphenol), 1,1'-bis (4-hydroxyphenyl) cyclohexane, 2,
2'-methylenebis (4-ethyl-6-t-butylphenol), 2,5-di-t-butylhydroquinone, pentaerythrityl-tetrakis [3- (3,5-di-t-).
A phenolic or hydroquinone antioxidant such as butyl-4-hydroxyphenyl) propionate may be added. Furthermore, bis [2-t-butyl-
4- (2'-octadecanyloxycarbonyl) ethyl-6-methyl-phenyl] phosphite, tris (4-
Methoxy-3,5-diphenyl) phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, bis (2,6-)
Oxidative stability by blending phosphorus-based antioxidants such as di-t-butyl-4-methylphenyl) pentaerythritol diphosphite and bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite It is possible to improve the sex. Among these compounds, compounds having a decomposition temperature (5% weight reduction) of 250 ° C. or higher are preferable. Moreover, when adding these antioxidants, it is added in the range of 0.05 to 5.0 parts by weight per 100 parts by weight of the cyclic olefin-based addition copolymer.

Since the cyclic olefin-based addition copolymer of the present invention contains a reactive silyl group having a specific structure,
The following 1) metal compounds, 2) inorganic acids, organic acids, 3) 50
A compound which acts as an acid by heating above ℃, and / or 4) 5 in the presence of water or steam
When the composition is blended with a compound that acts as an acid by heating to 0 ° C. or higher, it can be crosslinked in a short time under a relatively mild temperature condition of 50 to 200 ° C. Therefore, the resulting crosslinked product is substantially not subjected to oxidative deterioration due to heat, maintains the excellent optical characteristics of the cycloolefin-based addition copolymer, and further, because it is crosslinked, the heat resistance is high. Increased dimensional stability and solvent resistance
It has excellent chemical properties. In addition, the reactive silyl group having a specific structure in the copolymer not only contributes to crosslinking, but also enhances adhesion / adhesion and miscibility with other materials.
In addition, since the reactive silyl group in the cyclic olefin-based addition copolymer of the present invention has a specific structure, even if it is blended with the compounds of 1) to 4) above, it becomes a composition. The composition is well-balanced in terms of storage stability / handlability of the composition and activity of crosslinking reaction. Hereinafter, the crosslinking composition containing the cyclic olefin-based addition copolymer of the present invention will be described in detail.

1) Metal compound: Examples of metal compounds usable in the composition of the present invention include Al, Mg, Ga, Zn and B.
a, Ca, Sb, Si, Sn, Ce, Ti, Zr, V,
Examples thereof include metal compounds such as alkoxy compounds, allyloxy compounds, thiol compounds, β-diketone salts, organic carboxylic acid salts, oxides and halides of metals such as Y, Sm, Nd, Yb and Sc.

Specific examples of these compounds include aluminum compounds such as triisopropoxyaluminum, diethylaluminum methoxide, diethylaluminum allyloxide, diisobutylaluminum methoxide, and diisopropoxyethyl acetate aluminum, diisopropoxymagnesium, and diisopropoxymagnesium. Magnesium compounds such as butoxymagnesium, zinc compounds such as zinc acetate and zinc acetylacetonate, calcium compounds such as calcium acetate, gallium compounds such as gallium triisopropoxide and gallium tributoxide, barium diisopropoxide, barium nonylphenolate Such as barium compounds, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioleate, dibutyltin disteare Over preparative dibutyltin Zuma, dioctyl tin fumarate, tin octanoate, tin decanoate,
Tin compounds such as tin oleate, titanium tetraisopropoxide, titanium tetrabutoxide, titanium compounds such as titanium bis (ethylene glycoloxide), vanadium tetrabutoxide, vanadium compounds such as vanadyl triethoxide, antimony glycoloxide, antimony triacetate, Antimony compounds such as antimony trioxide, scandium triisopropoxide, scandium compounds such as scandium trioxide, cerium triisopropoxide, cerium compounds such as cerium trichloride, neodymium triisopropoxide, neodymium oxoisopropoxide, samarium Triisopropoxide, yttrium triisopropoxide, yttrium oxo isopropoxide, yttrium tris [tetraisopropoxide Carboxymethyl aluminum], and the like lanthanide compounds such as. Among these, Sn organic carboxylate is effective as a crosslinking catalyst in a small amount.

2) Inorganic acid, organic acid: hydrochloric acid, sulfuric acid, hydrofluoric acid, tetrafluoroboric acid, phosphorous acid, organic carboxylic acid, organic sulfonic acid, organic sulfinic acid, organic phosphoric acid and the like. 3) Compound that acts as an acid when heated to 50 ° C. or higher: counter anions are BF ₄ , PF ₄ , AsF ₆ , and Sb
Aromatic sulfonium salt, aromatic ammonium salt, aromatic pyridinium salt selected from F ₆ , B (C ₆ F ₅ ) _{4 and the} like,
Examples thereof include aromatic phosphonium salts, aromatic iodonium salts, hydrazinium salts, and metallocene iron salts. 4) Compounds that act as acids by heating to 50 ° C. or higher in the presence of water or steam: trialkyl phosphite, triaryl phosphite, dialkyl phosphite, monoalkyl phosphite , Hypophosphite, organic carboxylic acid secondary or tertiary alcohol ester, organic carboxylic acid hemiacetal ester, organic carboxylic acid trialkylsilyl ester, and the like.

The compounds listed in 1) to 4) above may be used alone or in combination of two or more. Here, the use of two or more kinds in combination may include, for example, the compound of 1) used in combination of two or more kinds, or the combination of the compounds of 1) and 2), for example. . Among the compounds listed in 1) to 4) above, the compound of 4) is preferable from the viewpoint of the balance between storage stability and handleability of the composition and activity of the cross-linking reaction. Particularly, a triester compound of phosphorous acid is particularly preferable. preferable.
In addition, when the composition of the present invention contains a polyfunctional alkoxy compound of a specific metal or a condensate of a polyfunctional alkoxy compound of a specific metal and / or specific metal oxide particles described later, the above 4) In addition to the compound, when the compound of the above 1), especially an organic carboxylic acid salt of Sn is used together, it becomes easy to obtain a crosslinked structure which is optically transparent and is effective in improving dimensional stability and solvent / chemical resistance.

The compounds used as catalysts for crosslinking in 1) to 4) above are blended in an amount of 0.0001 to 5.0 parts by weight per 100 parts by weight of the cyclic olefin addition copolymer of the present invention. Used. In addition, the crosslinking due to the formation of a siloxane bond by the hydrolysis / condensation of the reactive silyl group in the cyclic olefin-based addition copolymer of the present invention is 50
It is carried out in the range of up to 200 ° C. to give a crosslinked product.

The composition of the present invention contains, in addition to at least one selected from the cyclic olefin-based addition copolymer of the present invention and the compounds of the above 1) to 4), Si, Al,
A polyfunctional alkoxy compound of a metal selected from Ti and Zr, that is, a tetraalkoxy compound, a trialkoxy compound, a dialkoxy compound, and a condensation product (condensation degree: 3 to 30) of the polyfunctional alkoxy compound of these metals is selected. At least one compound can be added. When such a compound is blended, it becomes easy to obtain a crosslinked structure which is effective in improving dimensional stability and solvent / chemical resistance in the case of forming a crosslinked body.

Si, Al, Ti, Z which can be used in the present invention
Examples of polyfunctional alkoxy compounds of metals selected from r include, for example, alcohol salts of Si, Al, Ti, Zr and the like, aryl salts such as tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and methyltriethoxy. Examples thereof include silane, dimethyldimethoxysilane, cyclohexyltrimethoxysilane, methylcyclohexyldimethoxysilane, trimethoxyaluminum, triethoxyaluminum, tetraethoxytitanium and tetraethoxyzircon. Further, a condensate of the above compound (condensation degree: 3 to 30) can also be used.
Furthermore, these compounds may be used alone or in combination of two or more.

A tetraalkoxy compound of a polyfunctional alkoxy compound of a metal selected from these polyfunctional Si, Al, Ti, and Zr, or a condensate (condensation degree: 3 to 30) of a polyfunctional alkoxy compound of these metals is used. In this case, the amount is 5 to 60 parts by weight per 100 parts by weight of the cyclic olefin addition copolymer.

The composition of the present invention contains, in addition to at least one selected from the cyclic olefin-based addition copolymer of the present invention and the compounds of 1) to 4) above, silica, alumina, zirconia, titania. At least one metal oxide selected from diatomaceous earth, montmorillonite, tin oxide and the like can be blended. The average particle diameter of the metal oxide is 200 nm or less, preferably 100 nm.
It is the following. If the average particle size exceeds 200 nm, the optical transparency may be impaired. Since such metal oxides form a crosslinked structure by bonding with the reactive silyl group in the cyclic olefin addition copolymer of the present invention, a crosslinked structure effective for improving dimensional stability and solvent / chemical resistance is obtained. It will be easier.

The amount of the above metal oxide compounded is 1 to 40 per 100 weight of the cyclic olefin-based addition copolymer of the present invention.
It is compounded in parts by weight. When the blending amount is less than 1 part by weight, the hardness, elastic modulus and linear expansion coefficient of the crosslinked product obtained by crosslinking are insufficiently improved. On the other hand, if it exceeds 40 weight, the crosslinked product obtained by crosslinking may become brittle.

The cyclic olefin-based addition copolymer of the present invention can be used alone as a film or sheet by a melt extrusion method using a melt extruder or the like, or a hydrocarbon solvent or a halogenated hydrocarbon solvent. , Ketones,
Solution casting method in which the copolymer is dissolved in a solvent selected from polar solvents such as ethers, esters, amines, amides, and urea, cast on a steel belt or carrier film, and then dried to obtain a molded product. Can be used as a film or sheet.
Further, after the polymer is swollen in these solvents, the polymer can be molded and processed into a film or sheet while evaporating the solvent with an extruder. Further, the cyclic olefin-based addition copolymer of the present invention and the composition of the present invention have a reactive silyl group, and therefore have excellent adhesion and adhesiveness with other materials, and thus a coating material containing the copolymer or It is also useful as an adhesive.

However, in order to improve dimensional stability and solvent / chemical resistance, the composition of the present invention is formed and processed into a film, sheet or coating film, and then heated to 50 to 200 ° C. Depending on 50 to 20
A crosslinked product obtained by crosslinking in the presence of water or steam at 0 ° C. is preferred. The cyclic olefin-based addition copolymer of the present invention has a special reactive silyl group,
Even when the solution is stored in a state where the water content is 50 ° C. or less, the solution viscosity hardly increases. In this way, by adding a crosslinking agent to the solution of the copolymer to form a film or sheet, and then forming a crosslinked film or sheet, one having a uniform film thickness is stable. As a result, a product having a uniform film surface free from “warpage”, “waviness” and the like can be obtained. The solution casting method is preferably used for forming the composition into a film or sheet. When the composition of the present invention is molded by the melt extrusion method, cross-linking may progress during molding and a molded product may not be obtained.

The film or sheet containing the crosslinked product of the present invention is a TFT on a substrate containing the film or sheet.
Heat resistance, cleaning liquid resistance, transparency, adhesiveness / adhesion, dimensional stability, and liquid crystal resistance at the time of liquid crystal injection, which are required for substrate materials in processes such as exposure, development, and etching in forming (thin film transistor) Therefore, it is useful as a substrate for a flat display such as a liquid crystal display device or an electroluminescence display device.

The optical transparent material containing the cyclic olefin-based addition copolymer of the present invention or the composition of the present invention has excellent optical transparency, birefringence, heat resistance, adhesion / adhesion and moisture absorption resistance. Since it has a light guide plate, a polarizing film, a surface protection film, a light diffusion film, a retardation film, a transparent conductive film, an antireflection film, an OHP film, an optical disc, an optical fiber, a lens, an optical component, an electronic component, a coating agent, an adhesive agent. Further, it is useful for medical containers, containers and the like.

[0068]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. The molecular weight, total light transmittance,
Glass transition temperature, coefficient of linear expansion, water absorption, adhesion / adhesion,
The toluene swelling degree, tensile strength, elongation, and solution viscosity of the polymer composition were measured by the following methods. (1) Weight average molecular weight, number average molecular weight: Waters (WA
TERS) 150C type gel permeation chromatography (GPC) apparatus using an H-type column manufactured by Toso Co., Ltd., and measured at 120 ° C. using O-dichlorobenzene as a solvent. The obtained molecular weight is a standard polystyrene conversion value.

(2) Refractive index: In accordance with ASTM-D542, refractive index n ²⁵ _D of D line (589 nm) at 25 ° C.
Was measured. (3) Total light transmittance: in accordance with ASTM-D1003,
The total light transmittance was measured using a film having a thickness of 150 μm. (4) Tanδ peak temperature (glass transition temperature): Polymer glass at the peak temperature of dynamic viscoelasticity Tanδ (ratio E ″ / E ′ = Tanδ of storage elastic modulus E ′ and loss elastic modulus E ″) The transition temperature was measured. Rheovibron DDV-01FP (manufactured by Orientec) was used for measurement of dynamic viscoelasticity. Measurement frequency was 10 Hz, temperature rising rate was 4 ° C / min, vibration mode was single waveform, vibration amplitude was 2.5 μm. Obtained by using
It was determined by the peak temperature of Tanδ temperature dispersion.

(5) Coefficient of linear expansion: TMA (Thermal Mec
hanical Analysis / SS6100 (manufactured by Seiko Instruments Inc.)
The sample was fixed with a film thickness of 100 μm, a width of 3 mm, a length of 10 cm or more, and a chuck distance of 10 mm, and the temperature was raised from room temperature to about 200 ° C. to remove residual strain.
° C / min. The temperature was raised by and the linear expansion coefficient was determined from the extension of the chuck distance. (6) Water absorption rate: After being immersed in water at 23 ° C. for 24 hours,
The water absorption was measured from the weight change of the film or sheet.

(7) Adhesiveness / adhesiveness: 10 cm × 10 c
Aluminum is vapor-deposited on a test piece of m, and a notch is formed on this vapor-deposited film by a cutter so that 10 × 10 1 mm × 1 mm grids are formed, and a peeling test with cellophane tape is performed. The number of peeled blocks in 25 blocks was measured. (8) Toluene swelling degree: A film having a thickness of about 50 to 250 μm and a length and width of 2 cm × 2 cm was immersed in toluene at 25 ° C. for 3 hours, the weight of the film before and after the immersion was measured, and the swelling degree was calculated by the following formula. Toluene swelling degree (%) = (weight after dipping in toluene / weight before dipping in toluene) × 100 (9) Tensile strength, elongation (substitution characteristics of brittleness and cracking) According to JIS K7118, a test piece was pulled at a speed of 3
mm / min. It was measured at. (10) Solution viscosity of polymer composition The solution viscosity of the polymer is RE8 manufactured by Toki Sangyo Co., Ltd.
0L-type rotational viscometer, using 3 ^o xR14 as rotor, measured at 25 ° C..

Example 1 Bicyclo [2.2.1] hept-2-ene 1,187.5 mmol (111.6 g) as a monomer, 5-
[1 ', 4', 4'-Trimethyl-2 ', 6'-dioxa-1'-silacyclohexyl] -bicyclo [2.2.
1] hept-2-ene 62.5 mmol (14.9
g), 633 g of toluene as a solvent, and 15.0 mmol of styrene as a molecular weight modifier were charged into a 2,000 ml reactor under nitrogen. In advance, hexane solution of Ni octanoate was mixed with antimony hexafluoride at -10 ° C in a molar ratio of 1: 1.
And the precipitated Ni (SbF ₆ ) _{2 produced as a} by-product is removed, and a hexafluoroantimonic acid modified product of nickel octanoate diluted with a toluene solution is used as a Ni atom to form 0.25 mmol, methylalumoxane 2.50. And 0.75 mmol of boron trifluoride ethyl etherate were charged and polymerized. Polymerization was carried out at 30 ° C. for 3 hours and terminated with methanol. 95% conversion of monomer to copolymer
Met. Water 660 ml, lactic acid 47.5 in the copolymer solution
Millimol was added, and the mixture was stirred and mixed to react with the catalyst component, and the copolymer solution and water were allowed to stand and separate. The copolymer solution from which the aqueous phase containing the reaction product of the catalyst component was removed was put into 3 L of isopropanol to coagulate the copolymer, thereby removing the unreacted monomer and the remaining catalyst residue. The solidified copolymer was dried to obtain a copolymer A.

5- [1 ', 4', 4'-trimethyl-2 ', 6'-dioxa-1'-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene in the copolymer The content of the structure derived from was 4.8 mol%. The measurement is 270 MHz ¹ H-NMR measurement (nuclear magnetic resonance analysis)
(Measured and calculated from the ratio of the CH ₂ absorption of the Si—O—CH ₂ — group of 3.7 ppm and the total protons of the norbornene ring of 0.9 to 3.0 ppm. Solvent: D-toluene, TMS standard ). FIG. 1 shows a ¹ H-NMR chart of copolymer A, and FIG. 2 shows an infrared absorption spectrum of copolymer A. The polystyrene equivalent number average molecular weight (Mn) of the copolymer A is 95,000, and the weight average molecular weight (M
w) was 390,000 and Mw / Mn was 4.1. 10 g of the copolymer A was dissolved in 35.5 g of toluene, and pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and tris (2,4) were used as antioxidants. -Ge-t
-Butylphenyl) phosphite, polymer 1
0.9 parts by weight was added to 00 parts by weight. This copolymer solution is cast to form a film A having a thickness of 150 μm.
-1 was produced. Various physical properties were evaluated. The evaluation results are shown in Table 1.

To a polymer solution prepared by dissolving 10 g of copolymer A in 35.5 g of toluene, each of the above antioxidants was added 0.0
9 g and 0.14 g of tributyl phosphite were added, and the polymer solution was cast to form a film. The film was placed under reduced pressure at 200 ° C. for 2 hours to remove the solvent in the film. This film was exposed to steam at 150 ° C. for 2 hours to obtain a crosslinked film A-2 having a thickness of 150 μm. The solution viscosity (25 ° C.) of the polymer composition used for producing this film A-2 was 2,900 (centipoise:
cp). Further, when stored at 25 ° C. in a nitrogen atmosphere and the viscosity after 1 week was measured, it was 2,900 (c
There was no change in p). The evaluation results are shown in Table 1.

To a polymer solution prepared by dissolving 10 g of copolymer A in 35.5 g of toluene, each of the above antioxidants was added 0.0%.
9 g, tin (II) 2-ethylhexanoate 0.0012
g, 0.07 g of tributyl phosphite and 1.0 g of tetraethoxysilane were allowed to stand at 25 ° C. for 2 hours in an atmosphere having a humidity of 80%, and this polymer solution was cast to form a film. The solvent in the film was removed under reduced pressure at 200 ° C. for 2 hours. This film at 150 ℃,
The film was exposed to water vapor for 2 hours to obtain a crosslinked 150 μm-thick film A-3. The evaluation results are shown in Table 1.

Example 2 Bicyclo [2.2.1] hept-2-ene as a monomer
1,125 mmol, 5- [1 ', 4', 4'-tri
Methyl-2 ', 6'-dioxa-1'-silacyclohex
Sil] -bicyclo [2.2.1] hept-2-ene 12
Copolymerization was performed in the same manner as in Example 1 except that 5 mmol was used.
Body B is obtained. The conversion rate to the copolymer was 85%. Two
70 MHz¹Copolymer B obtained from 1 H-NMR measurement
5- [1'-methyl-4 ', 4'-dimethyl-in
2 ', 6'-Dioxa-1'-silacyclohexyl]-
Structure derived from bicyclo [2.2.1] hept-2-ene
The proportion of building units was 8.0 mol%. Copolymer B
Number average molecular weight in terms of styrene is 85,000, weight average
The average molecular weight was 35,000 and the Mw / Mn was 4.1.
It was In addition, in FIG. ¹H-NMR chart
4 shows the infrared absorption spectrum of copolymer B.
As in Example 1, a thickness of 150 μm of non-crosslinked fiber
Film B-2 cross-linked with Rum B-1, tetraalkoxy
A film B-3 cross-linked with silane was prepared.
It was Also, instead of tetraethoxysilane,
Colloidal silica surface treated with toxysilane (average particle size
(Diameter 10 nm) is SiO₂As 3% by weight in the polymer
The added film B-4 was produced. Of film B-2
The solution viscosity (25 ° C.) of the polymer composition used for production is
When the viscosity was measured in the same manner as in Example 1, it was 3,600.
(Cp), the viscosity (25 ° C) after storage at 25 ° C for 1 week is
It was 3,650 (cp). The evaluation results are shown in Table 1.

Example 3 1,187.5 mmol of bicyclo [2.2.1] hept-2-ene as a monomer, 5- [1'-phenyl-]
4 ', 4'-dimethyl-2', 6'-dioxa-1'-
A copolymer C was obtained in the same manner as in Example 1 except that 62.5 mmol of silacyclohexyl] -bicyclo [2.2.1] hept-2-ene was used. 270MHz ¹ H-N
5- [1′-phenyl-4 ′, 4′-dimethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -bicyclo [2.2.
1] The ratio of structural units derived from hept-2-ene is 4.
It was 2 mol%. In addition, the ¹ H-N of copolymer C is shown in FIG.
An MR chart and an infrared absorption spectrum of copolymer C are shown in FIG. The polystyrene equivalent number average molecular weight of the copolymer C is 99,000, and the weight average molecular weight thereof is 297,00.
At 0, Mw / Mn was 3.0. In the same manner as in Example 1, 150 μm thick uncrosslinked film C-1 and crosslinked film C-2 were prepared and evaluated for physical properties. Solution viscosity (2) of the polymer composition used for the production of the film C-2.
When the viscosity was measured at 5 ° C in the same manner as in Example 1, it was 2,200 (cp), and the viscosity (25 ° C) after storing at 25 ° C for 1 week was 2,250 (cp). The evaluation results are shown in Table 1.

Example 4 Bicyclo [2.2.1] hept-2-ene as a monomer
1,050 mmol, 5- [1'-methyl-4'-ethyl
Ru-4'-butyl-2 ', 6'-dioxa-1'-sila
Cyclohexyl] -bicyclo [2.2.1] hept-2
-Ene 75.0 mmol, 8-methyl-8-methoxyca
Rubonyl tetracyclo [4.4.0.1 ^2,51^7,10] Do
Deca-3-ene 125 mmol, as a molecular weight regulator
18 mmol of styrene was used, and toluene 6 was used as a solvent.
60 g was charged to a 2,000 ml reactor under nitrogen.
The reaction system was adjusted to 10 ° C., and triethylaluminum 0.
Of 20 mmol and 2.5 mmol of methylalumoxane
Mixture, boron trifluoride ethyl etherate 0.75
Limol is added in order, and finally with nickel octanoate.
Antimony hexafluoride reacted at -15 ° C at a molar ratio of 1: 1
0.25 millimolar of nickel compound
Polymer was added to initiate polymerization. Polymerize at 20 ℃ for 2 hours
Polymerization was stopped with ethanol. To Monomer Copolymer
The conversion rate was 89%. Thus obtained
Let the polymer be the copolymer D.

5- [1'-methyl-4'-ethyl-4'-butyl-2 ', 6'-dioxa-1'-silacyclohexyl in copolymer D obtained from 270 MHz ¹ H-NMR measurement ] -Bicyclo [2.2.1] hept-2-
The content of structural units derived from ene was 4.9 mol%. Moreover, the proportion of the structural unit derived from 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 1 ^7,10] dodeca-3-ene was 5.9 mol%. Further, FIG. 7 shows a ¹ H-NMR chart of the copolymer D, and FIG. 8 shows an infrared absorption spectrum of the copolymer D. GPC
The polystyrene-reduced number average molecular weight of copolymer D was 80,000 and the weight average molecular weight was 28,000.
And Mw / Mn was 3.5. Similar to Example 1,
Cast from a toluene solution of copolymer D
m non-crosslinked film D-1 and crosslinked film D
-2 was produced and the physical properties were evaluated. The solution viscosity (25 ° C.) of the polymer composition used to prepare the film D-2 was also measured in the same manner as in Example 1. Viscosity is 3,100 (cp)
The viscosity after storage for 1 week at 25 ° C is 3,200 (cp).
Met. The evaluation results are shown in Table 1.

Example 5 The monomer of Example 2, 5- [1 ', 4', 4'-trimethyl-2 ', 6'-dioxa-1'-silacyclohexyl] -bicyclo [2.2. 1] hept-2-ene 12
Instead of 5 mmol, 5- [1'-methyl-2 ',
A copolymer E was obtained in the same manner as in Example 2 except that 125 mmol of 6'-dioxa-1'-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene was used.
The conversion rate of the monomer to the copolymer was 89%. 270
5- [1'-methyl-2 ', 6'-dioxa-1'-silacyclohexyl] -bicyclo [2.2.1] hept- in copolymer E obtained from MHz ¹ H-NMR measurement
The content of the structural unit derived from 2-ene was 8.9 mol%. Further, FIG. 9 shows a ¹ H-NMR chart of the copolymer E, and FIG. 10 shows an infrared absorption spectrum of the copolymer E. The polystyrene-equivalent number average molecular weight of copolymer E is 77,000, and the weight average molecular weight is 270,000.
w / Mn was 3.5. As in Example 1, uncrosslinked film E-1 was crosslinked with film E-2 and 10% by weight of tetraethoxysilane was used to crosslink film E-.
3, and further, a cross-linked film E-4 was prepared using 3% by weight of colloidal silica (average particle size: 10 nm) hydrophobized with tetraethoxysilane. The physical properties of these were evaluated. The solution viscosity (25 ° C.) of the polymer composition used for producing the film E-2 was measured in the same manner as in Example 1. Solution viscosity (25 ° C) is 3,000 (cp), 2
The viscosity after storage at 5 ° C. for 1 week was 3,050 (cp). The evaluation results are shown in Table 1.

Example 6 Instead of the monomer used in Example 1, bicyclo [2.
2.1] Hept-2-ene 1,137.5 mmol, and 5- [1 ', 4', 4'-trimethyl-2 ', 6'-dioxa-1'-silacyclohexyl] -bicyclo [2.
2.1] hept-2-ene 50 mmol, more tetracyclo [4.4.0.1 ^{2, 5} 1 ^7,10] dodeca-3 except using ene 62.5 mmol, obtained in the same manner as in Example 1 A copolymer F was obtained. Conversion of monomer to copolymer is 94
%Met. The amount of bicyclo present unreacted in the polymerization solution [2.2.1] hept-2-ene and 3- tetracyclo [4.4.0.1 ^{2, 5} 1 ^7,10] cathodic-3-ene The ratio of both structural units in the copolymer was calculated from the gas chromatographic analysis. Also, 270 MHz ¹ H
-5- in the copolymer F obtained from the NMR measurement
[1 ', 4', 4'-Trimethyl-2 ', 6'-dioxa-1'-silacyclohexyl] -bicyclo [2.2.
1] of the structural unit derived from hept-2-ene of bicyclo [2.2.1] hept-2-ene and tetracyclo [4.4.0.1 ^2,5 1 ^7,10 ] dodeca-3-ene The total proportion was calculated. From these, tetracyclo [4.4.
The ratio of structural units derived from 0.1 ^{2,5 17,10} ] dodec-3-ene is 4.9 mol%, and 5- [1 ′, 4 ′,
4'-trimethyl-2 ', 6'-dioxa-1'-silacyclohexyl] -bicyclo [2.2.1] hept-2
The proportion of structural units derived from ene was 3.8 mol%. The ¹ H-NMR chart of the copolymer F is shown in FIG. 11, and the infrared absorption spectrum of the copolymer F is shown in FIG. The polystyrene equivalent number average molecular weight of the copolymer F is 8
6,000, weight average molecular weight 344,000, Mw
/ Mn was 4.0. A thickness of 150 as in Example 1
An uncrosslinked film F-1, having a thickness of μm, a crosslinked film F-2, and a film F-3 crosslinked using 10% by weight of dimethyldimethoxysilane were prepared and evaluated for physical properties. The solution viscosity (25 ° C.) of the polymer composition used for producing the film F-2 was measured in the same manner as in Example 1. The solution viscosity (25 ° C) was 3,500 (cp), and the viscosity (25 ° C) after storing at 25 ° C for 1 week was also 3,500 (cp). The evaluation results are shown in Table 1.

Comparative Example 1 Monomer of Example 1, 5- [1 ′, 4 ′, 4′-trimethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -bicyclo [2.2.1] ] 5-Triethoxysilyl-bicyclo [2.2.1] instead of hept-2-ene
A copolymer H was obtained in the same manner as in Example 1 except that hept-2-ene was used. The proportion of structural units derived from 5-triethoxysilyl-bicyclo [2.2.1] hept-2-ene in copolymer H determined from 270 MHz ¹ H-NMR measurement was 4.8 mol%. It was The number average molecular weight of copolymer H was 105,000, the weight average molecular weight was 367,000, and Mw / Mn was 3.5. As in Example 1, an uncrosslinked film H- having a thickness of 150 μm was used.
1. Crosslinked film H-2 and 10% by weight of tetraethoxysilane were used to make a crosslinked film H-3. The solution viscosity (25 ° C.) of the polymer composition used for producing the film H-2 was measured in the same manner as in Example 1. The solution viscosity (25 ° C.) was 2,500 (cp), and the viscosity (25 ° C.) after storage at 25 ° C. for 1 week was 10,000 (cp). The evaluation results are shown in Table 1.

Comparative Example 2 As the monomer of Comparative Example 1, bicyclo [2.2.1] hept-2-ene 1,125 mmol, 5-triethoxysilyl-bicyclo [2.2.1] hept-2. -En 125
Copolymer I was prepared in the same manner as in Comparative Example 1 except that 1 mmol of 1-hexene was used as a molecular weight modifier and 2.5 mmol of triethylaluminum was used as an organoaluminum compound as a catalyst component. Got The conversion rate of the monomer to the copolymer was 96%. The weight average molecular weight (Mw) of the copolymer I is 328,000,
The number average molecular weight (Mn) is 121,000 and Mw / Mn
Was 2.7. The proportion of structural units derived from 5-triethoxysilyl-bicyclo [2.2.1] hept-2-ene in copolymer I determined from 270 MHz ¹ H-NMR measurement was 4.9 mol%. . As in Comparative Example 1, non-crosslinked film I-1 and crosslinked film I-2 were prepared. The solution viscosity (25 ° C.) of the polymer composition used in the production of the film I-2 was measured in the same manner as in Example 1. The solution viscosity was 3,000 (cp), and the solution viscosity after storage at 25 ° C. for 1 week was 6,000 (cp). The evaluation results are shown in Table 1.

Comparative Example 3 Monomer of Example 1, 5- [1 ′, 4 ′, 4′-trimethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -bicyclo [2.2.1] ] Hept-2-ene 62.
Instead of 5 mmol, 5-methyldiethoxysilyl-
A copolymer J was obtained in the same manner as in Example 1 except that 62.5 mmol of bicyclo [2.2.1] hept-2-ene was used. The conversion rate of the monomer to the copolymer was 94%. The copolymer J has a weight average molecular weight of 345,000, a number average molecular weight of 128,000, and an Mw / Mn of 2.
It was 7. The proportion of structural units derived from 5-methyldiethoxysilyl-bicyclo [2.2.1] hept-2-ene in copolymer J determined from 270 MHz ¹ H-NMR measurement was 4.7 mol%. there were. An uncrosslinked film J-1 and a crosslinked film J-2 were prepared in the same manner as in Example 1. The solution viscosity (25 ° C.) of the polymer composition used for producing the film J-2 was measured in the same manner as in Example 1. The solution viscosity was 2,400 (cp), and the solution viscosity after storage at 25 ° C. for 1 week was 5,000 (cp). The evaluation results are shown in Table 1.

[0085]

[Table 1]

[0086]

EFFECTS OF THE INVENTION According to the present invention, a reactive silyl group having a specific structure is contained, and it has excellent optical transparency, heat resistance and adhesiveness, and by crosslinking, dimensional stability, solvent resistance,
A cycloolefin-based addition copolymer capable of obtaining a crosslinked product with improved chemical properties is obtained.

[Brief description of drawings]

FIG. 1 ¹ H-NMR of copolymer A obtained in Example 1
It is a chart.

FIG. 2 is an infrared absorption spectrum of the copolymer A obtained in Example 1.

FIG. 3 ¹ H-NMR of copolymer B obtained in Example 2
It is a chart.

FIG. 4 is an infrared absorption spectrum of the copolymer B obtained in Example 2.

FIG. 5 ¹ H-NMR of copolymer C obtained in Example 3
It is a chart.

6 is an infrared absorption spectrum of Copolymer C obtained in Example 3. FIG.

FIG. 7 ¹ H-NMR of copolymer D obtained in Example 4
It is a chart.

FIG. 8 is an infrared absorption spectrum of the copolymer D obtained in Example 4.

FIG. 9 ¹ H-NMR of copolymer E obtained in Example 5
It is a chart.

FIG. 10 is an infrared absorption spectrum of the copolymer E obtained in Example 5.

FIG. 11 ¹ H-NM of copolymer F obtained in Example 6
It is an R chart.

FIG. 12 is an infrared absorption spectrum of the copolymer F obtained in Example 6.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08F 236/00 C08F 236/00 4J002 C08J 5/18 CER C08J 5/18 CER 4J015 7/00 301 7/00 301 4J028 C08K 3/16 C08K 3/16 4J100 3/22 3/22 5/00 5/00 C08L 45/00 C08L 45/00 47/00 47/00 G02B 1/04 G02B 1/04 1/11 5 / 30 5/30 6/00 331 6/00 331 1/10 A (72) Inventor Mitsutaka Kaizu 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR Corporation (72) Inventor Toshihito Hayashi Chuo-ku, Tokyo Tsukiji 2-11-24 JR S Co., Ltd. (72) Inventor Kenzo Okita 2-11-24 Tsukiji, Chuo-ku, Tokyo J-SR Co., Ltd. F-term (reference) 2H038 AA51 2H049 BA02 BA06 BB22 BB42 2K009 AA02 CC03 CC09 CC22 CC42 4F071 AA39 AA78 AA81 AA86 AB15 AB18 AB26 AB30 AC05 AC07 AC09 AC13 AD06 AE02 AE17 BA02 07B01B01A01 AF30 AF45 AF01 AF30 AF45 AF54 AF58 AG05 AG28 AH05 A02A01 A02 0530 4J002 BK001 DD016 DD076 DE096 DE098 DE126 DE138 DE148 DG046 DH036 DJ008 DJ018 DK006 EB116 EC076 EC077 EE046 EF006 EG036 EG046 EH006 EJ076 EN136 EQ026 GP4G0E GH4 017 GH4 017 GH4 017 ZE0 GH0E046 GH0E046 GH0E046 GH0E046 AB00A AC45A AC47A AC48A BA00A BA01B BA02B BB00A BB01B BB02B BC12B BC13B BC15B BC16B BC17B BC19B BC25B BC27B CA17C CA18C CB03C EB02 AS25AR25 GA15 AR15 AR21 AR15 FA02 AR15 FA02 AR15 FA02 AR15 FA02 AR11 BA04P BA10P BA15P BA20P BA81H BB01P BB01Q BB03Q BB05Q BB07P BB07Q BB18P BC04P BC04Q BC15Q BC43P BC43Q BC51Q CA04 CA31 DA01 DA62 FA08 FA09 HA08 HA53 HB33 HE44 JA01 JA03 JA32 JA33 JA51 JA58

Claims (19)

[Claims] 1. A repeating unit (a) represented by the following formula (1) and a repeating unit (b) represented by the following formula (4), having a number average molecular weight of 10,000 to 1,000,000.
0 cyclic olefin addition copolymer. [Chemical 1] [In the formula (1), A ^{1 to} A ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, or the following formula (2): Alternatively, in the reactive silyl group represented by the following formula (3), at least one of A ^{1 to} A ⁴ represents a reactive silyl group. X is -CH ₂ -, or -O- are shown, m is 0 or 1. ] [Chemical 2] Wherein ^{(2), R 1, R} 2, R 3 each independently represent a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 20, n is an integer of 0-5. Further, Y represents a hydrocarbon residue of an aliphatic diol having 2 to 20 carbon atoms, an alicyclic diol, or an aromatic diol. ] [Chemical 3] Wherein ^{(3), R 1, R} 2 each independently represent a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 20, n is 0 to 5
Indicates an integer. Z represents a hydrocarbon residue of an aliphatic triol, alicyclic triol or aromatic triol having 4 to 20 carbon atoms. ] [Chemical 4] [In the formula (4), B ¹ , B ² , B ³ , and B ⁴ are each independently
A substituent selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, an alkenyl group, a halogenated hydrocarbon group, an alkoxy group and an allyloxy group, or-(CH ₂ ) _k The polar group represented by Y'is shown. Here, Y'is -C (O) OR ⁴ or -OC
(O) a R ^5, R ^4, R ⁵ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a cycloalkyl group, ant - group or a substituted group selected from group consisting of halogen substituents, , K are integers from 0 to 5. In addition, B ^{1 to} B ⁴ are alkenyl groups formed from B ¹ and B ² or B ³ and B ⁴ , B ¹ and B ³ , B ¹ and B ⁴ , B ² and B ³ or B ² and B ^4. Also included are cycloalkylene groups and cycloalkenylene groups formed from p shows the integer of 0-2. ] 2. A repeating unit (a) represented by the formula (1).
The cyclic olefin-based addition copolymer according to claim 1, wherein the reactive silyl group contained in is a reactive silyl group represented by the formula (2). 3. A repeating unit (a) represented by formula (1)
The reactive silyl group contained in is represented by the formula (2), and the diol residue has a carbon number of 2 to form a ring structure with a Si atom.
The cyclic olefin-based addition copolymer according to claim 1 or 2, which has a diol residue of 4. 4. The ratio of the repeating unit (a) represented by the formula (1) in the cyclic olefin-based addition copolymer is 0.5 to.
It is 30 mol%, The cyclic olefin system addition copolymer according to any one of claims 1 to 3. 5. The cyclic olefin-based addition copolymer according to any one of claims 1 to 4, which has a glass transition temperature of 200 to 400 ° C. 6. The cyclic olefin-based addition copolymer according to claim 1 and Sn, Al, Ga, Zn,
Ca, Ba, Ti, Zr, V, Sb, Sc, Ce, N
Containing at least one compound selected from the group consisting of alkoxy compounds, allyloxy compounds, thiol compounds, organic carboxylates, oxides, halides and β-diketone compounds of metals selected from d, Sm, Y and Yb. A cross-linking composition comprising: 7. A crosslinking composition comprising the cyclic olefin-based addition copolymer according to claim 1 and an organic acid and / or an inorganic acid. 8. A crosslinking composition comprising the cyclic olefin-based addition copolymer according to claim 1 and a compound which acts as an acid when heated to 50 ° C. or higher. 9. A compound which acts as an acid when heated to 50 ° C. or higher in the presence of the cyclic olefin-based addition copolymer according to any one of claims 1 to 5 and water or steam (however, (Excluding the compound according to Item 8). 10. Further, Si, Al, Ti and Zr
The crosslinking composition according to any one of claims 6 to 9, containing at least one compound selected from polyfunctional alkoxy compounds of metals selected from the above and condensates of polyfunctional alkoxy compounds of these metals. object. 11. The method according to claim 6, wherein at least one metal oxide selected from silica, alumina, zirconia, titania, diatomaceous earth, montmorillonite and tin oxide having an average particle diameter of 200 nm or less is blended. The composition for crosslinking according to Item 1. 12. The crosslinkable composition according to claim 6, wherein the reactive silyl group of the cyclic olefin addition copolymer in the crosslinking composition is hydrolyzed and condensed to form a siloxane bond and crosslink. A crosslinked body characterized in that 13. The cyclic olefin-based addition copolymer according to any one of claims 1 to 5, the crosslinking composition according to any one of claims 6 to 11, or the crosslinkable composition according to claim 12. An optical material comprising a crosslinked body. 14. The optical material according to claim 13, which is in the form of a thin film, a sheet or a film. 15. A crosslinked product, which is obtained by casting a solution in which the crosslinking composition according to any one of claims 6 to 11 is dissolved and molding the mixture, and then heating the solution to 50 to 200 ° C. to crosslink the solution. Manufacturing method. 16. A cross-linking composition comprising the cyclic olefin-based addition copolymer according to any one of claims 1 to 5 and a tin compound and a compound capable of generating an acid upon heating and hydrolysis. A method for producing a crosslinked body, which comprises crosslinking a film or sheet obtained by casting a solution in the presence of water or steam at 50 to 200 ° C. 17. The method for producing a crosslinked product according to claim 16, wherein a phosphite compound is used as a compound that generates an acid by heating and hydrolysis. 18. The cyclic olefin-based addition copolymer according to claim 1, wherein a compound selected from transition metal compounds of Ni, Co, and Pd is used as one component of a polymerization catalyst. Method for producing polymer. 19. A polymerization catalyst comprising an aromatic vinyl compound as a molecular weight modifier and a Ni compound, a superacid and / or a Lewis acid and methylalumoxane.
8. The method for producing a cyclic olefin-based addition copolymer according to item 8.