JP4487532B2 - Cyclic olefin addition copolymer, crosslinked product of the copolymer, method for producing the copolymer, composition for crosslinking, and use - Google Patents

Description

  The present invention is excellent in optical transparency, heat resistance, adhesion / adhesion and dimensional stability, and has a methoxysilyl group-containing cyclic olefin addition copolymer suitable for optical materials, a method for producing such a copolymer, and such copolymer The present invention relates to a crosslinking composition containing a coalescence and a film, sheet, and thin film formed by molding the copolymer or the crosslinking composition.

  In recent years, due to demands for lighter weight, smaller size, and higher density, liquid crystal display element parts such as lenses, sealing parts and other optical parts conventionally used with inorganic glass, backlights, light guide plates, TFT substrates, touch panels, etc. Replacement with optically transparent resin is progressing in such fields.

  However, in addition to optical transparency, such optically transparent resins have additional properties such as heat resistance, low water absorption, dimensional stability, adhesion / adhesion with other components, chemical resistance, and toughness. However, a resin material that satisfies all of these requirements has not been put into practical use.

  Patent Documents 1 to 6 are excellent in heat resistance and low water absorption, have a small linear expansion coefficient, excellent thermal dimensional stability, chemical resistance, and excellent adhesion and adhesion to other members. As a material, a cyclic olefin addition copolymer having a hydrolyzable silyl group and capable of crosslinking via the silyl group has been proposed.

  In these techniques, an addition copolymer of a cyclic olefin compound having an alkoxysilyl group as a hydrolyzable silyl group and norbornene (bicyclo [2.2.1] hept-2-ene) has been often used. It was. However, norbornene (bicyclo [2.2.1] hept-2-ene) homopolymers are soluble in halogenated hydrocarbon solvents, nitromethane, nitrobenzene, etc., depending on the type of catalyst and the molecular weight of the polymer. However, there is a problem that it does not necessarily dissolve in general general-purpose solvents such as toluene and cyclohexane, and such a problem is often not solved even by copolymerizing a cyclic olefin compound having an alkoxysilyl group.

  Non-Patent Documents 1 to 4 describe norbornene-based addition (co) polymers, but norbornene-based addition (co) polymers usually have a glass transition temperature as high as 250 ° C. or higher. A solution casting method (casting method) is often used for forming a sheet or the like.

As a solvent generally used in the solution casting method,
1) The addition polymer can be dissolved near room temperature and has high safety.
2) It should be moderately volatile and easy to remove from the molded product.
3) It must be general-purpose, easy to obtain and inexpensive.
In the past, methylene chloride and chloroform were often used. However, in recent years, alicyclic carbonization whose boiling point (under 1 atm) is in the range of 50 to 170 ° C. due to environmental load problems. One or more solvents are frequently selected from hydrogen compounds and aromatic hydrocarbon compounds such as cyclohexane, toluene, and xylene.

  Therefore, it is desired to dissolve a norbornene-based addition copolymer having a hydrolyzable silyl group in a general-purpose solvent such as cyclohexane or toluene at room temperature.

  However, in the conventional addition polymerization of a cyclic olefin compound having an alkoxysilyl group and norbornene, that is, by simply copolymerizing a mixture of both monomers using a nickel-based catalyst or a palladium-based catalyst, cyclohexane is not necessarily used. Addition copolymers that dissolve uniformly and transparently in a solvent such as toluene are not obtained. This is because the conventional polymerization method does not consider the reactivity of each of the cyclic olefin compound having an alkoxysilyl group and norbornene, and the obtained copolymer has a site where the structural unit derived from norbornene is unevenly distributed. This is presumably because it is present (the structural unit derived from the cyclic olefin compound having an alkoxysilyl group is also unevenly distributed). That is, as described above, norbornene homoaddition polymer is insoluble in cyclohexane and toluene. Therefore, when the chain of norbornene-derived structural units becomes long, cyclic ring having alkoxysilyl group in part of norbornene homoaddition polymer. This is considered to be due to the molecular structure in which structural units derived from olefinic compounds are bonded, and the properties of norbornene homo-addition polymer appear.

As a method for preventing such a phenomenon and ensuring the solubility in cyclohexane, toluene and the like, 1) increase the copolymerization ratio of the cyclic olefin compound having an alkoxysilyl group.
2) Although the bonding mode of the structural unit derived from norbornene is usually 2,3-bond, 2,7-bond is partially introduced to disturb the stereoregularity of the molecule.
3) A norbornene derivative having a long-chain alkyl group in the side chain is used instead of norbornene.
Such a method has been proposed.

  For example, Non-Patent Documents 5 to 8 describe that polynorbornene (addition polymer) having solubility in a part of solvent can be produced by selecting the type of catalyst component complex, the type of polymerization solvent, and the like. Has been.

  Among these, when a method for increasing the copolymerization ratio of the cyclic olefin compound having an alkoxysilyl group is used, the polymerization activity is lowered or the alkoxysilyl group reacts during the molding process to generate a gel, or When trying to obtain a cross-linked product, intramolecular cross-links and unreacted alkoxy groups remain, and an effective cross-linked network structure is not formed, and desired properties such as chemical resistance and a reduction in linear expansion coefficient are obtained. There may not be.

  On the other hand, the introduction of the 2,7-bond into the bonding mode of the structural unit derived from norbornene can be achieved by the specific nickel catalyst described in Patent Document 7, the cation catalyst, and the specific palladium catalyst described in Patent Document 8. The linear expansion coefficient of the obtained copolymer and a crosslinked product using such a copolymer may be increased, which may cause problems in thermal dimensional stability.

  Furthermore, even in the method using a norbornene derivative having a long-chain alkyl group in the side chain instead of norbornene, the linear expansion coefficient of the obtained copolymer and a crosslinked product using the copolymer is increased, and thermal dimensional stability is increased. May cause problems.

  In addition, the alkoxysilyl group is used for preventing gelation due to side reaction with the catalyst during the addition polymerization reaction and for the storage stability of the obtained addition copolymer, that is, for the residual catalyst and the storage environment. In order to prevent undesired crosslinking due to the influence of moisture and heat, a relatively stable ethoxysilyl group is often used. However, when trying to obtain a cross-linked product by cross-linking via an alkoxysilyl group, the thermal load on the addition copolymer is small and deterioration is not likely to occur. The crosslinking reaction did not proceed sufficiently, and the resulting crosslinked product sometimes had a large linear expansion coefficient, a variation in the linear expansion coefficient, or a change over time.

As a result of diligent investigation in view of such a situation, the present inventor has obtained a cyclic olefin compound having a structural unit (a) derived from bicyclo [2.2.1] hept-2-ene and a specific methoxysilyl group. The addition copolymer obtained by copolymerizing the derived structural unit (b) so that the structural unit (a) and the structural unit (b) are not unevenly distributed is 10 for both toluene and cyclohexane at 25 ° C. The inventors have found that a cyclic olefin addition copolymer that can be uniformly and transparently dissolved at a concentration of% by weight can be obtained, and the present invention has been completed. The inventor further found that the structural unit (b) has a content in a specific range, and that it is effective to use a specific palladium-based multicomponent catalyst as a catalyst, and thus the present invention has been completed. . In addition, a composition in which an acid generator is blended with the above addition copolymer is effective for obtaining a crosslinked product, and the crosslinked product obtained by crosslinking such a composition has an extremely small linear expansion coefficient, which makes it possible to achieve thermal dimensional stability. As a result, the present invention was completed.
US Pat. No. 5,912,313 US Pat. No. 6,031,058 US Pat. No. 6,455,650 JP 2002-327024 A JP 2003-160620 A JP 2003-48918 A Japanese National Patent Publication No. 9-508649 JP 11-158226 A Macromol. Chem. Rapid Commun. 12, 255-259 (1991) Macromol. Chem. Rapid Commun. 19, 251-256 (1998) Macromol. Symp. 133, 1-10 (1998) Organometallics 2001, 20, 2802-2812 Macromol. Chem. Phys. 2003, 204, 868-876 W. Risse et al. , J .; Mol. Catal. 1992, 76, 219-228 Macromol. Rapid Commun. 18, 689-697 (1997) Macromol. Chem. Phys. 197, 3435-3453 (1996)

  The present invention solves the problems of the conventional cyclic olefin-based addition copolymer having an alkoxysilyl group, has excellent heat resistance, high transparency, adhesion / adhesion to other members, and relates to dimensional stability. Norbornene (bicyclo [2.2.1] hepta), which has a low linear expansion coefficient and can be uniformly dissolved at a concentration of 10% by weight at 25 ° C. in both toluene and cyclohexane, which are general-purpose solvents, to form a transparent solution. It is an object to provide an addition copolymer of 2-ene) and a cyclic olefin compound having a specific methoxysilyl group. Furthermore, the present invention provides a method for producing such a copolymer, a composition for crosslinking using such a copolymer, a crosslinked body, and a film, sheet or film formed by molding such a copolymer or such crosslinked body. And

The cyclic olefin-based addition polymer of the present invention comprises 70 to 98 mol% of a structural unit (a) represented by the following formula (1) in all structural units and a structural unit represented by the following formula (2) ( a copolymer containing 2 to 20 mol% of b),
The number average molecular weight is 30,000 to 300,000,
When the copolymer was dissolved at 25 ° C. in toluene so as to be 10% by weight, the insoluble content was 0.1% by weight or less, and the wavelength of the toluene solution measured by a quartz cell having a light path length of 1 cm was 400 nm. And the transmittance is 85% or more, and
When the copolymer was dissolved in cyclohexane at 25 ° C. so as to be 10% by weight, the insoluble content was 0.1% by weight or less, and the wavelength of the cyclohexane solution measured with a quartz cell having an optical path length of 1 cm was 400 nm. der transmittance of 85% or more in is,
The structural unit (b) is a structural unit formed by addition polymerization of a specific monomer (1) represented by the following formula (4):
The ratio (Rm) of the specific monomer (1) in the monomer composition before the polymerization and the structural unit (b) derived from the specific monomer (1) in the produced copolymer in the initial stage of the polymerization The ratio r (r = Rp / Rm) to the ratio (Rp) satisfies 0.7 ≦ r ≦ 1.3 .

(In Formula (2) and Formula (4) , R ¹ is a substituent selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or an aryl group, X is a methoxy group, k is an integer of 0 to 2, n is 0 or 1.)

In addition, in such a cyclic olefin addition copolymer of the present invention, the structural unit (b) is at least a structural unit derived from 5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene. And / or 9-trimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 .
0 ^2,7 ] dodec-4-ene-derived structural units are preferably included.

  Moreover, it is also preferable that such a cyclic olefin type addition copolymer contains the structural unit (c) represented by the following general formula (3) in addition to the structural unit (a) and the structural unit (b).

(In the formula (3), A ^{1 to} A ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an aryl group, a trialkylsilyl group, an alkoxycarbonyl group, an alkoxy group, And an atom group selected from the group consisting of an ester group formed by A ¹ and A ² , an alkylene group formed by A ¹ and A ³ , and at least one of A ^{1 to} A ⁴ is an alkoxycarbonyl group, An aryl group and a substituent selected from an alkylene group formed by A ¹ and A ³ , m is an integer of 0 or 1)
The crosslinked product of cyclic olefin-based addition copolymer of the present invention is characterized by being formed by crosslinking the cyclic olefin-based addition copolymer of the present invention.

  The method for producing a cyclic olefin addition copolymer of the present invention is a method of addition polymerization of bicyclo [2.2.1] hept-2-ene and a compound represented by the following general formula (4), A palladium catalyst is used, and the compound represented by the general formula (4) is supplied continuously or sequentially to the polymerization system.

(In Formula (4), R ¹ is a substituent selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or an aryl group, X is a methoxy group, k is an integer of 0 to 2, and n is 0 or 1) .)
In such a method for producing a cyclic olefin addition copolymer of the present invention, it is preferable to produce the cyclic olefin addition copolymer of the present invention.

In the method for producing a cyclic olefin addition copolymer of the present invention, the palladium catalyst is a) a palladium compound,
b) ionic boron compounds,
c) A phosphine compound having a substituent selected from an alkyl group having 3 to 15 carbon atoms, a cycloalkyl group, and an aryl group and having a cone angle of 170 to 200, or the phosphine compound. Preference is given to multicomponent catalysts prepared from phosphonium salts and d) organoaluminum compounds.

  Further, in the method for producing a cyclic olefin-based addition copolymer of the present invention, the general formula in the initial polymer produced during the initial polymerization in which the conversion ratio of all monomers to the polymer is 5 to 20%. Ratio r (r = r) of the ratio Rp of the structural unit derived from the compound represented by (4) and the ratio Rm of the structural unit derived from the compound represented by the general formula (4) in all monomers to be subjected to polymerization Rp / Rm) preferably satisfies 0.7 ≦ r ≦ 1.3.

  The crosslinking composition of the present invention is characterized by containing the cyclic olefin addition copolymer according to the present invention and an acid generator.

  In such a crosslinking composition of the present invention, the acid generator is at least one selected from the group consisting of esters of secondary or tertiary alcohols and organic sulfonic acids and alkyl phosphites. It is preferable that it is a compound of these.

  The film, sheet or thin film of the present invention is characterized in that it is formed by molding the cyclic olefin addition copolymer of the present invention or the crosslinking composition of the present invention.

  Moreover, the film, sheet | seat, or thin film of this invention consists of the cyclic olefin type addition copolymer crosslinked material of the said invention, It is characterized by the above-mentioned.

  According to the present invention, derived from a specific cyclic olefin compound having a methoxysilyl group, which is excellent in optical transparency and heat resistance, has a small coefficient of linear expansion, and can be used as a material suitable for sheets and films for optical materials. A cyclic olefin copolymer in which the structural unit (a) and the structural unit (b) derived from another cyclic olefin compound are randomly arranged with a homogeneous composition distribution, and a cyclic olefin copolymer obtained by crosslinking the cyclic olefin copolymer These manufacturing methods can also be provided. In addition, according to the present invention, it is possible to provide a film, sheet or thin film that is excellent in optical transparency and heat resistance and has a small linear expansion coefficient.

  Hereinafter, the present invention will be specifically described.

  The cyclic olefin addition copolymer of the present invention has a structural unit (a) derived from bicyclo [2.2.1] hept-2-ene represented by the following formula (1): 70 to 98 mol%, (2) 2 to 20 mol% of a structural unit (b) derived from a cyclic olefin compound having a methoxysilyl group.

(In the formula (2), R ¹ is a substituent selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or an aryl group, X is a methoxy group, k is an integer of 0 to 2, and n is 0 or 1 It is.
)
Furthermore, the cyclic olefin addition copolymer of the present invention includes, in addition to the structural unit (a) and the structural unit (b), a structural unit (c) represented by the following general formula (3) in 2 to 20 mol% can be included.

(In the formula (3), A ^{1 to} A ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an aryl group, a trialkylsilyl group, an alkoxycarbonyl group, an alkoxy group, And an atom group selected from the group consisting of an ester group formed by A ¹ and A ² , an alkylene group formed by A ¹ and A ³ , and at least one of A ^{1 to} A ⁴ is an alkoxycarbonyl group, An aryl group and a substituent selected from an alkylene group formed by A ¹ and A ³ , m is an integer of 0 or 1)
The structural unit (a) of the cyclic olefin addition copolymer of the present invention is formed by addition polymerization of norbornene (bicyclo [2.2.1] hept-2-ene). The structural unit (b) is obtained by addition polymerization of a cyclic olefin compound having a methoxysilyl group represented by the following general formula (4) (hereinafter also referred to as “specific monomer (1)”). It is formed.

(In Formula (4), R ¹ is a substituent selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or an aryl group, X is a methoxy group, k is an integer of 0 to 2, and n is 0 or 1) .)
In the cyclic olefin addition copolymer of the present invention, the structural unit (c) that can be contained in addition to the structural units (a) and (b) is a cyclic olefin compound represented by the following general formula (5) ( (Hereinafter also referred to as “specific monomer (2)”) is subjected to addition polymerization, and further hydrogenated as necessary.

(In formula (5), A ^{1 to} A ⁴ and m are the same as in formula (3).)
In general, the presence or absence of uneven distribution of structural units (composition) in a copolymer produced by a copolymerization reaction of two types of monomers is described as two types of monomers (monomer A and monomer B). In the copolymer formed in the initial stage of polymerization (when the conversion ratio of all monomers to the polymer is 5 to 20%). It is found by comparing the proportion of structural units derived from A with the proportion of A in the monomer before polymerization.

  That is, the ratio (Rm) of the monomer A in the monomer composition before polymerization and the ratio (Rp) of the structural unit derived from the monomer A in the produced copolymer at the initial stage of polymerization are substantially the same. If there is, such a copolymer has substantially no uneven distribution of composition, and can be said to be a copolymer in which structural units derived from two types of monomers are randomly arranged. On the other hand, if the ratio (Rm) of the monomer A in the monomer composition before polymerization and the ratio (Rp) of the structural unit derived from the monomer A in the produced copolymer at the initial stage of polymerization are significantly different. Such a copolymer can be said to be a copolymer in which structural units derived from two types of monomers are unevenly distributed.

  Such homogeneity or uneven distribution of the copolymer depends on the ratio (Rm) of the monomer A in the monomer composition before the polymerization and the monomer A origin in the produced copolymer in the initial stage of the polymerization. The ratio r (r = Rp / Rm) to the ratio of structural units (Rp) can be expressed as an index. The closer the composition uniformity index r is to 1, the higher the composition uniformity.

  In the present invention, it is preferable that the composition uniformity index r for the specific monomer (1) satisfies 0.7 ≦ r ≦ 1.3, preferably 0.8 ≦ r ≦ 1.2.

  If there is an uneven distribution related to the composition in the copolymer, the solubility in a solvent may decrease. In the case of an addition copolymer of norbornene and a cyclic olefin compound having an alkoxysilyl group, toluene at 25 ° C. and It becomes difficult to uniformly dissolve at 10% by weight with respect to at least one of cyclohexane. Therefore, in order to obtain the cyclic olefin addition copolymer of the present invention, it is necessary to substantially eliminate the uneven distribution of the composition in the copolymer.

  When polymerization is carried out by charging all the monomers for obtaining the cyclic olefin-based addition copolymer of the present invention, that is, norbornene and the specific monomer (1), into the reaction vessel at once, the polymerization reaction is carried out. Initially, the composition of the monomer composition subjected to the reaction differs from the composition ratio of the structural units derived from each monomer in the copolymer. When toluene or cyclohexane is used as the polymerization solvent, the polymerization solution becomes cloudy. Or the formed copolymer may be precipitated. This is presumably because uneven distribution related to the above composition occurred in the produced copolymer due to the difference in the copolymerization reactivity ratio between norbornene and the specific monomer (1).

Therefore, in the present invention, in order to eliminate uneven distribution related to the composition of the copolymer, all norbornene used for the reaction is charged before the start of polymerization, and a part of the specific monomer (1) used for the reaction or It is preferable to add all of them continuously or sequentially to the polymerization system after the start of polymerization. By applying such a method, the structural unit (b) derived from the norbornene-derived structural unit (a) and the cyclic olefin compound having the specific methoxysilyl group (“specific monomer (1)”) is unevenly distributed. The addition copolymer present at random in the molecular chain is obtained, and the copolymer dissolves uniformly when dissolved at 10% by weight in both toluene and cyclohexane solvents at 25 ° C. .

  However, when a specific monomer (1) having substantially no difference in copolymerization reactivity with norbornene is used, the specific monomer (1) related to norbornene is collectively put into a reaction vessel. Even if toluene or cyclohexane is used as a reaction solvent for polymerization, the polymerization solution does not become cloudy or the formed copolymer does not precipitate. Also, the resulting copolymer is free from toluene and cyclohexane. The solubility may be equivalent to a copolymer obtained by adding a part or all of the specific monomer (1) continuously or sequentially to the polymerization system after the start of polymerization. In such a case, continuous or sequential addition of the specific monomer (1) may not be performed, and of course, it may be performed. Specifically, when the above-described composition uniformity index r for the specific monomer (1) satisfies 0.7 ≦ r ≦ 1.3 without performing continuous or sequential addition, preferably 0. When satisfying 0.8 ≦ r ≦ 1.2, and more preferably satisfying 0.9 ≦ r ≦ 1.1, the specific monomer (1) may not be added continuously or sequentially.

  Furthermore, when the proportion of the structural unit (b) in the cyclic olefin-based addition copolymer of the present invention is 2 to 20 mol%, preferably 5 to 15 mol% in all the structural units, the solubility in a general-purpose solvent increases. In addition to toluene and cyclohexane, for example, it can be uniformly dissolved in a single solvent or a mixed solvent selected from xylene, ethylbenzene, decalin, chlorobenzene, methylcyclohexane, ethylcyclohexane, chlorocyclohexane, and the like.

  In addition, by making the proportion of the structural unit (b) in the above range, the cyclic olefin-based addition copolymer of the present invention is excellent in adhesion and adhesion to other members, and also has a crosslinked body as a crosslinking composition. When obtained, the intermolecular crosslinking proceeds to obtain a crosslinked body having an appropriate crosslinking density, and the effect of greatly reducing the linear expansion coefficient is also obtained.

The specific monomer (1) represented by the general formula (4) used in the present invention can be obtained by a Diels-Alder reaction between cyclopentadiene and a vinylmethoxysilyl compound. That is, a compound having a methoxysilyl group-substituted bicyclo [2.2.1] hept-2-ene structure and a compound having a methoxysilyl group-substituted tetracyclododecene structure are obtained, and purification separation by distillation, etc. is performed. Thus, each compound can be obtained with a purity of 95% or more.
Specific examples of the specific monomer (1) include the following, but the present invention is not limited to these compounds.
5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-methyldimethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-dimethylmethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-ethyldimethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-cyclohexyldimethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-chlorodimethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-phenyldimethoxysilyl-bicyclo [2.2.1] hept-2-ene,
9-trimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-methyldimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-ethyldimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-4-
En,
9-cyclohexyldimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-phenyldimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-dimethylmethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . ^02,7 ] dodec-4-ene and the like.

Among these compounds,
5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-methyldimethoxysilyl-bicyclo [2.2.1] hept-2-ene 9-trimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-methyldimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene is preferred.

  The proportion of the structural unit (a) in the cyclic olefin-based addition copolymer of the present invention is usually 70 to 98 mol%, preferably 85 to 95 mol% in all the structural units. If it exceeds 98 mol%, the solubility of the copolymer in the solvent may be lost, or it may be difficult to obtain a crosslinked product having a reduced coefficient of linear expansion related to dimensional stability due to too few crosslinking sites. There is. Moreover, when the ratio is less than 70 mol%, mechanical strength falls, there is no toughness, and when it shape | molds to a film or a sheet | seat, it may become a weak thing.

  In the present invention, the structural unit (c) may be further introduced into the copolymer using a specific monomer (2). In such a case, the structural unit (c) is preferably introduced in a range of 2 to 20 mol% in all the structural units. By introducing the structural unit (c) in the above range, it is possible to impart the effect of reducing birefringence and the effect of improving the mechanical strength related to the “cracking” of the film or sheet. When the proportion of the structural unit (c) is less than 2 mol%, these effects may not be expected. On the other hand, when the proportion exceeds 20 mol%, the linear expansion coefficient increases or the polymerization activity decreases. Sometimes.

Specific examples of the specific monomer (2) in the present invention include the following compounds, but the present invention is not limited to these specific examples.
Tricyclo [5.2.1.0 ^2,6 ] dec-8-ene,
3-methyl-tricyclo [5.2.1.0 ^2,6 ] dec-8-ene,
Tricyclo [5.2.1.0 ^2.6 ] deca-3,8-diene,
5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-t-butoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-phenyl-bicyclo [2.2.1] hept-2-ene 5-benzyl-bicyclo [2.2.1] hept-2-ene 5-indanyl-bicyclo [2.2.1] hept-2- Enspiro [fluorene-9,4 ′,-tricyclo [5.2.1.0 ^2,6 ] dec-8′-ene,
9-phenyl-tetracyclo [6.2.1.1 ^3,6 0 ^2,7 ] dodec-4-ene,
9-methoxycarbonyl-tetracyclo [6.2.1.1 ^3,6 0 ^2,7 ] dodec-4-ene, 9-t-butoxycarbonyl-tetracyclo [6.2.1.1 ^3,6 0 ^{2, 7} ] Dodec-4-ene,
9-Benzyloxycarbonyl-tetracyclo [6.2.1.1 ^3,6 0 ^2,7 ] dodec-4-
En,
9-methyl-9-methoxycarbonyl-tetracyclo [6.2.1.1 ^3,6 0 ^2,7 ] dodec-4-ene,
9-methyl-9-ethoxycarbonyl-tetracyclo [6.2.1.1 ^3,6 0 ^2,7 ] dodec-4-ene,
And 9-methyl-9-t-butoxycarbonyl-tetracyclo [6.2.1.1 ^3,6 0 ^2,7 ] dodec-4-ene.

  The glass transition temperature of the cyclic olefin-based addition copolymer of the present invention is determined by the peak temperature of Tanδ temperature dispersion measured by dynamic viscoelasticity (storage elastic modulus: E ′, loss elastic modulus: E ″, Tanδ). = E ″ / E ′), usually 200 to 450 ° C., preferably 250 to 400 ° C., more preferably 300 to 380 ° C.

  When the glass transition temperature is less than 200 ° C., the heat resistance is inferior, and when it exceeds 450 ° C., the polymer becomes rigid and the linear expansion coefficient is reduced, but it may be easily broken.

  The molecular weight of the cyclic olefin addition copolymer of the present invention is measured by a gel permeation chromatography method using o-dichlorobenzene as a solvent at a temperature of 120 ° C., and has a polystyrene-equivalent number average molecular weight (Mn) of 30,000. ~ 300,000, weight average molecular weight (Mw) of 50,000 to 500,000, preferably number average molecular weight (Mn) of 50,000 to 200,000, weight average molecular weight (Mw) of 100,000 to 300,000 000.

  When the number average molecular weight (Mn) is less than 30,000 and the weight average molecular weight (Mw) is less than 50,000, the film or sheet is easily broken. Further, when the number average molecular weight (Mn) exceeds 300,000 and the weight average molecular weight (Mw) exceeds 500,000, the solution viscosity of the polymer is high when a film or sheet is produced by the casting method (solution casting method). Become too difficult to handle.

  The cyclic olefin-based addition copolymer of the present invention is excellent in solubility in both toluene and cyclohexane at 25 ° C., and when dissolved at 10% by weight, it is uniformly dissolved to obtain an almost transparent solution. Specifically, when the copolymer was dissolved in toluene at 25 ° C. so as to be 10% by weight, the insoluble content was 0.1% by weight or less, and the optical path length was measured with a 1 cm quartz cell. When the transmittance of the toluene solution at a wavelength of 400 nm is 85% or more, preferably 90% or more, and the copolymer is dissolved in cyclohexane at 25 ° C. so as to be 10% by weight, an insoluble content is obtained. Is 0.1 wt% or less, and the transmittance at a wavelength of 400 nm of the cyclohexane solution measured with a quartz cell having an optical path length of 1 cm is 85% or more, preferably 90% or more.

  Since the specific methoxysilyl group of the present invention has a higher reactivity than the ethoxysilyl group conventionally used, it is possible to use a specific polymerization catalyst to gel the resulting addition copolymer. It is necessary to prevent such as. Moreover, since the catalyst or catalyst residue remaining in the obtained load copolymer may cause gelation during storage, it is preferable to use a highly active catalyst that is effective even in a small amount. Furthermore, in removing the catalyst after the polymerization, there is a demand for an uncomplicated method in which the obtained addition copolymer does not gel, and the catalyst is also required to be easily removed.

In the present invention, as a polymerization catalyst satisfying the above conditions,
a) palladium compound b) ionic boron compound c) phosphine compound having a substituent selected from an alkyl group having 3 to 15 carbon atoms, a cycloalkyl group and an aryl group and having a cone angle of 170 to 200 Or a phosphonium salt obtained using the phosphine compound d) a multicomponent catalyst containing an organoaluminum compound is used.

Since such a catalyst has a very high polymerization activity, it can be polymerized with a small amount of catalyst, and it is easy to remove the catalyst with a compound such as alcohols, ethers, and ketones. When it is used, it is easy to make the palladium atom and the aluminum atom remaining in the addition copolymer each 10 ppm or less without gelling the obtained addition copolymer. Hereinafter, each component of such a catalyst will be described.
a) Palladium compound Examples of the palladium compound include palladium organic carboxylates, organic phosphites, organic phosphates, organic sulfonates, β-diketone compounds, halides, etc., which are dissolved in a hydrocarbon solvent. Palladium organic carboxylates and β-diketone compounds are preferred as compounds that are easy and have high polymerization activity.

Specific examples of these compounds include palladium acetate, propionate, maleate, fumarate, butyrate, adipate, 2-ethylhexanoate, naphthenate, oleate, and dodecanoate. , Neodecanoate, 1,2-cyclohexanedicarboxylate, 5-norbornene-2-carboxylate, benzoate, phthalate, terephthalate, naphthoate, etc., palladium organic carboxylate, palladium acetate Triphenylphosphine complex of palladium, tri (m-tolyl) phosphine complex of palladium acetate, organic carboxylic acid complex of palladium such as tricyclohexylphosphine complex of palladium acetate, dibutyl phosphite of palladium, dibutyl phosphate, dioctyl phosphate Salts, phosphites such as dibutyl phosphate, phosphates, para Palladium organic sulfonates such as um dodecylbenzenesulfonate, p-toluenesulfonate, bis (acetylacetonato) palladium, bis (hexafluoroacetylacetonato) palladium, bis (ethylacetoacetate) palladium, bis (Phenylacetoacetate) palladium β-diketone compounds such as palladium, dichlorobis (triphenylphosphine) palladium, dichlorobis [tri (m-tolylphosphine)] palladium, dibromobis [tri (m-tolylphosphine)] palladium, dichlorobis [tri (M-xylylphosphine)] palladium, dibromobis [tri (m-xylylphosphine)] palladium, an imidazole complex represented by [C ₃ H ₅ N ₂ ] ₂ [PdCl ₄ ], [Ph ₃ PCH ₂ C (O) CH ₃ ] ₂ [Pd ₂ Cl ₆ ]
Palladium halide complexes such as acetonyltriphenylphosphonium complex represented by the formula:
b) Compound selected from ionic boron compounds Examples of ionic boron compounds include triphenylcarbenium tetrakis (pentafluorophenyl) borate and triphenylcarbenium tetrakis [3,5-bis (trifluoromethyl) phenyl]. Borate, triphenylcarbenium tetrakis (2,4,6-trifluorophenyl) borate, triphenylcarbenium tetraphenylborate, tributylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) ) Borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diphenylanilinium tetrakis (pentafluorophenyl) borate, Lithium And mutetrakis (pentafluorophenyl) borate.
c) Phosphine Compound, Phosphonium Salt As the phosphine compound, a phosphine compound having a substituent selected from an alkyl group having 3 to 15 carbon atoms, a cycloalkyl group, and an aryl group and having a cone angle of 170 to 200 Is mentioned. Such a phosphine compound is a trivalent electron-donating phosphorus compound (tertiary phosphine compound) having an alkyl group, a cycloalkyl group, or an aryl group as a substituent.

The cone angle deg of the tertiary phosphine compound is C.I. A. Measured by Tolman (Chem. Rev. Vol. 77, 313 (1977)) with a model formed by three substituents of metal and phosphorus atoms, with the bond distance of metal atoms and phosphorus atoms being 2.28 mm. Is the cone angle.

In the present invention, the cone angle deg which can be used as the catalyst component c) is 17
Examples of phosphine compounds of 0 to 200 include tricyclohexylphosphine (172), di-t-butylphenylphosphine (170) trineopentylphosphine (180), tri (t-butyl) phosphine (182), and tri (pentafluorophenyl). Specific examples include phosphine (184), tri (o-tolyl) phosphine (194), and the like (the parenthesis represents a cone angle deg value).

In the present invention, the phosphonium salt that can be used as the catalyst component c) is a phosphonium salt obtained by reacting a phosphine compound having a cone angle deg of 170 to 200 as described above with a strong acid or a super strong acid. Can be mentioned. In particular,
Tricyclohexylphosphonium tetra (pentafluorophenyl) borate,
Tricyclohexylphosphonium tetra (3,5-ditrifluoromethylphenyl) borate,
Tricyclohexylphosphonium tetrafluoroborate,
Tricyclohexylphosphonium p-toluenesulfonate,
Tricyclohexylphosphonium trifluoromethanesulfonate,
Tri (o-tolyl) phosphonium tetra (pentafluorophenyl) borate,
Tri (t-butyl) phosphonium tetra (pentafluorophenyl) borate,
Tri (t-butyl) phosphonium hexafluoroantimonate,
Etc.
d) Organoaluminum compound Examples of organoaluminum compounds include alkylalumoxane compounds such as methylalumoxane, ethylalumoxane, butylalumoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, diisobutylaluminum hydride, diethylaluminum chloride, diethylaluminum fluoride. Ride, ethylaluminum sesquichloride, alkylaluminum dihalide and other alkylaluminum compounds and halogenated alkylaluminum compounds, or a mixture of the above alkylalumoxane compound and the above alkylaluminum compound are preferably used.

These catalyst components are used in the following amounts.
The palladium compound a) is used in the range of 0.001 to 0.05 mmol Pd atom per 1 mol of the monomer.
The ionic boron compound b) is used in the range of 0.1 to 20 mol per Pd atom.
The phosphine compound or phosphonium salt of c) is used in the range of 0.1 to 2.0 mol per Pd atom.
The organoaluminum compound d) is used in the range of 0.5 to 200 mol with respect to the Pd1 atom.

The cyclic olefin-based addition copolymer of the present invention uses an aliphatic hydrocarbon such as cyclohexane, cyclopentane, and methylcyclopentane, an alicyclic hydrocarbon solvent such as cyclohexane, cyclopentane, and methylcyclopentane. Hydrogen solvent, toluene, benzene, xylene,
One or more solvents selected from aromatic hydrocarbon solvents such as mesitylene, halogenated hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane, 1,1-dichloroethane, tetrachloroethane, chlorobenzene and dichlorobenzene It can be obtained by performing addition polymerization in a temperature range of -20 to 120 ° C.

  The molecular weight of the cyclic olefin addition copolymer of the present invention is adjusted by adding a compound selected from α-olefins such as ethylene and propylene, methyl acrylate, hydrogen, hydrosilane compounds, cyclopentadiene, and cyclopentene to the polymerization system. Of these, ethylene is preferred.

  When a cyclic olefin compound containing an olefinically unsaturated bond in the side chain substituent is used as a monomer, the resulting polymer contains an olefinically unsaturated bond, resulting in poor thermochemical stability, gelation, and discoloration. It may happen. Therefore, it is necessary to hydrogenate at least 90% or more, preferably 95% or more, more preferably 99% or more of the olefinically unsaturated bond of the polymer.

  The hydrogenation method is not particularly limited as long as it can efficiently hydrogenate carbon / carbon unsaturated bonds. In general, hydrogenation is performed in an inert solvent in the presence of a hydrogenation catalyst at a hydrogen pressure of 0.5 to 15 MPa and a reaction temperature of 0 to 200 ° C.

  Examples of the inert solvent include aliphatic hydrocarbons having 5 to 14 carbon atoms such as hexane, heptane, octane, and dodecane, alicyclic hydrocarbons having 5 to 14 carbon atoms such as cyclohexane, cycloheptane, cyclodecane, and methylcyclohexane, and benzene. Aromatic hydrocarbons having 6 to 14 carbon atoms such as toluene, xylene and ethylbenzene are preferably used, and among these, cyclohexane, methylcyclohexane, toluene and xylene are most preferably used.

Examples of the hydrogenation catalyst include group VIII metals such as nickel, palladium, platinum, cobalt, ruthenium and rhodium or compounds thereof such as carbon, alumina, silica, silica alumina,
A solid catalyst supported on a porous carrier such as diatomaceous earth, or a group IV-VIII organic carboxylate such as cobalt, nickel, palladium, a combination of β-diketone compound and organoaluminum or organolithium, ruthenium, rhodium, iridium, etc. A homogeneous catalyst such as a complex is used.

  The decatalyst of the addition-polymerized or further hydrogenated cyclic olefin-based addition copolymer of the present invention is a method of adsorbing a copolymer solution with an adsorbent such as diatomaceous earth, silica, alumina, activated carbon, ion exchange resin Removal method, adding a palladium compound, a polyfunctional amine compound in which an aluminum compound forms a chelate, an aminoalcohol compound, a phosphine compound, etc. to the copolymer solution, filtering, the copolymer solution being ethanol, propanol, etc. It can be carried out by a method such as coagulation removal in alcohols such as acetone or ketones such as acetone and methyl ethyl ketone.

  The copolymer can be recovered by a known method such as a method of directly removing the solvent from the copolymer solution or a method of coagulating and separating with a poor solvent such as the above alcohol or ketone.

Since the cyclic olefin addition copolymer of the present invention has a methoxysilyl group which is a hydrolyzable silyl group in the structural unit (b), it is crosslinked with a siloxane bond by hydrolysis and condensation in the presence of an acid. It can be set as the crosslinked body made. In such a crosslinked product, the structural unit (b) exists without being unevenly distributed in the molecule of the cyclic olefin addition copolymer, and as a result, the crosslinked site is not unevenly distributed, so that the crosslinked network is substantially uniformly distributed throughout the crosslinked material. Formed and the coefficient of linear expansion is greatly reduced. Moreover, since the crosslinked network is formed, it is excellent also in solvent resistance, chemical resistance, and liquid crystal resistance.

  In the present invention, a compound capable of generating an acid by the action of light or heat (acid generator) is blended in the cyclic olefin addition copolymer of the present invention, and then subjected to light irradiation or heat treatment to produce an acid. Can be generated to proceed with crosslinking to obtain the crosslinked product.

Examples of the acid generator used in the present invention include compounds selected from the group of the following 1), 2) and 3), and at least one selected from these is used as the copolymer of 100 weight of the present invention. It is used in the range of 0.001 to 5 weight per part.
1) An aromatic sulfonium salt, aromatic ammonium salt, aromatic pyridinium salt, aromatic phosphonium salt in which the counter anion is selected from BF ₄ , PF ₆ , AsF ₆ , SbF ₆ , B (C ₆ F ₅ ) _4, etc. Compounds that generate acid when heated to 50 ° C. or higher, such as aromatic iodonium salts, hydrazinium salts, iron salts of metallocenes,
2) Trialkyl phosphites, triaryl phosphites, dialkyl phosphites, alkyl phosphites, hypophosphites, esters of secondary or tertiary alcohols of organic carboxylic acids, Hemiacetal ester of organic carboxylic acid, trialkylsilyl ester of organic carboxylic acid, ester compound of organic sulfonic acid and secondary or tertiary alcohol, etc. in the presence or absence of water at 50 ° C. or higher A compound that generates acid when heated,
3) Diazonium salts, ammonium salts, iodonium salts, sulfonium salts, phosphoniums that generate Bronsted acids or Lewis acids upon irradiation with ultraviolet rays such as g rays, h rays, i rays, far ultraviolet rays, X rays, electron rays, etc. Onium salts such as salts, arsonium salts and oxonium salts, halogenated organic compounds such as halogen-containing oxadiazole compounds, halogen-containing triazine compounds and halogen-containing benzophenone compounds, other quinonediazide compounds, α, α-bis (sulfonyl) diazomethane compounds , Α-carbonyl-α-sulfonyldiazomethane compounds, sulfonyl compounds, organic acid ester compounds, organic acid amide compounds, organic acid imide compounds, and the like.

  Among these, the compound 2) is preferably used because it is compatible with the cyclic olefin copolymer of the present invention.

  For molding the cyclic olefin addition copolymer of the present invention or the crosslinking composition containing the copolymer, a solution casting method (casting method) is usually used to obtain a film, sheet or thin film.

  In the solution casting method (casting method), the addition copolymer or the crosslinking composition is usually dissolved in a solvent to prepare a predetermined concentration, and if necessary, after filtration and defoaming treatment, This is done by coating on top and removing the solvent. If the substrate is peeled off after the step of removing the solvent or after removal, a film or sheet is obtained, and if not peeled off, a film is obtained.

  The residual solvent content in the film, sheet or film obtained by the above method is 5000 ppm or less, preferably 2000 ppm or less, more preferably 1000 ppm or less. If the residual solvent content exceeds 5000 ppm, a large amount of volatile matter may be generated during processing under reduced pressure such as vapor deposition or sputtering on a film, sheet or coating, resulting in equipment contamination and reduced pressure reduction. In addition, the linear expansion coefficient may be increased and the dimensional stability may be deteriorated.

In addition, the method for reducing the residual solvent content is not particularly limited, and a known method such as multistage drying at different temperatures or heat drying under reduced pressure can be applied.
The residual solvent content can also be reduced by exposure to water vapor, immersion in a low-boiling halogen solvent such as methylene chloride or 1,2-dichloroethane, or exposure to the vapor, followed by further heating. .

When the crosslinking composition of the present invention is molded, it can be made into a crosslinked body by external heating or light irradiation in the presence of water or water vapor. Specific methods for obtaining a crosslinked product include, for example, the methods described below, but the present invention is not limited to these examples. 1) When a photoacid generator is used as the acid generator There are methods such as irradiating ultraviolet rays in an atmosphere having a humidity of 50% RH or higher, or irradiating ultraviolet rays in a state where water is present on the surface in advance by immersion or the like. Can be mentioned.
2) When a thermal acid generator is used Examples include a method of immersing in hot water at a temperature higher than the temperature at which the thermal acid generator generates acid (usually 50 ° C or higher), or exposing to water vapor at a similar temperature. It is done.

  Among these, a method of using a thermal acid generator and exposing to an unsaturated superheated steam at 120 to 250 ° C. is preferable because removal of the residual solvent can be promoted simultaneously with the crosslinking.

  For molding the cyclic olefin addition copolymer of the present invention or the crosslinking composition containing the copolymer, the glass transition temperature of the cyclic olefin addition copolymer is 280 in addition to the solution casting method as described above. When the temperature is lower than or equal to ° C, a melt molding method can also be applied.

  The cyclic olefin addition copolymer of the present invention and the composition for a crosslinked product thereof include a phenol-based antioxidant, a lactone-based antioxidant, and a phosphorus-based oxidation in order to further improve oxidation resistance and coloration resistance. At least one selected from an inhibitor and a thioether-based antioxidant can be added in an amount of 0.001 to 5 parts by weight per 100 parts by weight of the copolymer.

  The following compounds can be illustrated as a specific example of a phenolic antioxidant.

2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate,
2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol,
Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate,
2,2′-methylenebis (4-methyl-6-tert-butylphenol),
2,2′-methylenebis (4-ethyl-6-tert-butylphenol),
4,4′-butylidene-bis (6-tert-butylphenol),
4,4′-thiobis (3-methyl-6-tert-butylphenol),
Bis (3-cyclohexyl-2-hydroxy-5-methylphenyl) methane,
Pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate],
Triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate],
Examples of 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-bisoctylthio-1,3,5-triazine phosphorus antioxidants include the following compounds.

Bis [2-t-butyl-4- (2′-octadecanyloxycarbonyl) ethyl-6-methylphenyl] phosphite,
Tris (4-methoxy-3,5-diphenyl) phosphite,
Triphenyl phosphite,
Tris (nonylphenyl) phosphite,
Tris (dinonylphenyl) phosphite,
Tris (2,4-di-tert-butylphenyl) phosphite,
Tris (2-t-butyl-4-methylphenyl) phosphite,
Tris (cyclohexylphenyl) phosphite,
2,2′-methylenebis (4,6-di-t-butylphenyl) octyl phosphite,
Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite,
Bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite Examples of sulfur-based antioxidants include the following compounds.
Dilauryl-3,3′-thiodipropionate,
Distearyl-3,3′-thiodipropionate,
Dimyristyl-3,3′-thiodipropionate,
Pentaerythritol-tetrakis (β-lauryl-thio-propionate)
Examples of the lactone antioxidant include the following compounds.
5,7-di-t-butyl-3- (3,4-di-methylphenyl) -3H-benzofuran-2-one,
5,7-di-t-butyl-3- (2,5-di-methylphenyl) -3H-benzofuran-2-one,
5,7-di-t-butyl-3- (2,3-di-methylphenyl) -3H-benzofuran-2-one,
5,7-di-t-butyl-3- (4-methylphenyl) -3H-benzofuran-2-one,
5,7-di-t-butyl-3- (4-ethylphenyl) -3H-benzofuran-2-one,
5,7-di-t-butyl-3-phenyl-3H-benzofuran-2-one,
5,7-di-t-butyl-3-hydroxy-3H-benzofuran-2-one,
The cyclic olefin addition copolymer of the present invention includes other transparent resin-like cyclic olefin addition polymers, hydrogenated cyclic olefin ring-opening polymers, α-olefin and cyclic olefin addition copolymers, and crystals. Α-olefin polymer, rubbery ethylene and α-olefin copolymer having 3 or more carbon atoms, hydrogenated butadiene polymer, hydrogenated butadiene-styrene block copolymer, hydrogenated The isoprene-based polymer can be blended at a ratio of 10 to 90% by weight.

  These films and sheets can be used not only for optical material parts, but also for electronic and electrical parts, medical equipment, electrical insulating materials, and packaging materials.

  Optical materials include light guide plates, protective films, deflection films, retardation films, touch panels, transparent electrode substrates, optical recording substrates such as CD, MD, DVD, TFT substrates, color filter substrates, optical lenses, sealing Used for materials.

  As electronic / electrical parts, they are used for containers, trays, carrier tapes, separation films, cleaning containers, pipes, tubes, and the like.

As medical equipment, it is used for chemical containers, ampoules, syringes, infusion bags, sample containers, test tubes, blood collection tubes, sterilization containers, pipes, tubes and the like.
As the electrical insulating material, it is used as a coating material for electric wires and cables, an insulating material for office automation equipment such as a computer, a printer, and a copying machine, and an insulating material for a printed circuit board.

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

The molecular weight, total light transmittance, glass transition temperature, film warpage, film surface state, tensile strength / elongation, and residual solvent amount in the polymer composition were measured by the following methods.
(1) Molecular weight Using a H type column manufactured by Tosoh Corporation with a 150C gel permeation chromatography (GPC) apparatus manufactured by WATERS, the molecular weight was measured at 120 ° C. using o-dichlorobenzene as a solvent. The obtained molecular weight is a standard polystyrene equivalent value.
(2) Total light transmittance Based on ASTM-D1003, the total light transmittance was measured about the film of thickness 150 micrometers.
(3) Glass transition temperature The glass transition temperature is measured at the peak temperature of the temperature dispersion of Tan δ (ratio of storage elastic modulus E ′ and loss elastic modulus E ″, Tan δ = E ″ / E ′) measured by dynamic viscoelasticity. did. Measurement of dynamic viscoelasticity using Leo Vibron DDV-01FP (manufactured by Orientec), measuring frequency 10Hz, heating rate 4 ° C / min, excitation mode single waveform, excitation amplitude 2.5μm Was used to measure the peak temperature of Tan δ.
(4) Tension coefficient linear expansion TMA (Thermal Mechanical Analysis) SS6100 (manufactured by Seiko Instruments Inc.)
A film piece having a thickness of about 150 μm, a length of 10 mm, and a width of 10 mm is fixed upright and fixed as a test shape, and a load of 1 g is applied by a probe. In order to remove the thermal history of the film, from room temperature to 200 ° C., 5 ° C./min. And then again from room temperature to 5 ° C / min. The linear expansion coefficient was determined from the slope of elongation of the film piece between 50 ° C and 150 ° C.
(5) Tensile strength / elongation (alternative measurement of brittleness / cracking)
In accordance with JIS K7113, the test piece was pulled at a speed of 3 mm / min. Measured with
(6) Composition analysis in addition copolymer in copolymerization reaction and index of composition uniformity During the copolymerization reaction, the polymerization was stopped with isopropyl alcohol when the conversion rate of the monomer to the polymer was 5 to 20%. , The alkoxysilyl group and ester group of the resulting polymer are 270 MHz ¹ H-
The content in the resulting copolymer was determined by measurement with an NMR (proton nuclear magnetic resonance) (solvent: C ₆ D ₆ ) apparatus.

The methoxy group used an absorption of 3.5 ppm (CH _{3 of} SiOCH ₃ ), and the ethoxy group used an absorption of 3.9 ppm (CH _{2 of} SiOCH ₂ CH ₃ ). The methyl ester group used 3.5 ppm absorption (—C (O) OCH ₃ ).

^When the characteristic absorption of ¹ H-NMR overlapped, the residual monomer in the polymer solution was analyzed by gas gromatogram to determine the amount introduced into the copolymer.

From these analyses, the composition in the copolymer at the initial stage of polymerization was analyzed. The uniformity of the produced copolymer is determined by the ratio of the “specific monomer (in the initial copolymerization relative to the ratio (Rm) of the“ specific monomer (1) ”in all the monomers before the start of polymerization” (Rm). The ratio (r) of the ratio (Rp) of structural units derived from “1)” was used as an index. (Uniformity index: r = Rp / Rm)
0.7 ≦ r ≦ 1.3: Good copolymer composition uniformity. The closer r is to 1, the higher the uniformity. r <0.7: “Specific monomer (1)” does not easily enter the copolymer, and the uniformity of the composition is poor.
r> 1.3: “Specific monomer (1)” easily enters the copolymer, resulting in poor composition uniformity.
(7) Measurement of light transmittance of copolymer solution 9 g (10.4 ml) of toluene was used with respect to 1 g of the copolymer and dissolved at 25 ° C.
A weight% toluene solution was prepared. Further, 9 g of cyclohexane (11
. 6 ml) and dissolved at 25 ° C. to prepare a 10 wt% cyclohexane solution.

The light transmittance of a 10 wt% toluene solution and a 10 wt% cyclohexane solution of the copolymer was measured at 25 ° C. at a wavelength of 400 nm with a HITACHI U-2010 type spectroaltimeter using a quartz cell having an optical path length of 1 cm. .

Production of Copolymer 49.1 g of dehydrated toluene with 6 ppm water in a 100 ml glass pressure bottle, 12.3 g of cyclohexane, 9-trimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene 7 mmol (1.96 g) and bicyclo [2.2.1] hept-2-ene 93 mmol (8.75 g) were charged, and the charging port was a hole with a rubber packing. Sealed with an open crown.

Furthermore, 30 ml of gaseous ethylene was charged as a molecular weight regulator through a rubber packing in a pressure bottle.

A pressure bottle containing a solvent and a monomer was heated to 75 ° C., and catalyst components palladium 2-ethylhexanoate (0.0013 milligram atom as Pd atom), triphenylcarbenium pentafluorophenylborate 0.0013 mmol, Polymerization was started by sequentially adding 0.0033 mmol of tricyclohexylphosphine and 0.0067 mmol of triethylaluminum.

15 minutes after the start of the polymerization, a part of the polymer solution is sampled from the polymerization system, the conversion of the solid to the polymer of the monomer, and 9-trimethoxysilyl-tetracyclo [6.2. 1.1 ^3,6 . 0 ^2,7 ] The proportion of structural units derived from dodec-4-ene is ¹ H-N at 270 MHz.
Obtained from MR. The conversion was 19%, and 9-trimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . The proportion of structural units derived from [0 ^2,7 ] dodec-4-ene was 6.9 mol%. From this, the index r of composition uniformity of the copolymer was 0.99.

  The copolymerization reaction was carried out at 75 ° C. for 3 hours, but the polymer solution was transparent without becoming cloudy. From the measurement of the solid content of the polymer solution, the conversion rate to the polymer was 99%.

  The polymer solution was put into 2 liters of isopropanol to coagulate the copolymer. After coagulation, the copolymer A was obtained by drying under reduced pressure at 80 ° C. for 17 hours.

  When 1.0 g of the obtained copolymer A was added to 10.4 ml of toluene at 25 ° C. and stirred, a transparent solution was obtained, and there was no insoluble matter fractionated by filtration with a filter having a pore size of 30 μm. Further, when measured at a wavelength of 400 nm using a quartz cell with an optical path length of 1 cm, the transmittance of the copolymer A in a toluene solution was 98.9%.

  Further, 1.0 g of the obtained copolymer A was added to 11.6 ml of cyclohexane at 25 ° C. and stirred. As a result, a transparent solution was obtained, and there was no insoluble matter fractionated by filtration with a filter having a pore size of 30 μm. Further, when measured at a wavelength of 400 nm using a quartz cell having an optical path length of 1 cm, the transmittance of the copolymer A in a cyclohexane solution was 98.5%.

9-Trimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . The proportion of structural units derived from [0 ^2,7 ] dodec-4-ene was 6.9 mol% as determined from ¹ H-NMR at 270 MHz. The molecular weight was 74,000 in terms of number average molecular weight (Mn), 185,000 in terms of weight average molecular weight (Mw), and the glass transition temperature (Tg) was 360 ° C.
A ¹ H-NMR chart of copolymer A is shown in FIG.

Moreover, when the metal which remains in the copolymer A was analyzed by atomic absorption analysis, Pd was 1 ppm and Al was 2.5 ppm.
Production of Film 10 g of copolymer A was dissolved in a mixed solvent of 10 ml of methylcyclohexane and 40 ml of xylene, and pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxy) was used as an antioxidant. Phenyl) propionate] and tris (2,4-di-t-butylphenyl) phosphite are each 0.6 parts by weight with respect to 100 parts by weight of the polymer, and p-toluenesulfonic acid cyclohexyl ester is used as a crosslinking agent. 0.07 weight part was added with respect to 100 weight part of coalescence.

  This polymer solution is filtered through a membrane filter having a pore size of 10 μm to remove foreign matters, and then cast on a polyester film at 25 ° C., and the temperature of the atmosphere is gradually raised to 50 ° C., and the solvent is dried to form a film. It was.

  After the residual solvent in the film became 5 to 10%, it was exposed to 180 ° C. superheated steam under 1 atm for 1 hour to make a cross-linked film. The film was exposed to a methylene chloride vapor atmosphere at 25 ° C. for 30 minutes to remove residual solvent.

  Then, methylene chloride was removed by vacuum drying at 80 ° C. for 30 minutes to produce a crosslinked film A-1 having a thickness of 150 μm. The evaluation results are shown in Table 1.

9-trimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . Polymerization was carried out in the same manner as in Example 1 except that the amounts used of 0 ^2,7 ] dodec-4-ene and bicyclo [2.2.1] hept-2-ene were changed to 10 mmol and 90 mmol, respectively. .

The conversion rate of the monomer into the polymer for 18 minutes after the initiation of polymerization was 18%, and 9-trimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . The proportion of structural units derived from [0 ^2,7 ] dodec-4-ene was 9.9 mol%. The polymerization system did not become cloudy until the completion of polymerization for 4 hours after the start, and the conversion rate to the polymer was 99%.

  For the obtained copolymer B, the solubility in toluene and cyclohexane and the light transmittance of the solution were evaluated in the same manner as in Example 1. When dissolved in any solvent, the solution became a transparent solution, and the pore size There was no insoluble matter fractionated by filtration through a 30 μm filter, the transmittance of the toluene solution was 99.2%, and the transmittance of the cyclohexane solution was 98.4%.

The number average molecular weight (Mn) of the copolymer B was 63,000, the weight average molecular weight (Mw) was 167,000, and the glass transition temperature (Tg) was 375 ° C. In addition, 9-trimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . The proportion of structural units derived from [0 ^2,7 ] dodec-4-ene was 9.8 mol%. A ¹ H-NMR chart of copolymer B is shown in FIG.

  Further, a crosslinked film B-1 having a thickness of 150 μm was obtained in the same manner as in Example 1 except that the copolymer B was used instead of the copolymer A. The evaluation results are shown in Table-1.

The amount of bicyclo [2.2.1] hept-2-ene and 9-trimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 0 ^2,7 ] dodec-4-ene used is 85 mmol and Polymerization was carried out in the same manner as in Example 1 except that the amount was 15 mmol.

The conversion rate of the monomer into the polymer for 15 minutes after the start of the polymerization was 15%, and 9-trimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . The ratio of structural units derived from structural units derived from [0 ^2,7 ] dodec-4-ene was 14.8 mol%. The polymerization system did not become cloudy until the completion of polymerization for 4 hours after the start, and the conversion rate to the polymer was 99%.

  For the obtained copolymer C, the solubility in toluene and cyclohexane and the light transmittance of the solution were evaluated in the same manner as in Example 1. When dissolved in any solvent, the solution became a transparent solution, and the pore diameter There was no insoluble matter fractionated by filtration through a 30 μm filter, the transmittance of the toluene solution was 99.2%, and the transmittance of the cyclohexane solution was 98.1%.

The number average molecular weight (Mn) of the copolymer C was 62,000, the weight average molecular weight (Mw) was 157,000, and the glass transition temperature (Tg) was 370 ° C. In addition, 9-trimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . The proportion of structural units derived from [0 ^2,7 ] dodec-4-ene was 14.8 mol%. The ¹ H-NMR chart of copolymer C is shown in FIG.
Shown in

  Further, a crosslinked film C-1 having a thickness of 150 μm was obtained in the same manner as in Example 1 except that the copolymer C was used instead of the copolymer A. The evaluation results are shown in Table-1.

Bicyclo [2.2.1] hept-2-ene instead of 90 mmol bicyclo [2.2
. 1] 80 mmol of hepta-2-ene and 95% of endo form tricyclo [5.2.1
. Polymerization was carried out in the same manner as in Example 2 except that 10 mmol of 0 ^2,6 ] dec-8-ene was used.

The conversion rate of the monomer into the polymer for 20 minutes after the start of the polymerization was 19%, and 9-trimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . The proportion of structural units derived from 0 ^2,7 ] dodec-4-ene was 9.9%. The polymerization system did not become cloudy until the completion of the polymerization for 5 hours after the start, and the conversion to a polymer was 98%.

  For the obtained copolymer D, the solubility in toluene and cyclohexane and the light transmittance of the solution were evaluated in the same manner as in Example 1. There was no insoluble matter fractionated by filtration through a 30 μm filter, the transmittance of the toluene solution was 98.5%, and the transmittance of the cyclohexane solution was 99.0%.

The number average molecular weight (Mn) of the copolymer D was 62,000, the weight average molecular weight (Mw) was 166,000, and the glass transition temperature (Tg) was 360 ° C. Further, 9-trimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 ... In copolymer D was determined from gas chromatographic analysis of residual monomer and ¹ H-NMR analysis at 270 MHz. The proportion of structural units derived from 0 ^2,7 ] dodec-4-ene is 9.8 mol%, and the structure derived from tricyclo [5.2.1.0 ^2,6 ] dec-8-ene is 95% endo. The unit ratio was 6.0 mol%. A ¹ H-NMR chart of copolymer D is shown in FIG.

  Further, a film D-1 having a thickness of 150 μm crosslinked was obtained in the same manner as in Example 1 except that the copolymer D was used instead of the copolymer A. The evaluation results are shown in Table-1.

9-trimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . Example 2, except that 10 mmol of 5-trimethoxyoxysilylbicyclo [2.2.1] hept-2-ene was used instead of 10 mmol of 0 ^2,7 ] dodec-4-ene, and was sequentially added to the polymerization system. Polymerization was carried out in the same manner as described above. That is, before the start of polymerization, 90 mmol of bicyclo [2.2.1] hept-2-ene and 4 mmol of 5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene were added together with a solvent and a catalyst. The pressure bottle was charged and 0.75 mmol was added 15 minutes after the start of polymerization, and then 0.75 mmol was added to the polymerization system 7 times every 15 minutes.

  The conversion rate of the monomer into the polymer for 15 minutes after the start of the polymerization is 18%, derived from 5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene in the resulting polymer at that time The ratio of the structural unit was 9.7 mol%, and the copolymer composition uniformity index r was 2.1.

The copolymerization reactivity ratio of bicyclo [2.2.1] hept-2-ene (NB) and 5-trimethoxytoxylsilylbicyclo [2.2.1] hept-2-ene (NMS) is Fineman.
When determined by the -Ross method, r (NB) = 0.53 and r (NMS) = 2.05, and in order to make the composition in the resulting copolymer uniform, 5-trimethoxytoxoxy in the monomer composition It was confirmed that the proportion of silylbicyclo [2.2.1] hept-2-ene (NMS) may be copolymerized at a smaller proportion than the proportion in the produced copolymer.

  Further, the conversion rate of the monomer into the polymer 3 hours after the completion of the addition of all 5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene was 99%, and the polymer at that time The proportion of structural units derived from 5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene was 9.8 mol%.

  For the obtained copolymer E, the solubility in toluene and cyclohexane and the light transmittance of the solution were evaluated in the same manner as in Example 1. When dissolved in any solvent, the solution became a transparent solution, and the pore diameter There was no insoluble matter fractionated by filtration through a 30 μm filter, the transmittance of the toluene solution was 99.0%, and the transmittance of the cyclohexane solution was 98.0%.

The copolymer E thus obtained had a number average molecular weight (Mn) of 69,000, a weight average molecular weight (Mw) of 187,000, and a glass transition temperature (Tg) of 365 ° C. A ¹ H-NMR chart of copolymer E is shown in FIG.

  Further, a film E-1 having a thickness of 150 μm crosslinked was obtained in the same manner as in Example 1 except that the copolymer E was used instead of the copolymer A. The evaluation results are shown in Table-1.

  A cross-linked film E-2 having a film thickness of 150 μm was obtained in the same manner as in Example 5 except that the superheated steam temperature in producing the cross-linked film in Example 5 was changed from 180 ° C. to 150 ° C. . The evaluation results are shown in Table-1.

  35 ml of gaseous ethylene as molecular weight regulator, palladium acetate as catalyst component (0.0005 milligram atom as Pd atom), 0.0006 millimole of triphenylcarbenium pentafluorophenylborate, 0.0005 millimole of tricyclohexylphosphonium 2-ethylhexanoate, triethylaluminum Polymerization was carried out in the same manner as in Example 2 except that 0.0025 mmol was used.

The conversion rate of the monomer into the polymer for 12 minutes after the initiation of the polymerization was 19%, and 9-trimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . The proportion of structural units derived from 0 ^2,7 ] dodec-4-ene was 9.8 mol%, and the copolymer composition uniformity index r was 0.98. Until the polymerization was completed in 3 hours, the polymerization system did not become cloudy and the conversion rate to the polymer was 98%.

  For the obtained copolymer F, the solubility in toluene and cyclohexane and the light transmittance of the solution were evaluated in the same manner as in Example 1. When dissolved in any solvent, the solution became a transparent solution, and the pore size There was no insoluble matter fractionated by filtration through a 30 μm filter, the transmittance of the toluene solution was 98.9%, and the transmittance of the cyclohexane solution was 98.5%.

The number average molecular weight (Mn) of the copolymer F was 65,000, the weight average molecular weight (Mw) was 178,000, and the glass transition temperature (Tg) was 370 ° C. Further, 9-trimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 ... In copolymer F was determined from gas chromatographic analysis of residual monomer and ¹ H-NMR analysis at 270 MHz. The proportion of structural units derived from [0 ^2,7 ] dodec-4-ene was 9.8 mol%.

Further, copolymer F was used in place of copolymer A, and tributyl phosphite was used instead of cyclohexyl ester of p-toluenesulfonic acid in an amount of 1.4 with respect to 100 parts by weight of polymer F.
A crosslinked film F-1 having a film thickness of 150 μm was obtained in the same manner as in Example 1 except that parts by weight were added. The evaluation results are shown in Table-1.

To a 100 ml pressure bottle, 48 g of toluene as a solvent, 82.0 mmol of bicyclo [2.2.1] hept-2-ene, 9-trimethoxysilyl-tetracyclo [6.2.1
. 1 ^3,6 . 0 ^2,7 ] dodec-4-ene 3.0 mmol, 9-methyl-9-methoxycarbonyl-tetracyclo [6.2.1.1 ^3,6 . [0 ^2,7 ] 15.0 mmol of dodeca-4-ene was charged and sealed with a perforated crown with rubber packing.

30 ml of 1 atm ethylene gas was charged through a rubber packing, and then the pressure bottle was set to 75 ° C., palladium acetate as Pd atoms, 0.001 milligram atoms, tricyclohexylphosphine 0.001 millimoles, triphenylcarbenium pentafluoro. Charge 0.0012 mmol of phenylborate and 0.005 mmol of triethylaluminum,
Polymerization was performed.

The conversion rate of the monomer into the polymer for 16 minutes after the start of the polymerization was 19%, and 9-trimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . The proportion of structural units derived from [0 ^2,7 ] dodec-4-ene was 2.8 mol%. The polymerization system did not become cloudy until the polymerization was completed in 9 hours, and the conversion rate to the polymer was 98%. Further, 9-trimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . The proportion of structural units derived from 0 ^2,7 ] dodec-4-ene is 2.8 mol%, and 9-methyl-9-methoxycarbonyl-tetracyclo [6.2.1.1 ^3,6 . The proportion of structural units derived from [0 ^2,7 ] dodec-4-ene was 9.0 mol%.

  As a result of measuring the metal remaining in the copolymer G by atomic absorption analysis, Pd was 0.5 ppm and Al was 2.5 ppm.

  For the obtained copolymer G, the solubility in toluene and cyclohexane and the light transmittance of the solution were evaluated in the same manner as in Example 1. When dissolved in any solvent, the solution became a transparent solution, and the pore size There was no insoluble matter fractionated by filtration through a 30 μm filter, the transmittance of the toluene solution was 92.0%, and the transmittance of the cyclohexane solution was 89.0%.

  A chart of 1H-NMR of copolymer G is shown in FIG.

  Further, a crosslinked film G-1 having a thickness of 150 μm was obtained in the same manner as in Example 1 except that the copolymer G was used instead of the copolymer A. The evaluation results are shown in Table-1.

Comparative Example 1
The same procedure as in Example 5 was conducted except that 10 mmol of 5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene was completely added before the start of polymerization, and the polymerization reaction was carried out without sequential addition. Polymerization was performed.

  The conversion rate of the monomer into the polymer for 20 minutes after the initiation of polymerization was 18%, and it was derived from 5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene in the resulting polymer at that time. The proportion of structural units was 21 mol%, and the copolymer composition uniformity index r was 2.1. One hour after the start of polymerization, the polymer solution started to become slightly cloudy.

The copolymerization reactivity ratio of bicyclo [2.2.1] hept-2-ene (NB) and 5-trimethoxytoxylsilylbicyclo [2.2.1] hept-2-ene (NMS) is Fineman.
When determined by the -Ross method, r (NB) = 0.53, r (NMS) = 2.05, the composition in the resulting copolymer becomes non-uniform, and the bicyclo [2.2.1 in the copolymer] It is considered that the portion having a large proportion of structural units derived from hepta-2-ene is insoluble in toluene, cyclohexane and the like at 25 ° C., and the copolymer solution becomes cloudy or the copolymer is precipitated.

  Thereafter, the polymerization was continued for 3 hours. The conversion ratio of the monomer after polymerization into a polymer was 90%.

  About the obtained copolymer H, it carried out similarly to Example 1, and evaluated the solubility to toluene and a cyclohexane. A 15% insoluble content was dissolved in toluene and a 8% insoluble content was dissolved in cyclohexane by filtration through a filter having a pore diameter of 30 μm. In addition, it melt | dissolved in the mixed solvent (volume ratio 1: 4) of methylcyclohexane and xylene of 50 degreeC.

  The copolymer H thus obtained had a number average molecular weight (Mn) of 63,000, a weight average molecular weight (Mw) of 182,000, and a glass transition temperature (Tg) of 365 ° C. Moreover, the ratio of the structural unit derived from 5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene in the copolymer F was 10.5 mol%.

  A crosslinked film H-1 having a film thickness of 150 μm was obtained in the same manner as in Example 1 except that the copolymer H was used in place of the copolymer A and the film-forming solvent was changed to 50 ° C. The evaluation results are shown in Table-1.

Comparative Example 2
Using 5 mmol of 5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene and 95 mmol of bicyclo [2.2.1] hept-2-ene, 5-trimethoxysilyl-bicyclo [2 2.2.1] Polymerization was carried out in the same manner as in Example 5 except that 5 mmol of hepta-2-ene was charged before starting polymerization.

  The conversion rate of the monomer into the polymer for 20 minutes after the initiation of polymerization was 18%, and it was derived from 5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene in the resulting polymer at that time. The proportion of structural units was 11 mol%. The polymer solution became cloudy 1 hour after the start of polymerization, and the copolymer became insoluble after 4 hours, and the conversion rate to the polymer was 95%.

The obtained copolymer I was evaluated for solubility in toluene and cyclohexane in the same manner as in Example 1. As a result, insoluble in both toluene and cyclohexane at 25 ° C., white turbidity and uniformity It did not dissolve transparently. The transmittance of the toluene solution was 5.4%, and the transmittance of the cyclohexane solution was 1.9%. In addition, it melt | dissolved in the methylcyclohexane heated at 60 degreeC and o-dichlorobenzene of 120 degreeC.

  The number average molecular weight (Mn) of the copolymer I was 83,000, the weight average molecular weight (Mw) was 202,000, and the glass transition temperature (Tg) was 365 ° C. Moreover, the ratio of the structural unit derived from 5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene in the copolymer I was 5.5 mol%.

  A crosslinked film I-1 having a thickness of 150 μm was obtained in the same manner as in Example 1 except that the copolymer H was used in place of the copolymer A and the film forming solvent was replaced with methylcyclohexane heated to 60 ° C. Got. The evaluation results are shown in Table-1.

Comparative Example 3
5-trimethoxysilyl - bicyclo [2.2.1] hept-2-ene instead of using 10 mmol of 6-trimethoxysilyl - hexacyclo [10.2.1.1 ^{3, 10.} 1 ^5,8
0 ^2,11 . Polymerization was carried out in the same manner as in Comparative Example 1 except that 10 mmol of [ ^4,9 ] heptadeca-13-ene was used.

Conversion of monomer to polymer of 20 minutes after polymerization initiation was 14% 6-trimethoxysilyl product polymer at that time - hexacyclo [10.2.1.1 ^{3, 10.} 1 ^5,8 0 ^2,11 . 0 ^4,9] heptadec-13 ratio of the structural units derived ene was 2 mol%. 30 minutes after the start of polymerization, the polymer solution began to become cloudy, and after 1 hour, the polymer began to precipitate. The conversion rate to the polymer after 4 hours was 50%.

6 trimethoxysilyl - hexacyclo [10.2.1.1 ^{3, 10.} 1 ^5,8 0 ^2,11 . 0 ^4,9 ] heptadeca-13-ene has a methoxysilyl group in the side chain substituent, but is a cycloolefin compound having a very large ring structure called hexacycloheptadecene, so that it is a copolymerizable reaction. And the polymerization activity was inferior.

  The copolymer J thus obtained did not dissolve in toluene and cyclohexane at 25 ° C., but dissolved in o-dichlorobenzene at 120 ° C. at a concentration of 10% by weight.

The number average molecular weight (Mn) of the polymer J was 53,000, the weight average molecular weight (Mw) was 142,000, and the glass transition temperature (Tg) was 365 ° C. Further, the copolymer J in 6-trimethoxysilyl - hexacyclo [10.2.1.1 ^{3, 10.} 1 ^5,8 0 ^2,11 . 0 ^4,9] heptadec-13 ratio of the structural units derived ene was 3.2 mol%.

  A crosslinked film was not made.

Comparative Example 4
Instead of 90 mmol of bicyclo [2.2.1] hept-2-ene, 5-hexyl-
Polymerization was carried out in the same manner as in Comparative Example 1 except that 90 mmol of bicyclo [2.2.1] hept-2-ene was used.

  The conversion rate of the monomer into the polymer 25 minutes after the start of the polymerization was 18%, and it was derived from 5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene in the resulting polymer at that time. The proportion of structural units was 22 mol%. The conversion to polymer after 4 hours was 80%.

  For the obtained copolymer K, the solubility in toluene and cyclohexane and the light transmittance of the solution were evaluated in the same manner as in Example 1. When dissolved in any solvent, the solution became a transparent solution, and the pore size There was no insoluble matter fractionated by filtration through a 30 μm filter, the transmittance of the toluene solution was 95.0%, and the transmittance of the cyclohexane solution was 98.0%.

  The number average molecular weight (Mn) of the copolymer K was 43,000, the weight average molecular weight (Mw) was 142,000, and the glass transition temperature (Tg) was 270 ° C. Moreover, the ratio of the structural unit derived from 5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene in the copolymer K was 13.5 mol%.

  A crosslinked film K-1 having a film thickness of 150 μm was obtained in the same manner as in Example 1 except that the copolymer K was used instead of the copolymer A. The evaluation results are shown in Table-1. The obtained film K-1 had a very large linear expansion coefficient.

Comparative Example 5
9-trimethoxysilyl-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene 5-triethoxysilyl-bicyclo [2.2.1] hepta instead of 10 mmol
Polymerization was carried out in the same manner as in Example 5 except that 10 mmol of 2-ene was used. That is, 4 mmol of 5-triethoxysilyl-bicyclo [2.2.1] hept-2-ene was charged into a pressure bottle together with other monomers, a solvent and a catalyst before the start of polymerization, and 0.75 mmol after 15 minutes. And then 0.75 mmol was added to the polymerization system 7 times every 15 minutes.

  The conversion rate of the monomer into the polymer for 20 minutes after the initiation of polymerization was 18%, and it was derived from 5-triethoxysilyl-bicyclo [2.2.1] hept-2-ene in the resulting polymer at that time. The proportion of structural units was 9.5 mol%, and the index r for the copolymer composition uniformity was 2.2. The polymerization reaction was completed after 2.5 hours. At that time, the conversion ratio of the monomer to the polymer was 93%, and 5-triethoxysilyl-bicyclo [2.2.1] in the resulting polymer was obtained. The proportion of structural units derived from hepta-2-ene was 9.7 mol%.

  For the obtained copolymer L, the solubility in toluene and cyclohexane and the light transmittance of the solution were evaluated in the same manner as in Example 1. When dissolved in any solvent, the solution became a transparent solution, and the pore diameter There was no insoluble matter fractionated by filtration through a 30 μm filter, the transmittance of the toluene solution was 99.0%, and the transmittance of the cyclohexane solution was 98.2%.

  The number average molecular weight (Mn) of the copolymer L was 71,000, the weight average molecular weight (Mw) was 177,000, and the glass transition temperature (Tg) was 370 ° C.

  A crosslinked film L-1 having a thickness of 150 μm was obtained in the same manner as in Example 1 except that the copolymer L was used instead of the copolymer A. The evaluation results are shown in Table-1.

Comparative Example 6
9-trimethoxysilyltetracyclo [6.2.1.1 ^3,6 . Polymerization was conducted in the same manner as in Example 1, except that 100 mmol of bicyclo [2.2.1] hept- ² -ene was used without using 0 ^2,7 ] dodec-4-ene. went.

  From 15 minutes after the start of polymerization, the polymer solution became cloudy, and after 1 hour, the polymer solution was solidified. The polymer was taken out after 4 hours. Conversion of the monomer to polymer was 92%.

The copolymer M thus obtained was evaluated for solubility in toluene and cyclohexane in the same manner as in Example 1. As a result, it was insoluble in both toluene and cyclohexane at 25 ° C. Further, it was not dissolved in cyclohexane, toluene, chlorobenzene, or o-dichlorobenzene heated to 75 ° C.
A crosslinked film was not made.

FIG. 1 shows the ¹ H-NMR spectrum of copolymer A obtained in Example 1. FIG. 2 shows the ¹ H-NMR spectrum of copolymer B obtained in Example 2. FIG. 3 shows the ¹ H-NMR spectrum of copolymer C obtained in Example 3. FIG. 4 shows the ¹ H-NMR spectrum of copolymer D obtained in Example 4. FIG. 5 shows the ¹ H-NMR spectrum of copolymer E obtained in Example 5. FIG. 6 shows the ¹ H-NMR spectrum of copolymer G obtained in Example 8.

Claims (7)

A method of addition polymerization of bicyclo [2.2.1] hept-2-ene and a compound represented by the following general formula (4), which is represented by the general formula (4) using a palladium catalyst. A method for producing a cyclic olefin-based addition copolymer, which comprises supplying a compound continuously or sequentially to a polymerization system.

(In Formula (4), R ¹ is a substituent selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or an aryl group, X is a methoxy group, k is an integer of 0 to 2, and n is 0 or 1) .) The cyclic olefin addition copolymer is
A copolymer containing 70 to 98 mol% of the structural unit (a) represented by the following formula (1) and 2 to 20 mol% of the structural unit (b) represented by the following formula (2) in all the structural units. Because
The number average molecular weight is 30,000 to 300,000,
When the copolymer was dissolved at 25 ° C. in toluene so as to be 10% by weight, the insoluble content was 0.1% by weight or less, and the wavelength of the toluene solution measured by a quartz cell having a light path length of 1 cm was 400 nm. And the transmittance is 85% or more, and
When the copolymer was dissolved in cyclohexane at 25 ° C. so as to be 10% by weight, the insoluble content was 0.1% by weight or less, and the wavelength of the cyclohexane solution measured with a quartz cell having an optical path length of 1 cm was 400 nm. The method for producing a cyclic olefin-based addition copolymer according to claim 1, wherein the transmittance is 85% or more.

(In the formula (2), R ¹ is a substituent selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or an aryl group, X is a methoxy group, k is an integer of 0 to 2, and n is 0 or 1 .)   The said cyclic olefin addition copolymer contains 5-15 mol% of said structural units (b) in all the structural units, The manufacturing method of the cyclic olefin addition copolymer of Claim 2 characterized by the above-mentioned. In the cyclic olefin addition copolymer, the structural unit (b) is at least a structural unit derived from 5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene and / or 9-trimethoxy. Silyl-tetracyclo [6.2.1.1 ^3,6 . The process for producing a cyclic olefin addition copolymer according to claim 2 or 3, comprising a structural unit derived from 0 ^2,7 ] dodec-4-ene. The cyclic olefin-based addition copolymer contains a structural unit (c) represented by the following general formula (3) in addition to the structural unit (a) and the structural unit (b). 5. A method for producing a cyclic olefin addition copolymer according to any one of 4 above.

(In the formula (3), A ^{1 to} A ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an aryl group, a trialkylsilyl group, an alkoxycarbonyl group, an alkoxy group, And an atom group selected from the group consisting of an ester group formed by A ¹ and A ² , an alkylene group formed by A ¹ and A ³ , and at least one of A ^{1 to} A ⁴ is an alkoxycarbonyl group, An aryl group and a substituent selected from an alkylene group formed by A ¹ and A ³ , m is an integer of 0 or 1) Palladium-based catalyst
a) a palladium compound,
b) ionic boron compounds,
c) A phosphine compound having a substituent selected from an alkyl group having 3 to 15 carbon atoms, a cycloalkyl group, and an aryl group and having a cone angle of 170 to 200, or the phosphine compound. 6. The process for producing a cyclic olefin addition copolymer according to claim 1, wherein the catalyst is a multicomponent catalyst prepared from a phosphonium salt and d) an organoaluminum compound.   The ratio Rp of the structural unit derived from the compound represented by the general formula (4) in the initial polymer produced during the initial polymerization in which the conversion ratio of all monomers to the polymer is 5 to 20%, Ratio r (r = Rp / Rm) with the ratio Rm of the structural unit derived from the compound represented by the general formula (4) in all monomers to be subjected to polymerization satisfies 0.7 ≦ r ≦ 1.3. The manufacturing method of the cyclic olefin type addition copolymer in any one of Claims 1-6 characterized by the above-mentioned.

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