JP2010024349A - Norbornene-based resin solution and method for producing the same, norbornene-based resin film produced by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a norbornene-based resin film having excellent solvent resistance and thermal deformation resistance while maintaining its high transparency. <P>SOLUTION: The norbornene-based resin solution is produced by heating a solution of a norbornene-based resin obtained by (co)polymerizing a monomer containing at least one compound having a specific structure, and a resin composition comprising at least one hydroxide selected from the group consisting of a potassium hydroxide, a sodium hydroxide, a calcium hydroxide and a magnesium hydroxide. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a norbornene-based resin solution, a method for producing the same, and a norbornene-based resin film using the same. More specifically, the present invention relates to an alkali-treated cyclic norbornene-based resin solution, a production method thereof, and a norbornene-based resin film using the same.

  Norbornene-based resins are attracting attention as materials for various optical components because they are excellent in transparency, heat resistance, chemical resistance, and the like. However, in order to more widely apply norbornene resin as an optical component, higher heat resistance is required, and in terms of mechanical strength, norbornene resin is inferior in toughness compared to other transparent resins. There is a need for further improvements.

For example, Patent Document 1 discloses a polarizing film in which a norbornene-based resin sheet is laminated on a polarizing film as a protective layer. When a polarizing film using the norbornene-based resin sheet is incorporated in a liquid crystal display element, Peeling or deformation from the element occurs due to long-term use. This is due to the deformation of the film due to external heat and mechanical stress.
JP-A-6-511117

  An object of this invention is to provide the norbornene-type resin film which is excellent in solvent resistance and heat-deformability, maintaining high transparency.

  As a result of intensive investigations to solve the above problems, the present inventors have found that the deformation temperature of the film is increased by forming the norbornene resin on the film after alkali treatment, thereby completing the present invention. It came.

  That is, the norbornene-based resin solution of the present invention includes a norbornene-based resin solution obtained by (co) polymerizing a monomer containing at least one compound represented by the following formula (1), potassium hydroxide, It is characterized by heating a resin composition containing at least one hydroxide selected from the group consisting of sodium hydroxide, calcium hydroxide and magnesium hydroxide.

(Wherein, R ¹ to R ⁴ are each independently a hydrogen atom, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom group may monovalent to contain; substituted or unsubstituted carbon A hydrocarbon group having 1 to 15 atoms; or a group represented by —R ⁵ —COOR ^6. R ⁵ represents a single bond; a substituted or unsubstituted methylene group; R ⁶ represents a linear or branched alkylene group which may contain an etheric oxygen atom, and R ⁶ contains a substituted or unsubstituted linear, branched or cyclic etheric oxygen atom. Or a substituted or unsubstituted aryl group, provided that at least one of R ^{1 to} R ⁴ represents a group represented by —R ⁵ —COOR ^6. and .R ¹ and R ^2, or R ³ and R ⁴ are phase It may be bonded to form an alkylidene group, R ¹ and R ^2, R ³ and R ^4, or R ² and R ^3, bonded to each other monocyclic or polycyclic carbon ring Alternatively, a heterocyclic ring may be formed, and R ¹ and R ⁴ or R ² and R ³ may be bonded to each other to form a double bond, or R ¹ and R ⁴ And R ² and R ³ may be bonded to each other to form a triple bond, x represents 0 or an integer of 1 to 3, and y represents 0 or 1.)
The norbornene-based resin is preferably a (co) polymer obtained by ring-opening (co) polymerizing a monomer containing at least one compound represented by the above formula (1).

The heating temperature of the resin composition is preferably in the range of 30 to 180 ° C.
Potassium hydroxide may be sufficient as the said hydroxide, and it is preferable to contain in the resin composition in the quantity of 0.1-5 weight part with respect to 100 weight part of norbornene-type resin.

Moreover, norbornene-based resin film of the present invention, that is formed by using a norbornene-based resin solution of the present invention is characterized, observed 1810cm ^-1 ~1610cm ^-1 of IR spectrum obtained by measuring by FT-IR Calculated from the area of the absorption peak of the ester group carbonyl (peak A) and the area of the absorption peak (peak B) of the antisymmetric stretching vibration of the carboxylate group carbonyl observed at 1610 cm ^{−1 to} 1520 cm ^−1. Preferably, the alkali modification rate is 0.01 to 0.5.

(Alkali modification rate) = (Area of peak B) / (Area of peak A)
Furthermore, the norbornene-based resin film of the present invention preferably has a content of at least one element selected from the group consisting of potassium, sodium, calcium and magnesium of 0.05 to 4% by weight.

  Moreover, the manufacturing method of the norbornene-type resin solution of this invention is the (co) polymerization process which obtains norbornene-type resin by (co) polymerizing the monomer containing the at least 1 sort (s) of compound represented by the said Formula (1). Mixing the norbornene resin with at least one hydroxide selected from the group consisting of potassium hydroxide, sodium hydroxide, calcium hydroxide and magnesium hydroxide to obtain a resin composition; and It comprises a heating step of heating the resin composition to obtain a norbornene resin solution.

  In the present invention, when a film is formed using a norbornene-based resin solution, a norbornene-based resin film excellent in solvent resistance and heat distortion resistance is obtained while maintaining high transparency.

  The norbornene-based resin solution of the present invention includes a norbornene-based resin solution obtained by (co) polymerizing a monomer containing at least one compound represented by the above formula (1), potassium hydroxide, hydroxide It is characterized by heating a resin composition containing at least one hydroxide selected from the group consisting of sodium, calcium hydroxide and magnesium hydroxide.

Hereinafter, the present invention will be specifically described.
<Norbornene resin>
The “norbornene-based resin” is a monomer or monomer composition containing at least one norbornene-based compound (hereinafter, also referred to as “monomer composition”) (co) polymerized and required. Depending on the above, it is a resin obtained by further hydrogenation.

  The “norbornene compound” is not particularly limited as long as it is a compound having a norbornene skeleton, but is preferably a compound represented by the following formula (1).

In the above formula (1), R ^{1 to} R ⁴ each independently represent a hydrogen atom; a halogen atom; a monovalent group that may contain an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom; substituted hydrocarbon group having 1 to 15 carbon atoms; or a group represented by -R ⁵ -COOR ^6.

R ⁵ represents a single bond; a substituted or unsubstituted methylene group; or a linear or branched alkylene group having 2 to 8 carbon atoms, which may contain an etheric oxygen atom.
R ⁶ represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 15 carbon atoms which may contain an etheric oxygen atom; or a substituted or unsubstituted aryl group .

Provided that at least one of R ¹ to R ⁴ represents a group represented by -R ⁵ -COOR ^6.
R ¹ and R ² , or R ³ and R ⁴ may be bonded to each other to form an alkylidene group, and R ¹ and R ² , R ³ and R ⁴ , or R ² and R ³ may be bonded to each other to form a monocyclic or polycyclic carbocyclic or heterocyclic ring, and R ¹ and R ⁴ , or R ² and R ³ may be bonded to each other to form A double bond may be formed, or R ¹ and R ⁴ and R ² and R ³ may be bonded to each other to form a triple bond.

x represents 0 or an integer of 1 to 3, and y represents 0 or 1.
(Monomer composition)
The norbornene-based compound contained in the monomer composition is represented by, for example, the above formula (1).

In the above formula (1), R ¹ and R ² or R ³ and R ⁴ may be bonded to each other to form an alkylidene group. R ¹ and R ² , R ³ and R ⁴ Or R ² and R ³ may be bonded to each other to form a monocyclic or polycyclic carbocyclic ring, or a monocyclic or polycyclic heterocyclic ring, R ¹ and R ⁴ , or R ² and R ³ may be bonded to each other to form a double bond, or R ¹ and R ⁴ and R ² and R ³ are bonded to each other to form a triple bond. You may do it.

Here, “R ¹ and R ² are bonded to each other to form an alkylidene group” means that ^one of R ¹ and R ² is eliminated and the remaining group is bonded to the ring structure by a double bond. It means the state (shown in the following formula (2)). The same applies to R ³ and R ⁴ .

  Examples of the “carbocycle or heterocycle” include alicyclic and aromatic rings.

The norbornene compounds represented by the above formula (1) may be used alone or in combination of two or more.
Examples of norbornene compounds represented by the above formula (1) include the following compounds, but are not limited to these compounds.
5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5- (2′-methoxy) ethoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-ethoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5- (2′-ethoxy) ethoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-n-propoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-iso-propoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5- (1′-methyl) -propoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-n-butoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-iso-butoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-tert-butoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-n-hexyloxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-phenoxyethylcarbonyl-bicyclo [2.2.1] hept-2-ene,
5-phenylcarbonyloxy-bicyclo [2.2.1] hept-2-ene,
5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-methyl-5-phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-methyl-5-phenoxyethylcarbonyl-bicyclo [2.2.1] hept-2-ene,
8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8 phenoxycarbonyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene,
8-phenoxyethylcarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-phenylcarbonyloxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (DMN),
8-methyl-8- (2′-methoxy) ethoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-ethoxycarbonyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene,
8-methyl-8- (2′-ethoxy) ethoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-n-propoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-iso-propoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8- (1′-methyl) -propoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-n-butoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-iso-butoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-tert-butoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-n-hexyloxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-phenoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-phenoxyethylcarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
The type and amount of the norbornene compound are appropriately selected according to the required characteristics.

Of the norbornene-based compound represented by the above formula (1), a structure containing at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom (hereinafter referred to as “a”) A compound having a “polar structure”) is preferable in terms of excellent adhesion and adhesion to other materials. In particular, in the above formula (1), R ¹ and R ³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, preferably at least one is a methyl group, and R ² or R ⁴ is A compound having a polar structure and the other being a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms is preferred in that the water absorption (wet) property of the resulting resin is reduced.

Furthermore, a norbornene-based compound in which the group having a polar structure is a group represented by the following formula (3) is suitable because it has a good balance between the heat resistance and water absorption (wet) property of the resulting resin.
-R ⁵ -COOR ⁶ (3)
In the above formula (3), R ⁵ is a single bond; a substituted or unsubstituted methylene group; or a linear or branched alkylene having 2 to 8 carbon atoms, which may contain an etheric oxygen atom Represents a group. R ⁶ represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 15 carbon atoms which may contain an etheric oxygen atom; or a substituted or unsubstituted aryl group .

In the above formula (3), the smaller the number of carbon atoms of R ⁵ , the higher the glass transition temperature of the obtained norbornene-based resin hydrogenated product and the better the heat resistance. It is preferable that the monomer having 0 carbon atoms is more preferable in terms of easy synthesis.

In the above formula (3), R ⁶ tends to decrease the water absorption (wetness) of the resulting norbornene-based resin as the number of carbon atoms increases, but also tends to decrease the glass transition temperature. From the viewpoint of maintaining the number of carbon atoms, such as methyl group, ethyl group, n-propyl group, iso-propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc. Are preferably alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl and hexyl groups, and phenyl groups.

When the alkyl group and the phenyl group have a substituent, examples of the substituent include a carboxyl group, a hydroxyl group, a halogen atom, and an ester group.
In the above formula (1), the norbornene-based compound in which an alkyl group having 1 to 3 carbon atoms, particularly a methyl group, is bonded to the carbon atom to which the group represented by the above formula (3) is bonded is characterized by heat resistance and water absorption. It is preferable in terms of balance with (wet) property.

  In the above formula (1), when x represents 0 or 1 and y represents 0 or 1, the norbornene compound is highly reactive, and a norbornene resin can be obtained in a high yield, norbornene having high heat resistance This is preferable in that a resin-based hydrogenated product can be obtained and industrially easily available.

In obtaining the norbornene-based resin, the monomer composition can be polymerized with a monomer that can be copolymerized with the norbornene-based compound within a range that does not impair the object of the present invention.
The “copolymerizable monomer” is not particularly limited as long as it does not have a group represented by the above formula (3) and can be copolymerized with the norbornene-based compound.
Cyclic olefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, cyclododecene;
Non-conjugated cyclic polyenes such as 1,4-cyclooctadiene, dicyclopentadiene (DCP), cyclododecatriene;
Α-olefins such as ethylene;
Bicyclo [2.2.1] hept-2-ene (NB),
5-methyl-bicyclo [2.2.1] hept-2-ene,
5-ethyl-bicyclo [2.2.1] hept-2-ene,
5-cyclohexyl-bicyclo [2.2.1] hept-2-ene,
5-phenyl-bicyclo [2.2.1] hept-2-ene,
5- (4-biphenyl) -bicyclo [2.2.1] hept-2-ene,
5-vinyl-bicyclo [2.2.1] hept-2-ene,
5-ethylidene-bicyclo [2.2.1] hept-2-ene,
5,5-dimethyl-bicyclo [2.2.1] hept-2-ene,
5,6-dimethyl-bicyclo [2.2.1] hept-2-ene,
5-fluoro-bicyclo [2.2.1] hept-2-ene,
5-chloro-bicyclo [2.2.1] hept-2-ene,
5-bromo-bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-bicyclo [2.2.1] hept-2-ene,
5,6-dichloro-bicyclo [2.2.1] hept-2-ene,
5,6-dibromo-bicyclo [2.2.1] hept-2-ene,
5-hydroxy-bicyclo [2.2.1] hept-2-ene,
5-hydroxyethyl-bicyclo [2.2.1] hept-2-ene,
5-cyano-bicyclo [2.2.1] hept-2-ene,
5-amino-bicyclo [2.2.1] hept-2-ene,
Tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
Tricyclo [4.4.0.1 ^2,5 ] undec-3-ene,
7-methyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7-ethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7-cyclohexyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7-phenyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7- (4-biphenyl) -tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7,8-dimethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7,8,9-trimethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
8-methyl-tricyclo [4.4.0.1 ^2,5 ] undec-3-ene,
8-phenyl-tricyclo [4.4.0.1 ^2,5 ] undec-3-ene,
7-fluoro - tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene,
7-chloro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7-bromo-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7,8-dichloro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7,8,9-trichloro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7-chloromethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7-dichloromethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7-trichloromethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7-hydroxy-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7-cyano-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
7-amino - tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene,
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
Pentacyclo [7.4.0.1 ^2,5 . 1 ^8,11 . 0 ^7,12] pentadeca-3-ene,
Hexacyclo [8.4.0.1 ^2,5 . 1 ^7,14 . 1 ^9,12 . 0 ^8,13] -heptadec-3-ene,
8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene,
8-cyclohexyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-phenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8- (4-biphenyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene,
8,8-Dimethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,9-dimethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-fluoro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-chloro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-Bromo-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,8-Dichloro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,9-Dichloro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,8,9,9- tetrachloro - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene,
8-hydroxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-hydroxyethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-hydroxyethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-cyano-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-amino-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] norbornene compounds other than the norbornene compound represented by the above formula (1) such as dodec-3-ene.

These copolymerizable monomers may be used alone or in combination of two or more.
(Polymerization method)
The method for polymerizing the norbornene resin is not particularly limited as long as the monomer composition containing the norbornene compound can be polymerized. For example, the ring-opening described in JP-A-2008-76552 Polymerization can be performed by the same polymerization method as (co) polymerization or addition (co) polymerization, and a norbornene-based resin can be hydrogenated in the same manner as the hydrogenation reaction described in the publication.

(UV absorber)
The norbornene-based resin may be added with an ultraviolet absorber. The ultraviolet absorber absorbs ultraviolet rays, thereby suppressing the generation of active radical species that cause the norbornene-based resin to deteriorate, preventing the deterioration of coloring and transparency caused by the deterioration, and transmitting ultraviolet rays to the polarizing film. And has a role of preventing deterioration of the polarizing film. As the ultraviolet absorber, a benzotriazole derivative is particularly preferably used.

  The melting point of the benzotriazole derivative is preferably Tg−35 ° C. to Tg + 75 ° C., particularly preferably Tg−30 ° C. to Tg + 70 ° C. with respect to the glass transition temperature (hereinafter also referred to as “Tg”) of the norbornene resin. When the melting point of the benzotriazole derivative is lower than Tg-35 ° C., the volatility of the benzotriazole derivative increases, and the benzotriazole derivative and its decomposition product may adhere to a norbornene resin film or a film molding machine. On the other hand, when the melting point of the benzotriazole derivative is higher than Tg + 75 ° C., the benzotriazole derivative bleeds on the surface of the norbornene-based resin film at the time of film molding or the like and solidifies on the surface without being compatible because the melting point is high during the cooling process. Therefore, it may adhere to the roll or norbornene resin film surface.

  The addition amount of the ultraviolet absorber is usually 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the norbornene resin. When the addition amount of the ultraviolet absorber is less than 0.1 parts by weight, a sufficient ultraviolet absorption effect is not seen, and the effect of the present invention is hardly exhibited. Moreover, when it exceeds 20 weight part, the transmittance | permeability in the visible region of the obtained norbornene-type resin film may fall.

The proportion of the benzotriazole derivative in the total ultraviolet absorber is usually 10% by weight or more, preferably 50% by weight or more.
(Other additives)
To the norbornene-based resin, an additive such as an antioxidant can be further added as long as the object of the present invention is not impaired.

  Examples of the “antioxidant” include pentaerythrityl tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl)] propionate, 2,6-di-tert-butyl-4-methylphenol. 2,2′-dioxy-3,3′-di-t-butyl-5,5′-dimethyldiphenylmethane, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ] Methane etc. are mentioned. Of these, pentaerythrityltetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl)] propionate is preferred.

  Moreover, when manufacturing a norbornene-type resin film by the below-mentioned casting, manufacture of a resin film can be made easy by adding a leveling agent and an antifoamer.

  These additives may be added together with the norbornene resin when the norbornene resin film is produced, or may be added before the norbornene resin is produced. The addition amount is appropriately selected according to the desired properties, but is usually 0.01 to 5.0 parts by weight, preferably 0.05 to 2.0 parts by weight, with respect to 100 parts by weight of the norbornene resin. It is desirable that

(Characteristics of norbornene resin)
The glass transition temperature (Tg) of the norbornene resin is usually 120 ° C. or higher, preferably 130 ° C. or higher. When Tg is within the above range, a norbornene-based resin film having high reliability even in long-term use can be obtained.

  The number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC) of a norbornene resin is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and particularly preferably 1.5. The weight average molecular weight (Mw) is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,000,000, and particularly preferably 30,000 to 500,000.

  The logarithmic viscosity (sample concentration: 0.5 g / dL) of the norbornene resin measured in chloroform at 30 ° C. using an Ubbelohde viscometer is preferably 0.2 to 2.0 dL / g, more preferably 0. .35 to 1.0 dL / g, particularly preferably 0.4 to 0.85 dL / g.

When the number average molecular weight, weight average molecular weight, and logarithmic viscosity of the norbornene resin are within the above ranges, a norbornene resin film that is excellent in mechanical strength and hardly damaged can be obtained.
<Resin composition>
The “resin composition” used in the present invention is a solution of a norbornene resin obtained by (co) polymerization of a monomer containing at least one compound represented by the above formula (1), hydroxylation It contains at least one hydroxide selected from the group consisting of potassium, sodium hydroxide, calcium hydroxide and magnesium hydroxide.

  The “norbornene-based resin solution” is a solution in which the obtained norbornene-based resin is dissolved in a polymerization solvent after (co) polymerization reaction, or is isolated by distilling off the polymerization solvent. A solution obtained by dissolving the norbornene-based resin in a solvent may be used.

  The “polymerization solvent” and “solvent” are not particularly limited as long as they dissolve the norbornene-based resin and the hydroxide. For example, alkanes such as pentane, hexane, heptane, octane, nonane, decane; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chloroform, Halogenated alkanes such as tetrachloroethylene; halogenated aryl compounds such as chlorobenzene; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate, and dimethoxyethane; Ether, tetrahydrofuran, organic solvent having a volatility such as ethers such as dimethoxyethane. These can be used individually by 1 type or in mixture of 2 or more types. Such a solvent is used in an amount of 100 to 1,000 parts by weight, preferably 200 to 500 parts by weight, based on 100 parts by weight of the norbornene-based resin.

As the “hydroxide”, potassium hydroxide (KOH) is preferable because of its good solubility in various solvents.
The hydroxide is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 8 parts by weight, and particularly preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the norbornene resin. It is contained in the resin composition. It is preferable that the content (parts by weight) of the hydroxide is within the above numerical range because the increase in viscosity during the reaction is small and a uniform reaction is possible.

<Norbornene resin solution>
The “norbornene resin solution” of the present invention is obtained by heating the above resin composition to a temperature of preferably 30 to 180 ° C., more preferably 50 to 120 ° C., and particularly preferably 90 to 120 ° C. . If the heating temperature is less than 30 ° C, the time required for the reaction may become longer. On the other hand, if it exceeds 180 ° C, the pressure in the reaction vessel may rise rapidly due to a rapid reaction.

  The resin solution viscosity of the norbornene resin solution is preferably 0.5 to 50 Pa · s, more preferably 1 to 30 Pa · s, and particularly preferably 2 to 25 Pa · s. When the resin solution viscosity of the norbornene-based resin solution is within the above range, the film thickness is uniform during film production by the casting method, which is preferable. The resin solution viscosity is, for example, a rotary viscometer (TVE-33H type) manufactured by Toki Sangyo Co., Ltd., and a rotor (3 ° × R24 type) is set and held at 25 ° C. The viscosity of the resin solution was measured with a measurement range H at a rotation speed at which the torque output was in the range of 20% to 80%.

(Manufacturing method of norbornene resin solution)
The method for producing a norbornene-based resin solution according to the present invention includes (co) polymerizing a monomer containing at least one compound represented by the above formula (1) to obtain a norbornene-based resin, A mixing step of mixing a norbornene-based resin with at least one hydroxide selected from the group consisting of potassium hydroxide, sodium hydroxide, calcium hydroxide and magnesium hydroxide to obtain a resin composition; and the resin It is characterized by comprising a heating step of heating the composition to obtain a norbornene resin solution.

[(Co) polymerization step]
The (co) polymerization step is a step of obtaining a norbornene-based resin by (co) polymerizing a monomer containing at least one compound represented by the above formula (1).

The (co) polymerization reaction is the same as described above.
[Mixing process]
The mixing step is a norbornene-based resin obtained in the (co) polymerization step and at least one hydroxide selected from the group consisting of potassium hydroxide, sodium hydroxide, calcium hydroxide and magnesium hydroxide. To obtain a resin composition.

  It is desirable that the hydroxide be dissolved in a solvent in advance before mixing. The “solvent” is not particularly limited as long as it dissolves norbornene-based resin and hydroxide. For example, isopropanol, n-butanol and the like have 3 to 8 carbon atoms, preferably 3 to 5 carbon atoms. The alcohol is desirable. The concentration of the hydroxide previously dissolved in the solvent is usually 0.1 to 30% by mass, preferably 1 to 20% by mass. It is preferable that the hydroxide concentration is within the above range in that the reaction with the norbornene resin is uniform and the change rate can be easily controlled.

Although the specific example of a mixing process is shown below, it is not limited to this.
A glass separable flask equipped with a stirring blade was charged with 100 parts by weight of the norbornene-based resin obtained in the above (co) polymerization step, 300 parts by weight of toluene was added thereto, and the mixture was stirred at room temperature for 5 hours. The norbornene resin is dissolved in toluene.

Next, a resin composition is obtained by adding 1.2 parts by weight of potassium hydroxide dissolved in 17 parts by weight of n-butanol while stirring.
[Heating process]
The heating step is a step of heating the resin composition obtained in the mixing step to obtain a norbornene resin solution.

As described above, the heating temperature is preferably 30 to 180 ° C.
The heating time is 1 to 24 hours, preferably 5 to 24 hours, particularly preferably 10 to 24 hours. When the heating temperature and time are within the above ranges, the amount of solvent remaining in the obtained norbornene-based resin film is small, and the mechanical strength of the film is not impaired.

(Use of norbornene resin solution)
Applications of the norbornene resin solution include cast films and coating films. Among these, a cast film is preferable because it retains high transparency and is further excellent in solvent resistance and heat distortion resistance.

<Norbornene resin film>
The norbornene resin film of the present invention is formed using the norbornene resin solution of the present invention.

(Manufacturing method of norbornene resin film)
The norbornene-based resin film can be suitably formed by casting (cast molding) the resin composition.

  That is, for example, the norbornene-based resin film is formed by applying the resin composition on a substrate such as a steel belt, a steel drum, or a polyester film, drying the solvent, and then peeling the coating film from the substrate. Thus, a norbornene resin film can be obtained.

  The amount of residual solvent in the norbornene-based resin film obtained by cast molding is preferably as small as possible, usually 3% by weight or less, preferably 1% by weight or less, more preferably 0.5% by weight or less. When the residual solvent amount is within the above range, the film is less likely to be deformed or changed with time, and a norbornene-based resin film having a desired function can be obtained.

(Characteristics of norbornene resin film)
Norbornene resin film "alkaline denaturation rate", the film was measured by FT-IR, an absorption peak of the ester group carbonyl observed at 1810cm ^-1 ~1610cm ^-1 obtained IR spectrum (peak A) It is calculated according to the following formula from the area and the area of the absorption peak (peak B) of the antisymmetric stretching vibration of the carboxylate group carbonyl observed at 1610 cm ^{−1 to} 1520 cm ⁻¹ , preferably 0.01 to 0 0.5, more preferably 0.01 to 0.3.

(Alkali modification rate) = (Area of peak B) / (Area of peak A)
When the alkali modification rate is within the above range, it is preferable from the viewpoint of achieving both high solvent resistance and high heat distortion temperature of the alkali-modified norbornene resin film.

  The at least one element selected from the group consisting of potassium, sodium, calcium and magnesium contained in the norbornene resin film is preferably 0.05 to 4% by weight, more preferably 0.1 to 3% by weight, particularly Preferably it is 0.5 to 2 weight%. It is preferable that the content of the element obtained by measurement by the fluorescent X-ray method is in the above range since the viscosity increase of the modification reaction solution is small and the solvent resistance after modification and the heat distortion temperature are increased.

  The “total light transmittance” of the norbornene resin film is not particularly limited, but it is usually 80 to 95%, preferably 85 to 95%, more preferably 90 to 95%. The “haze” is not particularly limited, but is usually 0.1 to 2%, preferably 0.1 to 1%, more preferably 0.1 to 0.5%.

  The total light transmittance and haze are measured using a haze-light transmittance measuring machine, for example, a commercially available haze-light transmittance measuring machine (Haze-Gard Plus type) manufactured by Gardner. Can do.

  As a “solvent resistance evaluation” of a norbornene-based resin film, the film (thickness: 100 μm) cut to 10 mm × 30 mm is immersed in a solvent (toluene or methylene chloride) at room temperature for 20 minutes, and then the film maintains its shape. “○” indicates that the solvent can be pulled up as it is from the solvent, “Δ” indicates that the film shape is not maintained but it cannot be lifted from the solvent, and the film is completely dissolved in the solvent. When “×” is used, an evaluation of “Δ” or more is preferable in each of toluene and methylene chloride.

  The “film deformation temperature” of the norbornene-based resin film is not particularly limited, but is usually 100 to 300 ° C., preferably 120 to 300 ° C., more preferably 140 to 300 ° C.

  In addition, the measuring method of a film deformation temperature is 4 mm in width, 20 mm in length, and thickness using a thermomechanical device (TMA; Thermal Mechanical Analysis), for example, SS6100 (manufactured by Seiko Instruments Inc.) that is commercially available. While raising the norbornene-based resin film prepared to 50 to 200 μm from 25 ° C. to 350 ° C. at 10 ° C./min, a tensile test was performed in the long side direction with an applied load of 10 g, and the norbornene-based resin film at that time The elongation rate is recorded, and the temperature at which the elongation rate starts to increase rapidly due to the softening of the norbornene-based resin film is obtained by the tangential method, and the temperature (° C.) is defined as “film deformation temperature”.

  The “thickness” of the norbornene-based resin film is not particularly limited, but is usually 5 to 500 μm, preferably 10 to 150 μm, more preferably 20 to 100 μm. When the thickness of the film is within the above range, a norbornene resin film having sufficient strength can be obtained, and a norbornene resin film having good birefringence, transparency, and appearance can be obtained.

  Since the norbornene-based resin film of the present invention is superior in solvent resistance and heat distortion resistance as compared with conventional ones, optical discs, optical fibers, optical lenses, mirrors, semiconductor encapsulants, transparent conductive films for LCDs It is suitable for a low retardation film for LCD, a touch panel, a glass substitute optical plate material, a transparent heat-resistant coating material, and the like.

Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these. “Parts” represents “parts by weight” unless otherwise specified.
Various physical properties of the norbornene-based resin, norbornene-based resin solution and norbornene-based resin film obtained in the synthesis examples and the examples were measured according to the methods described in (1) to (11) below.

(1) Hydrogenation rate ¹ H-NMR was measured using Bruker's AVANCE 500 as a nuclear magnetic resonance spectrometer (NMR) and d-chloroform as a measurement solvent. After calculating the composition of the monomer from the integral value of 5.1 to 5.8 ppm vinylene group, 3.7 ppm methoxy group, and 0.6 to 2.8 ppm aliphatic proton, the hydrogenation rate of the norbornene resin (%) Was calculated.

(2) Glass transition temperature [Tg]
Using a DSC6200 manufactured by Seiko Instruments Inc., the rate of temperature increase was measured at 20 ° C. per minute under a nitrogen stream. The glass transition temperature [Tg] (° C) of the norbornene-based resin is plotted on the differential scanning calorimetry curve with the maximum differential peak temperature (point A) of the differential differential scanning calorific value and the temperature -20 ° C from the maximum peak temperature (point B). , And the intersection of the tangent line on the baseline starting from point B and the tangent line starting from point A.

(3) Number average molecular weight [Mn], weight average molecular weight [Mw] and molecular weight distribution [Mw / Mn]
Gel permeation chromatography (manufactured by Tosoh Corporation HLC-8220GPC, column: Tosoh Corporation guard column _{H XL -H, TSK gel G7000H XL} , TSKgel GMH XL 2 present, sequentially connecting the TSK gel G2000H _XL, solvent: Tetrahydrofuran, flow rate: 1 mL / min, sample concentration: 0.7 to 0.8% by weight, injection amount: 70 μL, measurement temperature: 40 ° C., detector: RI (40 ° C.), standard material: manufactured by Tosoh Corporation The number average molecular weight [Mn], the weight average molecular weight [Mw] and the molecular weight distribution [Mw / Mn] of the norbornene resin were measured using TSK standard polystyrene.

(4) Logarithmic viscosity Using an Ubbelohde viscometer, the logarithmic viscosity (dL / g) of the norbornene resin was measured at 30 ° C. in chloroform (sample concentration: 0.5 g / dL).

(5) Viscosity of Resin Solution A rotor (3 ° × R24 type) was set on a rotary viscometer (TVE-33H type) manufactured by Toki Sangyo Co., Ltd. and held at 25 ° C. 1 mL of norbornene-based resin solution was injected into the rotor with a syringe, and the viscosity (Pa · s) of the resin solution was measured at a measurement range H at a rotation speed at which the torque output was in the range of 20% to 80%.

(6) Alkali modification rate Infrared absorption spectrum of norbornene resin film was measured with FT-IR (FT / IR-4100 type) manufactured by JASCO, and the absorption peak of ester group carbonyl observed at 1810 cm ^{−1 to} 1610 cm ^−1. The area of (peak A), the area of the absorption peak (peak B) of the reverse symmetrical stretching vibration of the carboxylate group carbonyl observed in 1610 cm ^{−1 to} 1520 cm ⁻¹ was calculated. Next, the alkali modification rate (%) of the norbornene resin film was determined from the following formula.

(Alkali modification rate) = (Area of peak B) / (Area of peak A)
(7) Potassium content First, a calibration curve of fluorescence intensity and potassium content was prepared.

  That is, potassium laurate (manufactured by Wako Pure Chemical Industries, Ltd.) was previously blended with norbornene-based resin, and the potassium contents were 0.1 wt%, 0.2 wt%, 0.5 wt%, 1 A norbornene-based resin solution having a concentration of 0.0% by weight and 2.0% by weight was prepared, and films having a thickness of about 100 μm were prepared by a casting method.

  Fluorescence intensity peculiar to potassium element contained in the film (average value of n = 2) was measured using a fluorescent X-ray measuring apparatus (MAGiX PRo type) manufactured by Spectris Corporation PANalytical Division, and the numerical value and film A calibration curve between the fluorescence intensity and the potassium content was prepared from the amount of potassium contained therein.

  Next, the norbornene-based resin film produced in the example was used as a test piece, and the fluorescence intensity derived from potassium atoms contained in the test piece was measured with the above apparatus (average value of n = 2). From this, the potassium content (%) in the test piece was determined.

(8) Total light transmittance, haze Using a haze-light transmittance measuring machine (Haze-Gard Plus type) manufactured by Gardner, the total light transmittance (%) and haze (%) of the norbornene-based resin film are measured. did.

(9) Evaluation of solvent resistance A norbornene-based resin film having a thickness of 100 μm was cut into 10 mm × 30 mm, and the film was immersed in toluene or methylene chloride at room temperature for 20 minutes. After immersion, the film maintains its shape and can be pulled up as it is from the solvent `` ○ '', the film shape of the undissolved one is not maintained, and what can not be pulled up from the solvent `` △ '', The case where the film was completely dissolved in the solvent was designated as “x”.

(10) Film deformation temperature A norbornene-based resin film prepared to have a width of 4 mm, a length of 20 mm, and a thickness of 50 to 200 μm using a thermomechanical device (TMA; Thermal Mechanical Analysis) / SS6100 (manufactured by Seiko Instruments Inc.). While the temperature was raised from 25 ° C. to 350 ° C. at 10 ° C./min, the applied load was 10 g, and a tensile test was performed in the long side direction. The elongation rate of the film was recorded, and the temperature at which the elongation rate began to increase rapidly due to softening of the film was determined by the tangential method, and the temperature was defined as the film deformation temperature (° C.).

(11) Tensile yield strength, tensile yield elongation, tensile fracture strength, and tensile fracture elongation A tensile test is performed at a test speed of 15 mm / min using an Instron tensile tester (model 5564) according to JIS-K7127. The tensile yield strength (MPa), tensile yield elongation (%), tensile fracture strength (MPa), and tensile fracture elongation (%) of the film were determined. In addition, the test piece which consists of a norbornene-type resin film was cut | judged and used for No. 2 1/2 size with the dumbbell sample cutter.

[Synthesis Example 1]
Represented by the following formula (4) 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3-dodecene (DNM) 100 parts, 1-hexene (molecular weight regulator) 18 parts, and toluene (solvent for ring-opening polymerization reaction) 300 parts were charged in a nitrogen-substituted reaction vessel, The solution was heated to 80 ° C. Next, 0.2 parts of a toluene solution of triethylaluminum (0.6 mol / liter) as a polymerization catalyst and a toluene solution of methanol-modified tungsten hexachloride (concentration 0.025 mol / liter) were added to the solution in the reaction vessel. 0.9 part was added and this solution was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

1,000 parts of the ring-opening polymer solution thus obtained was charged into an autoclave, and 0.12 part of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution. Then, the hydrogenation reaction was performed by heating and stirring for 3 hours under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C.

  After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover the coagulated product, and dried to obtain a hydrogenated polymer (hereinafter also referred to as “resin A”).

Table 1 shows the physical property values according to the above (1) to (4) of the resin A thus obtained.
[Synthesis Example 2]
71 parts of DNM, 15 parts of dicyclopentadiene (DCP) represented by the following formula (5), and 1 part of bicyclo [2.2.1] hept-2-ene (NB) represented by the following formula (6) Then, 18 parts of 1-hexene (molecular weight regulator) and 200 parts of toluene (solvent for ring-opening polymerization reaction) were charged into a nitrogen-substituted reaction vessel and heated to 100 ° C.

  To this, 0.4 parts of a toluene solution of triethylaluminum (0.6 mol / liter) and 1.8 parts of a methanol-modified tungsten hexachloride toluene solution (concentration 0.025 mol / liter) were added and reacted for 1 minute. Next, 10 parts of DCP and 3 parts of NB were added over 5 minutes, and the mixture was further reacted for 45 minutes, whereby DNM / DCP / NB = 69.77 / 26.01 / 4.23 (wt%). A polymer was obtained.

Next, the obtained copolymer solution was placed in an autoclave, and 200 parts of toluene was further added. Next, 1 part of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a reaction modifier and RuHCl (CO) [P (C ₆ H ₅ )] as a hydrogenation catalyst _After adding 0.006 part of ₃ and heating to 155 ° C., hydrogen gas was charged into the reactor, and the pressure was adjusted to 10 MPa. Thereafter, the reaction was carried out at 165 ° C. for 3 hours while maintaining the pressure at 10 MPa. After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. The reaction solution is poured into a large amount of methanol to separate and recover a coagulated product, which is dried to obtain a hydrogenated polymer (hereinafter also referred to as “resin B”).

Table 1 shows physical property values according to the above (1) to (4) of the resin B thus obtained.
[Synthesis Example 3]
A hydrogenated polymer (hereinafter also referred to as “resin C”) was prepared in the same manner as in Synthesis Example 1 except that DNM 225 parts and NB 25 parts were used as monomers and the amount of 1-hexene added was 27 parts. Obtained.

  Table 1 shows the physical property values according to the above (1) to (4) of the resin C thus obtained.

[Example 1]
In a glass separable flask equipped with a stirring blade, 100 parts of resin A was charged, 300 parts of toluene was added thereto, and the mixture was stirred at room temperature for 5 hours to dissolve resin A in toluene. Next, 1.2 parts of KOH dissolved in 17 parts of n-butanol was added with stirring, and the temperature was raised to 90 ° C. After further stirring for 5 hours, the mixture was cooled to room temperature to obtain an alkali-modified resin solution. To this resin solution, pentaerythrityltetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl)] propionate as an antioxidant is added in an amount of 0.5 part to 100 parts of the resin in the resin solution The resin solution was filtered using a membrane filter made by ADVANTEC having a pore size of 5 μm. The obtained resin solution (physical property values relating to (5) above are shown in Table 2) was cast at 25 ° C. using an applicator so that the thickness after drying was 100 μm, and allowed to stand at room temperature for 12 hours. And then kept under vacuum at 80 ° C. for 2 hours and further at 150 ° C. for 12 hours to obtain a norbornene resin film A.

Table 2 shows the physical property values of the obtained film A according to the above (6) to (11).
[Example 2]
In Example 1, the norbornene system was the same as in Example 1 except that 100 parts of Resin A was dissolved in 400 parts of toluene and 3 parts of KOH was dissolved in 17 parts of n-butanol. A resin film B was obtained.

Table 2 shows the physical property values of the obtained film B according to the above (6) to (11).
[Example 3]
In Example 2, a norbornene resin film C was obtained in the same manner as in Example 2 except that the resin B was used instead of the resin A.

Table 2 shows physical property values of the obtained film C according to the above (6) to (11).
[Example 4]
In Example 2, a norbornene-based resin film D was obtained in the same manner as in Example 2 except that the resin C was used instead of the resin A.

Table 2 shows physical property values of the obtained film D according to the above (6) to (11).
[Comparative Example 1]
A glass separable flask equipped with a stirring blade was charged with 100 parts of resin A, 300 parts of toluene was added thereto, and stirred at room temperature for 5 hours to dissolve resin A in toluene (no alkali modification). A solution was obtained. To this resin solution, pentaerythrityltetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl)] propionate as an antioxidant is added in an amount of 0.5 part to 100 parts of the resin in the resin solution The resin solution was filtered using a membrane filter made by ADVANTEC having a pore size of 5 μm. The obtained resin solution was cast at 25 ° C. using an applicator so that the thickness after drying was 100 μm, allowed to stand at room temperature for 12 hours to evaporate the solvent, and then at 80 ° C. under vacuum for 2 hours. Holding at 150 ° C. for 12 hours, a norbornene-based resin film E was obtained.

Table 2 shows physical property values of the obtained film E according to the above (6) to (11).
[Comparative Example 2]
In Comparative Example 1, a norbornene-based resin film F was obtained by the same method except that the resin B was used instead of the resin A.

Table 2 shows physical property values of the obtained film F according to the above (6) to (11).
[Comparative Example 3]
In Comparative Example 1, a norbornene resin film G was obtained in the same manner except that the resin C was used instead of the resin A.

  Table 2 shows physical property values of the obtained film G according to the above (6) to (11).

  As shown in Table 2, by adding an alcohol solution of KOH to the resin A, B, and C solution and heat-treating it, an alkali-modified norbornene-based resin solution capable of forming a film by a casting method is obtained. It was revealed that the cast film of the resin solution also has sufficient transparency and strength as a norbornene resin film.

  Norbornene-based resin films A to D obtained from alkali-modified resin solutions have higher solvent resistance than norbornene-based resin films E to G obtained from alkali-untreated solutions, and are organic such as toluene and methylene chloride. It was found that the solubility in a solvent is very low, and the heat distortion temperature is improved by +4 to + 50 ° C. with respect to a film made of an alkali-unmodified solution. Further, the tensile fracture strength of the film was different depending on the resin composition, but the tensile fracture elongation of the film A was improved 4 to 7 times, and the tensile fracture strength of the film C was improved 1.5 times.

  That is, it has been clarified that a norbornene-based resin that gives a norbornene-based resin film having high solvent resistance and heat-resistant deformation property and excellent toughness can be obtained through such an alkali-denaturing reaction.

  Compared with conventional norbornene resin film, the norbornene resin film of the present invention, which is superior in solvent resistance, heat denaturation and toughness, is a heat resistant optical disk, optical fiber, optical lens, mirror, semiconductor encapsulant, transparent conductive film for LCD It is suitable for a low retardation film for LCD, a touch panel, a glass substitute optical plate material, a transparent heat-resistant coating material, and the like.

Claims (9)

A solution of a norbornene-based resin obtained by (co) polymerizing a monomer containing at least one compound represented by the following formula (1):
A norbornene resin solution obtained by heating a resin composition containing at least one hydroxide selected from the group consisting of potassium hydroxide, sodium hydroxide, calcium hydroxide and magnesium hydroxide .

(Wherein R ^{1 to} R ⁴ each independently represents a hydrogen atom; a halogen atom; a monovalent group that may contain an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom; a substituted or unsubstituted carbon; A hydrocarbon group having 1 to 15 atoms; or a group represented by —R ⁵ —COOR ⁶ .
R ⁵ represents a single bond; a substituted or unsubstituted methylene group; or a linear or branched alkylene group having 2 to 8 carbon atoms, which may contain an etheric oxygen atom.
R ⁶ represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 15 carbon atoms which may contain an etheric oxygen atom; or a substituted or unsubstituted aryl group .
However, at least one of R ^{1 to} R ⁴ represents a group represented by —R ⁵ —COOR ⁶ .
R ¹ and R ² or R ³ and R ⁴ may be bonded to each other to form an alkylidene group,
R ¹ and R ² , R ³ and R ⁴ , or R ² and R ³ may be bonded to each other to form a monocyclic or polycyclic carbocyclic or heterocyclic ring,
R ¹ and R ^4, or R ² and R ^3, they may form a double bond are bonded to each other, or, R ¹ and R ^4, and R ² and R ³ are, They may be bonded to each other to form a triple bond.
x represents 0 or an integer of 1 to 3, and y represents 0 or 1. )   The norbornene-based resin is a (co) polymer obtained by ring-opening (co) polymerizing a monomer containing at least one compound represented by the formula (1). 1. The norbornene-based resin solution described in 1.   The norbornene-based resin solution according to claim 1 or 2, wherein a heating temperature of the resin composition is in a range of 30 to 180 ° C.   The norbornene-based resin solution according to any one of claims 1 to 3, wherein the hydroxide is potassium hydroxide.   The norbornene according to any one of claims 1 to 4, wherein the hydroxide is contained in the resin composition in an amount of 0.1 to 5 parts by weight with respect to 100 parts by weight of the norbornene-based resin. Resin solution.   A norbornene resin film formed using the norbornene resin solution according to any one of claims 1 to 5. Area of the absorption peak (peak A) of the ester group carbonyl observed at 1810cm ^-1 ~1610cm ^-1 of IR spectrum obtained by measuring by FT-IR, and carboxylate observed at 1610cm ^-1 ~1520cm ^-1 The norbornene-based resin according to claim 6, wherein the alkali modification rate calculated according to the following formula from the area of the absorption peak (peak B) of the reverse symmetric stretching vibration of the group carbonyl is 0.01 to 0.5. the film.
(Alkali modification rate) = (Area of peak B) / (Area of peak A)   The norbornene-based resin film according to claim 6 or 7, wherein the content of at least one element selected from the group consisting of potassium, sodium, calcium and magnesium is 0.05 to 4% by weight. . (Co) polymerization step of (co) polymerizing a monomer containing at least one compound represented by the following formula (1) to obtain a norbornene-based resin,
A mixing step of mixing the norbornene-based resin with at least one hydroxide selected from the group consisting of potassium hydroxide, sodium hydroxide, calcium hydroxide and magnesium hydroxide to obtain a resin composition; and The manufacturing method of the norbornene-type resin solution characterized by including the heating process which heats a resin composition and obtains a norbornene-type resin solution.

(Wherein R ^{1 to} R ⁴ each independently represents a hydrogen atom; a halogen atom; a monovalent group that may contain an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom; a substituted or unsubstituted carbon; A hydrocarbon group having 1 to 15 atoms; or a group represented by —R ⁵ —COOR ⁶ .
R ⁵ represents a single bond; a substituted or unsubstituted methylene group; or a linear or branched alkylene group having 2 to 8 carbon atoms, which may contain an etheric oxygen atom.
R ⁶ represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 15 carbon atoms which may contain an etheric oxygen atom; or a substituted or unsubstituted aryl group .
However, at least one of R ^{1 to} R ⁴ represents a group represented by —R ⁵ —COOR ⁶ .
R ¹ and R ² or R ³ and R ⁴ may be bonded to each other to form an alkylidene group,
R ¹ and R ² , R ³ and R ⁴ , or R ² and R ³ may be bonded to each other to form a monocyclic or polycyclic carbocyclic or heterocyclic ring,
R ¹ and R ⁴ or R ² and R ³ may be bonded to each other to form a double bond, or R ¹ and R ⁴ , and R ² and R ³ are They may be bonded to each other to form a triple bond.
x represents 0 or an integer of 1 to 3, and y represents 0 or 1. )