JP4876596B2 - Film comprising a norbornene compound addition polymer - Google Patents

Description

  The present invention relates to a film having excellent dimensional stability comprising a norbornene compound addition polymer. More specifically, the present invention relates to a film having a small dimensional change even when the use environment temperature and humidity are changed, comprising a norbornene compound addition polymer.

In the field of optical parts such as lenses, liquid crystal display elements, display substrates such as color filters and EL display element substrates, and optical materials such as backlights and light guide plates, inorganic glass has been generally used. However, inorganic glass has drawbacks such as fragility, lack of flexibility, large specific gravity, poor processability, etc., and is insufficient to meet the recent demands for weight reduction, miniaturization and high density, Therefore, there is a strong demand for replacement with transparent resin.
When a transparent resin is used for an optical material, very high performance is required in terms of heat resistance, chemical resistance, low water absorption and the like in addition to transparency. For example, in the manufacture of a display element substrate, processing at a high temperature is necessary in the step of laminating a metal or metal oxide thin film, but deformation of the substrate due to heat, dimensional variation due to water absorption, etc. are serious problems. However, acrylic resins and polycarbonate resins conventionally used for optical materials have the disadvantage of low heat resistance and high water absorption, and are not satisfactory.

Therefore, a cyclic olefin addition polymer has been proposed as a resin that satisfies transparency, heat resistance, chemical resistance, low water absorption and optical properties, and a liquid crystal display substrate material using this polymer has been proposed (patent) Reference 1).
Cyclic olefin addition polymers, particularly polynorbornene, have a high glass transition temperature of 250 ° C. or higher, and are thus excellent in heat distortion resistance during high-temperature processing. Moreover, since polynorbornene has extremely low hygroscopicity, it has excellent dimensional stability against changes in humidity in the environment of use, and furthermore has a characteristic that it has excellent dimensional stability against thermal fluctuations because its linear expansion coefficient is as low as about 55 ppm. .
However, polynorbornene has a problem that it cannot be formed into a film by a casting method because of its low solubility in general solvents.

For this reason, various measures for improving polynorbornene have been studied. (1) Addition copolymer with α-olefin such as ethylene (Patent Document 2), (2) Substituted norbornene having a linear hydrocarbon group and Addition copolymer (Patent Literature 3), (3) addition copolymer with norbornene compound having specific cyclic saturated hydrocarbon group (Patent Literature 4), and (4) addition of norbornene compound having polar group Polymers (Patent Documents 5 and 6) and the like have been proposed.
However, the norbornene / ethylene copolymer (1) has a problem that it is difficult to produce a polymer having a glass transition temperature of 200 ° C. or higher, and the linear expansion coefficient becomes as high as about 70 to 100 ppm. It was. Similarly, the addition copolymer of (2) with a substituted norbornene having a linear hydrocarbon group also has the problems of a decrease in glass transition temperature and an increase in linear expansion coefficient. Further, the addition copolymer (3) with a norbornene compound having a specific cyclic saturated hydrocarbon group is troublesome and impractical to synthesize such a specific norbornene compound, and the solubility in general solvents is not necessarily improved. It is not always done. Furthermore, as the norbornene copolymer having a polar group (4), a copolymer with a norbornene compound having a long-chain ester group or a silyl group as a polar group is exemplified, but the problem of high water absorption There is a problem that the linear expansion coefficient is greatly increased.

JP-A-5-61026 JP-A-6-202091 JP-A-8-198919 JP 2004-51949 A Japanese National Patent Publication No. 11-505880 JP 2002-114826 A

  Accordingly, an object of the present invention is to provide a film comprising a norbornene compound addition polymer, which is excellent in heat resistance and dimensional stability as well as transparency, chemical resistance and optical properties, and uses thereof. More specifically, a film comprising a norbornene compound addition polymer, having a high glass transition temperature, a low water absorption rate, a low linear expansion coefficient, and a film which can be dissolved in a general solvent, and uses thereof are provided. It is.

  As a result of intensive studies to solve the above problems, the inventors of the present invention contain a repeating unit of an unsubstituted norbornene compound monomer and a repeating unit of a norbornene compound monomer having a specific substituent. It was found that the norbornene compound addition polymer film was excellent in solubility in general solvents while maintaining heat resistance and low water absorption, and further had a low linear expansion property. It came to complete.

Thus, according to the present invention, the repeating unit (a) and the repeating unit (b) are composed only of the following, and the molar ratio [(a) / (b)] of the repeating unit (a) to the repeating unit (b) is 70 / A film comprising a norbornene compound addition polymer having a weight average molecular weight of 300,000 to 700,000 and a number average molecular weight of 80,000 to 350,000 is provided. .
Repeating unit (a): A repeating unit of a norbornene compound monomer that is composed of only carbon and hydrogen and in which all the carbons are involved in the structure of the condensed ring skeleton.
Repeating unit (b): a part of hydrogen of a norbornene compound monomer composed only of carbon and hydrogen and all the carbons are involved in the structure of the condensed ring skeleton, only a functional group having 2 or less carbon atoms Or a repeating unit of a norbornene compound monomer having a structure substituted with only a functional group having 2 or less carbon atoms and a hydrocarbon group having 2 or less carbon atoms.
In the film of the present invention, the norbornene compound addition polymer is a 2-norbornene monomer or tetracyclo [6.2.1.1 ^3,6 . A norbornene addition polymer having a repeating unit of 0 ^2,7 ] dodec-4-ene monomer is preferable.
The film of the present invention preferably has a linear expansion coefficient of 70 ppm / ° C. or less.
The film of the present invention preferably has a water absorption of 0.1% by weight or less.

The film of the present invention may be a laminate of transparent conductive films.
Further, the film of the present invention may be a laminate of gas barrier films.
The film of the present invention is suitable as an optical film.
Moreover, the film of this invention is suitable as a member for display elements.
In the present invention, “film” is a concept that includes both “film” and “sheet” that are strictly distinguished by their thickness.

  The film comprising the norbornene compound addition polymer of the present invention is useful as an optical material because it has excellent heat resistance and solubility in general solvents in addition to transparency and optical properties, and also has low water absorption and linear expansion coefficient. .

[Norbornene compound addition polymer]
The norbornene compound addition polymer for obtaining the film of the present invention comprises only the following repeating unit (a) and repeating unit (b), and the molar ratio of repeating unit (a) to repeating unit (b) [(a) / (B)] is a norbornene compound addition polymer in the range of 70/30 to 98/2.

[Repeating unit (a)]
The repeating unit (a) is a repeating unit of a norbornene compound monomer composed of only carbon and hydrogen, and all the carbons are involved in the structure of the condensed ring skeleton.
Examples of such a repeating unit (a) include a repeating unit represented by the general formula (1).

Here, in the general formula (1), R ^{1 to} R ⁴ are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and are bonded to each other when they are a hydrocarbon group having 1 to 20 carbon atoms. Thus, a ring structure having no substituent is formed. m is an integer of 0-2.
Here, specific examples of the ring structure include cyclopentane ring, cyclopentene ring, cyclohexane ring, cyclohexene ring, benzene ring, cyclooctane ring, cyclooctene ring, norbornane ring, etc. A ring structure is included.

  The repeating unit (a) can be obtained by addition polymerization of the norbornene compound (A) represented by the general formula (2).

Here, R ^{1 to} R ⁴ and m are the same as those in the general formula (1).

Specific examples of such norbornene compound (A) include 2-norbornene, dicyclopentadiene, tricyclo [5.2.1.0 ^2,6 ] dec-8-ene, and tricyclo [6.2.1.0. ^2,7 ] undec-9-ene, tricyclo [6.2.1.0 ^2,7 ] undeca-4,9-diene, tricyclo [8.2.1.0 ^2,9 ] tridec-11-ene, Tricyclo [8.2.1.0 ^2,9 ] trideca-5,11-diene, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7] dodeca-4-ene, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as “1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene”), tetracyclo [10.2.1 0.0 ^2,11 . 0 ^4,9 ] pentadeca-4,6,8,13-tetraene (also referred to as “1,4-methano-1,4,4a, 9,9a, 10-hexahydroanthracene”), pentacyclo [9.2 1.1 ^{3, 9} . 0 ^2,10] pentadeca-12-ene, pentacyclo [9.2.1.1 ^3,9. 0 ^2,10] pentadeca-5,12-diene, pentacyclo [9.2.1.1 ^4,7. 0 ^2,10] pentadeca-12-ene, and the like.

Of these, 2-norbornene and tricyclo [5.2.1.0 ^2,6 ] deca which have no unsaturated bond other than the norbornene ring from the viewpoint of the balance between heat resistance, low water absorption and low linear expansion coefficient. 8-ene, tricyclo [6.2.1.0 ^2,7 ] undec-9-ene, tricyclo [8.2.1.0 ^2,9 ] tridec-11-ene, tetracyclo [6.2.1. 1 ^3,6 . 0 ^2,7 ] dodec-4-ene, pentacyclo [9.2.1.1 ^3,9 . 0 ^2,10] pentadeca-12-ene and pentacyclo [9.2.1.1 ^4,7. 0 ^2,10] pentadeca-12-ene are preferred, 2-norbornene and tetracyclo [6.2.1.1 ^{3, 6.} 0 ^2,7 ] dodec-4-ene is particularly preferred.

[Repeating unit (b)]
The repeating unit (b) is composed of only carbon and hydrogen, and a part of hydrogen of the norbornene compound monomer in which all the carbons are involved in the structure of the condensed ring skeleton is a functional group having 2 or less carbon atoms. Alone or a repeating unit of a norbornene compound monomer having a structure substituted with only a functional group having 2 or less carbon atoms and a hydrocarbon group having 2 or less carbon atoms.
Here, the functional group having 2 or less carbon atoms refers to a functional group having 2 or less carbon atoms, or a hydrocarbon group having 2 or less carbon atoms, or a functional group having 2 or less carbon atoms. A group having a structure substituted with a hydrogen atom having a total carbon number of 2 or less and a functional group hydrogen having a carbon number of 2 or less per se with a hydrocarbon group having a carbon number of 2 or less. It is a concept that includes those having 2 or less carbon atoms.
As an example of such a repeating unit (b), the repeating unit shown by General formula (3) can be mentioned, for example.

Here, in General Formula (3), R ^{5 to} R ⁸ are a hydrogen atom, a functional group having 2 or less carbon atoms, or a hydrocarbon group having 1 or 2 carbon atoms, and among R ^{5 to} R ⁸ At least one of is a functional group having 1 or 2 carbon atoms. n is an integer of 0-2.

  Specific examples of the hydrocarbon group having 1 or 2 carbon atoms include a methyl group, an ethyl group, a methylidene group, an ethylidene group, a vinyl group, and a vinylidene group.

  Specific examples of functional groups having 2 or less carbon atoms include hydroxyl group, mercapto group, amino group, methoxy group, ethoxy group, methoxycarbonyl group, acetoxy group, epoxyethyl group, acetyl group; cyano group; hydroxymethyl group, hydroxy group Examples include an ethyl group, an N-methylamino group, an N-ethylamino group, an N, N-dimethylamino group, a methylthio group, and an ethylthio group.

  The repeating unit (b) can be obtained by addition polymerization of the norbornene compound (B) represented by the general formula (4).

Here, R ^{5 to} R ⁸ and n are the same as in general formula (3).

Specific examples of such norbornene compound (B) include alkoxy groups having 2 or less carbon atoms such as 5-methoxy-2-norbornene, 5-ethoxy-2-norbornene, and 5,6-dimethoxy-2-norbornene. Norbornenes having a methoxycarbonyl group such as 5-methoxycarbonyl-2-norbornene and 5-methyl-5-methoxycarbonyl-2-norbornene; norbornenes having an acetoxy group such as 5-acetoxy-2-norbornene Norbornenes having an epoxyethyl group such as 5-epoxyethyl-2-norbornene; norbornenes having an acetyl group such as 5-acetyl-2-norbornene; 5-cyano-2-norbornene, 5-methyl-5-cyano -Norvo having a cyano group such as 2-norbornene Nornes; norbornenes having an N, N-dimethylamino group such as 5- (N, N-dimethylamino) -2-norbornene; carbon numbers such as 5-methylthio-2-norbornene and 5-ethylthio-2-norbornene , Norbornenes having an alkylthio group of 2 or less; 9-methoxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethoxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9,10-dimethoxytetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having a C 2 or less alkoxy group such as 0 ^2,7 ] dodec-4-ene. 0 ^2,7 ] dodec-4-enes; 9-methoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-methoxycarbonyltetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having a methoxycarbonyl group such as 0 ^2,7 ] dodec-4-ene. 0 ^2,7 ] dodec-4-enes; 9-acetoxytetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having an acetoxy group such as 0 ^2,7 ] dodec-4-ene. 0 ^2,7 ] dodec-4-enes; 9-epoxyethyltetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having an epoxyethyl group such as 0 ^2,7 ] dodec-4-ene. 0 ^2,7 ] dodec-4-enes; 9-acetyltetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having an acetyl group such as 0 ^2,7 ] dodec-4-ene. 0 ^2,7 ] dodec-4-enes; 9-cyanotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-cyanotetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having a cyano group such as 0 ^2,7 ] dodec-4-ene. 0 ^2,7 ] dodec-4-enes; 9- (N, N-dimethylamino) -tetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having an N, N-dimethylamino group such as 0 ^2,7 ] dodec-4-ene. 0 ^2,7 ] dodec-4-enes; 9-methylthiotetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylthiotetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having an alkylthio group having 2 or less carbon atoms, such as 0 ^2,7 ] dodec-4-ene. 0 ^2,7 ] dodec-4-enes.

In the present invention, it is essential that the functional group in the repeating unit (b) has 2 or less carbon atoms.
Use of a compound having a repeating unit of a norbornene compound monomer having a functional group having more than 2 carbon atoms (for example, a triethoxysilyl group) as a substituent increases the water absorption rate and the linear expansion coefficient.

  The molar ratio [(a) / (b)] of the repeating unit (a) to the repeating unit (b) in the norbornene compound addition polymer used in the present invention is (a) / (b) = 70/30 to 98. It is necessary to be within the range of / 2, preferably 75/25 to 98/2, more preferably 80/20 to 98/2. If the ratio of the repeating unit (a) is lower than this range, the water absorption rate is increased. Conversely, if it is higher than this range, the solubility is deteriorated.

The norbornene compound addition polymer used in the present invention has a polystyrene-reduced weight average molecular weight (Mw) of 300,000 to 700,000 obtained by measurement by gel permeation chromatography, and a number average molecular weight of 80,000. It must be ˜350,000.
If the weight average molecular weight or number average molecular weight exceeds the above upper limit, the film will not dissolve in the solvent. Conversely, if the weight average molecular weight or number average molecular weight is lower than the lower limit, the film tends to crack.
The weight average molecular weight is preferably in the range of 350,000 to 650,000.
Moreover, it is preferable that a number average molecular weight exists in the range of 100,000-300,000.

  The film made of the norbornene compound addition polymer of the present invention preferably has a linear expansion coefficient of 70 ppm / ° C. or less, more preferably 68 ppm / ° C., and still more preferably 65 ppm / ° C.

  The film comprising the norbornene compound addition polymer of the present invention preferably has a water absorption of 0.1% by weight or less, more preferably 0.08% by weight or less, and still more preferably 0.06% by weight or less.

The film comprising the norbornene compound addition polymer of the present invention is excellent in solubility in a general solvent. For example, it is soluble in aromatic hydrocarbons such as toluene and xylene; alicyclic hydrocarbons such as cyclohexane and decalin; halogenated hydrocarbons such as chloroform and chlorobenzene;
Therefore, a film can be easily formed from the norbornene compound addition polymer as a solution of these solvents.

[Production of norbornene compound addition polymer]
In order to obtain the norbornene compound addition polymer used in the present invention, the norbornene having the norbornene compound (A) represented by the general formula (2) and the norbornene compound (B) represented by the general formula (4) as essential components The compound monomer mixture may be subjected to addition polymerization in the presence of a polymerization catalyst.

The polymerization catalyst for obtaining the norbornene compound addition polymer used in the present invention is not particularly limited.
Specific examples include polymerization catalysts such as [6-methoxynorbornen-2-yl-5-palladium (cyclooctadiene)] hexafluorophosphate described in JP-A-11-505880; pamphlet of International Publication No. 2000/20472 Polymerization catalyst such as (allyl) palladium chloride dimer / tricyclohexylphosphine / lithium tetrakis (pentafluorophenyl) borate / 2.5 ether described above; (phenyl) palladium bis (triphenylphosphine) described in JP-A-2001-098035 A polymerization catalyst comprising a Group 10 transition metal catalyst such as a polymerization catalyst such as iodide / methylaluminoxane; can be mentioned as a suitable example.

  An olefinically unsaturated bond may be present in the norbornene compound addition polymer obtained by the above method, and those obtained by hydrogenating the olefinically unsaturated bond can also be suitably used.

The hydrogenation reaction may be carried out by a generally known method, that is, by contacting with hydrogen in the presence of a hydrogenation catalyst.
As a hydrogenation catalyst, a solid catalyst in which a group 8-10 transition metal such as nickel, palladium, platinum, cobalt, ruthenium, rhodium or a compound thereof is supported on a porous carrier such as carbon, alumina, silica, silica alumina, diatomaceous earth, etc. Used in combination with organic carboxylate of group 4-10 metal such as cobalt, nickel, palladium, β-diketone compound and organoaluminum or organolithium; homogeneous catalyst such as complex of ruthenium, rhodium, iridium, etc. It is done.

It is preferable to remove the catalyst after the addition polymerization reaction and / or the hydrogenation reaction.
As a method for removing the catalyst, a method of removing by adsorption with an adsorbent such as silica, alumina, activated carbon, etc .; a method of removing with an ion exchange resin; a method of adding a chelating agent to insolubilize the catalyst residue and filtering; a large amount of polymer solution And a method of solidifying by adding to a poor solvent such as methanol and acetone.

  Recovery of the norbornene compound addition polymer after the addition polymerization reaction can be performed by a known method such as a method of directly removing the solvent from the polymer solution or a method of coagulating and separating with a poor solvent such as methanol. Further, a molded product may be produced by using the solution after the polymerization reaction or the solution after removing the catalyst as it is for cast molding.

[Film made of norbornene compound addition polymer]
The film comprising the norbornene compound addition polymer of the present invention can be used as an optical component, an electrical insulating component, an electrical / electronic component, an electronic component sealant, a medical device, a packaging material, and the like.
The film comprising the norbornene compound addition polymer of the present invention may be composed only of the norbornene compound addition polymer, and the norbornene compound polymer and other transparent resin (for example, cyclic olefin addition polymer, hydrogenated) Cyclic olefin ring-opening polymer, addition copolymer of α-olefin and cyclic olefin, crystalline α-olefin polymer, further copolymer of rubbery ethylene and α-olefin having 3 or more carbon atoms, A hydrogenated butadiene polymer, a hydrogenated butadiene / styrene block copolymer, a hydrogenated isoprene polymer, or the like may be used.

When forming the film of the present invention comprising a norbornene compound addition polymer, various additives may be blended as necessary.
Such additives include fillers, antioxidants, phosphors, ultraviolet absorbers, antistatic agents, light stabilizers, near infrared absorbers, colorants such as dyes and pigments, lubricants, plasticizers, flame retardants. And a crosslinking agent.

Examples of the filler include oxides of metals such as silicon, titanium, aluminum, and zirconium.
Examples of the antioxidant include a phenolic antioxidant, a lactone antioxidant, a phosphorus antioxidant, a thioether antioxidant, and the like.
The phosphor is excited by receiving light and emits light having a wavelength longer than the excitation wavelength.For example, when sealing an optical element, the wavelength of the blue region to the ultraviolet region where the optical element emits light is changed. In response, it is used to emit light in the visible region.
The method for blending these additives is not particularly limited.
In order to obtain the film of the present invention comprising a norbornene compound addition polymer, a known molding method may be used.

  The norbornene compound addition polymer used in the present invention is easily dissolved in an organic solvent. Therefore, the organic solvent solution can be coated or cast on a steel belt, a carrier film or the like, and then formed into a film by a solution casting method in which a molded product is obtained through a drying step.

The organic solvent solution of the norbornene compound addition polymer used in the present invention may be impregnated into a woven or non-woven fabric such as glass cloth and then dried to form a film containing the woven or non-woven fabric.
Further, after swelling the norbornene compound addition polymer used in the present invention with an organic solvent, the polymer can be formed and processed into a film while the solvent is evaporated by an extruder.

Moreover, after pouring the organic solvent solution of the norbornene compound addition polymer used for this invention in a type | mold, it can also shape | mold by evaporating a solvent. Furthermore, after the organic solvent solution is attached to a specific part or substrate, the solvent can be evaporated to form the film.
Furthermore, the norbornene compound addition polymer used in the present invention can be made into a polymer blend composition blended with another thermoplastic resin, and then formed into a film by a melt extrusion method using a melt extruder or the like.

  The thickness of the film can be selected depending on the purpose of use, but is usually 1 to 1,000 μm, preferably 2 to 500 μm. When the thickness of the film is within this range, the time required for film formation is short, and the resulting film is excellent in strength.

  Since the film comprising the norbornene compound addition polymer of the present invention has a total light transmittance of 70% or more, preferably 80% or more, more preferably 85% or more, it is suitable as an optical material and a display element member. Can be used.

[Transparent conductive film laminate film]
The film made of the norbornene compound addition polymer of the present invention may be a laminate of transparent conductive films (sometimes referred to as “transparent conductive film laminate film”).
Specifically, inorganic substances such as inorganic oxides, inorganic nitrides or inorganic sulfides (for example, indium tin oxide (ITO), aluminum oxide, silicon oxide, titanium oxide, zinc oxide, tungsten oxide, aluminum nitride, silicon nitride) , Titanium nitride, cadmium sulfide, zinc sulfide, zinc selenide, or the like), and a transparent conductive film is stacked by a film forming method such as a vacuum film forming method (for example, sputtering method, vapor deposition method, CVD method).
The film thickness of the transparent conductive film can be appropriately selected within a range of 50 to 4,000 mm.

  The transparent conductive film laminated film of the present invention has a total light transmittance of 70% or more, preferably 80% or more, more preferably 85% or more, and therefore can be suitably used as an optical material and a display element member. it can.

In the transparent conductive film laminated film of the present invention, an adhesive layer may be provided between the film comprising the norbornene compound addition polymer and the transparent conductive film for the purpose of improving the smoothness of the film and the adhesion to the transparent conductive film. Good. The adhesive layer is obtained by applying a resin varnish and removing the solvent by drying. In this case, a resin having a film-forming property after removing the solvent, that is, a varnish to which a solid resin is added is preferable from the viewpoint of uniform application. Specific examples of the resin for this purpose include photo-curable resins such as so-called acrylic prepolymers such as epoxy diacrylate, urethane diacrylate, and polyester diacrylate; o-cresol novolac type, bisphenol type epoxy type, urethane type, Examples include acrylic, urea, melamine, and unsaturated polyester thermosetting resins; electron beam curable resins. Among these, a photocurable resin is preferable from the viewpoint of productivity and cost.
As a method for forming the cured resin film, there are a gravure coating method, a reverse roll coating method, a kiss roll coating method and the like, and any method may be used.

The transparent conductive film laminated film of the present invention may have a gas barrier layer on the side opposite to the transparent conductive film. The gas barrier layer may be formed of an inorganic material or an organic material. Examples of the inorganic material that can be used include silicon oxide, aluminum oxide, and indium oxide, and examples of the organic material include polyvinyl alcohol, an ethylene-vinyl alcohol copolymer, and polyamide.
The thickness of the gas barrier layer is desirably 100 to 2,000 mm in the case of an inorganic material and 500 to 10,000 mm in the case of an organic material.
These inorganic materials can be formed by known means such as sputtering, ion plating, resistance heating, and CVD. In the case of an organic material, it can be formed by dissolving it in a solvent, applying it by the coating method as described above, and drying it.
An adhesive layer may be provided between the film and the gas barrier layer.
Further, a protective coat layer may be laminated on the gas barrier layer to protect it. The protective coat layer is preferably formed by the same method as the adhesive layer.

〔Color filter〕
A color filter can be obtained by laminating a color filter layer on a film made of the norbornene compound addition polymer of the present invention or a color filter substrate made of the transparent conductive film laminated film of the present invention. As a lamination method, a known pigment dispersion method, dyeing method, electrodeposition method, printing method, transfer method, or the like can be used.
For example, in the pigment dispersion method, a black matrix is formed on a color filter substrate by a sputtering method or a vacuum deposition method using a chromium compound such as metal chromium, chromium oxide, or chromium nitride, or a metal light shielding film such as nickel and tungsten alloy. Then, a photosensitive resin composition (color resist) in which a red pigment is dispersed is applied to the entire surface by a spin coating method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. , Exposure through a mask and development after exposure to form red pixels. In the same procedure, blue, green pixels are applied, exposed and developed to form three color pixels. The order in which the three color pixels are formed is not particularly determined and is arbitrarily selected. In the case where the black matrix portion between the pixels is concave, the protective film may be formed by covering the surface with a transparent resin such as epoxy resin or acrylic resin for smoothing. Also, when forming the black matrix, the above-described pigment dispersion method may be employed. Specifically, a photosensitive resin (black resist) in which a black pigment is dispersed may be applied, exposed and developed.

Examples of the constituents of the color resist and black resist compositions and the methods of coating, exposing and developing include constituents and methods described in JP-A-2004-56151, JP-A-2004-347831, etc. Can be used. Also, a known method can be used for the printing method. For example, the ink and the printing method described in JP-A-6-347637, JP-A-11-326622, and JP-A-2004-333971 are used. Can do.
Since the film made of the norbornene compound addition polymer of the present invention has high resistance to chemicals such as resist, ink, developer, etc., the substrate may be deformed or cracks may occur in the color filter laminating process. There is no.

  For color filter substrates and black matrix forming substrates, corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as silane coupling agents and urethane resins, etc., as necessary, for improving surface properties such as adhesion May be performed. When performing the thin film formation process of various resin, the film thickness is 0.01-10 micrometers normally, Preferably it is the range of 0.05-5 micrometers.

  The above color filter can be used as a color filter of a liquid crystal display device, and can also be used as a part of components such as a color display and a liquid crystal display device.

[Optical parts]
The film made of the norbornene compound addition polymer of the present invention is a color filter substrate, light guide plate, protective film, polarizing film, retardation film, touch panel, transparent electrode substrate, optical recording substrate such as CD, MD, DVD, It can be suitably used as an optical component such as a TFT substrate, a liquid crystal display substrate, an organic EL display substrate, an optical transmission waveguide, optical lenses, a sealing material, or the like.
Among them, members for display elements, specifically, color filter substrates, light guide plates, protective films, polarizing films, retardation films, touch panels, transparent electrode substrates, TFT substrates, liquid crystal display substrates, organic EL display substrates, etc. Can be suitably used.

  The film comprising the norbornene compound-added polymer of the present invention can be used not only for optical parts but also for electrical insulating parts, electrical / electronic parts, electronic parts sealants, medical equipment, and packaging materials.

[Electrical insulation parts]
Since the film comprising the norbornene compound addition polymer of the present invention has excellent heat resistance and a low coefficient of linear expansion, it is not thermally deformed by the soldering process, and there is no decrease in mechanical properties due to thermal degradation. Ideal as an insulation component.
Examples of the electrical insulating parts include coating materials for electric wires and cables, insulating materials for OA equipment such as computers, printers, and copiers, and insulating parts for flexible printed boards. Particularly, it is preferably used as a flexible printed board. It is done.

[Electric / Electronic Parts]
Electrical / electronic components include containers, trays, carrier tapes, separation films, cleaning containers, pipes, tubes, etc., sealing materials for semiconductor elements, optical elements (light emitting diodes, etc.), sealing materials for integrated circuits, over Used for coating materials.

[Electronic component encapsulant]
The film comprising the norbornene compound addition polymer of the present invention has a low water absorption rate and is excellent in heat resistance, transparency and electrical properties, and thus is useful as a sealing material for electronic parts. Electronic components include integrated circuit components including semiconductor chips such as CPUs and DRAMs; semiconductor components such as diodes, transistors, and light emitting elements (LEDs); general electronic components such as resistors, capacitors, inductors, ceramic filters, and thermistors. Can be mentioned. Especially, it is preferable as LED element sealing materials, such as a blue LED element, an ultraviolet light emission LED element, and a white LED element, especially as a sealing material of these surface mount type LED.

  The electronic component sealing method can be performed by attaching an organic solvent solution of the norbornene compound addition polymer used in the present invention to the electronic component to be sealed and evaporating and removing the solvent. At this time, a conventional sealing method, such as a transfer molding method, a potting method, or a coating method, can be used. In the case of the transfer molding method, the norbornene compound-added polymer solid content containing a small amount of an organic solvent is softened by heating, and then injected into a mold equipped with an electronic component for molding, and a small amount of the solvent is removed by evaporation. In the potting method, an electronic component to be sealed is filled with a high-viscosity norbornene compound addition polymer solution and dried. In the coating method, a norbornene compound addition polymer solution is coated on an electronic component to be sealed, particularly an electronic substrate, etc. by a method such as a roll coating method, a curtain coating method, a screen printing method, a spin coating method, a dipping method, and the like. Is removed by evaporation.

[Medical equipment]
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.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. The present invention is not limited to these examples. In addition, unless otherwise indicated, the part and% in an Example are a basis of weight.
Moreover, the test and evaluation in an Example and a comparative example were performed with the following method.

(1) Weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer
It is measured as a polystyrene conversion value by gel permeation chromatography (GPC) using tetrahydrofuran or chloroform as a solvent.
(2) Copolymerization ratio of polymer
Obtained by ¹ H-NMR measurement.
(3) Water absorption rate It calculates | requires from the weight change after immersing a film piece in 23 degreeC water for 24 hours.
(4) Glass transition temperature (Tg)
It is measured at the temperature of the inflection point of the storage elastic modulus E ′ measured by dynamic viscoelasticity. The measurement of dynamic viscoelasticity uses DMS6100 (manufactured by Seiko Instruments Inc.), the measurement frequency is 10 Hz, the heating rate is 5 ° C./min, the excitation mode is a single waveform, and the excitation amplitude is 5.0 μm. The temperature at the inflection point of the storage elastic modulus E ′ is measured using the object.

(5) Linear expansion coefficient Using TMA (Thermal Mechanical Analysis) / SDTA840 (manufactured by METTLER TOLEDO), a film piece having a film thickness of 100 μm, a length of 15.4 mm, and a width of 5.95 mm was fixed upright and fixed. A 1 g weight is applied by the probe. In order to remove the thermal history of the film, the temperature was once raised from room temperature to 300 ° C. at 5 ° C./min. The linear expansion coefficient is obtained from the inclination of the elongation of the film pieces in between.
(6) Total light transmittance A film having a film thickness of 100 μm is measured in a wavelength range of 400 to 700 nm using an ultraviolet / visible spectrometer (trade name “V-550” manufactured by JASCO).
(7) Film strength (presence or absence of cracking during bending)
The film strength was evaluated by the presence or absence of occurrence of cracks in the folded portion when a 100 μm thick film prepared from a toluene solution was folded at the center and overlapped.

Example 1
(Synthesis of norbornene compound addition polymer (A))
A nitrogen-substituted glass reactor was charged with 0.77 part of (allyl) palladium (tricyclohexylphosphine) chloride and 1.14 parts of lithium tetrakis (pentafluorophenyl) borate, followed by 2 parts of toluene to prepare a catalyst solution. .
Next, in a pressure-resistant glass reactor equipped with a nitrogen-replaced stirrer, 1,650 parts of 2-norbornene (NB; molecular weight = 94), 300 parts of 5-acetoxy-2-norbornene (NBOAc; molecular weight = 152), as a molecular weight regulator 405 parts of styrene and 7,200 parts of toluene as a polymerization solvent were added, and the above catalyst solution was added to initiate polymerization. After reacting at 60 ° C. for 1.5 hours, the polymerization reaction solution is poured into a large amount of methanol to completely precipitate the polymer, washed by filtration, dried under reduced pressure at 50 ° C. for 18 hours, and then copolymer (A) 1 , 550 parts were obtained.
The obtained copolymer (A) was soluble in toluene, chloroform and the like. The number average molecular weight (hereinafter sometimes abbreviated as “Mn”) of the copolymer (A) is 157,000, and the weight average molecular weight (hereinafter sometimes abbreviated as “Mw”) is 403,000. The composition ratio of NB unit / NBOAc unit in the copolymer (A) was 95/5 (mol / mol). The evaluation results of the properties of the copolymer (A) are shown in Table 1.
A 10% by weight toluene solution of the copolymer (a) was prepared and cast on a flat polytetrafluoroethylene sheet. After removing toluene by evaporation under an air stream at room temperature for 24 hours, 80% The film was vacuum-dried at 24 ° C. for 24 hours to obtain a film having a thickness of 100 μm.
Table 1 shows the results of measuring the glass transition temperature, the water absorption rate, and the linear expansion coefficient of the obtained film piece.

(Example 2)
(Synthesis of norbornene compound addition polymer (B))
Into a pressure-resistant glass reactor equipped with a stirrer substituted with nitrogen, 1,650 parts of 2-norbornene (NB; molecular weight = 94), 9-methoxycarbonyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene (TCDMA; molecular weight = 218) 688 parts, 430 parts of styrene as a molecular weight regulator and 7,200 parts of toluene as a polymerization solvent, the same catalyst solution used in Example 1 Was added to initiate the polymerization. After reacting at 60 ° C. for 2.5 hours, the polymerization reaction solution is poured into a large amount of methanol to completely precipitate the polymer, washed by filtration, dried under reduced pressure at 50 ° C. for 18 hours, and copolymer (B) 2 , 100 parts were obtained.
The obtained copolymer (B) was soluble in toluene, chloroform and the like. The Mn of the copolymer (B) was 217,000, the Mw was 564,000, and the NB unit / TCDMA unit composition ratio in the copolymer (B) was 85/15 (mol / mol). Table 1 shows the evaluation results of the properties of the copolymer (B).
A film having a thickness of 100 μm was obtained from this copolymer (B) in the same manner as in Example 1.
Table 1 shows the results of measuring the glass transition temperature, the water absorption rate, and the linear expansion coefficient of the obtained film piece.

(Example 3)
(Synthesis of norbornene compound addition polymer (C))
Example 1 is used except that 324 parts of 5-methyl-5-methoxycarbonyl-2-norbornene (NBMMA; molecular weight = 166) is used in place of 300 parts of 5-acetoxy-2-norbornene (NBOAc; molecular weight = 152). Similarly, 1,780 parts of copolymer (C) were obtained.
The obtained copolymer (C) was soluble in toluene, chloroform and the like. Mn of the copolymer (C) was 192,000, Mw was 504,000, and the composition ratio of NB units / NBMAA units in the copolymer (C) was 92/8 (mol / mol). Table 1 shows the evaluation results of the properties of the copolymer (C).
A film having a thickness of 100 μm was obtained from this copolymer (C) in the same manner as in Example 1.
Table 1 shows the results of measuring the glass transition temperature, the water absorption rate, and the linear expansion coefficient of the obtained film piece.

Example 4
(Synthesis of norbornene compound addition polymer (D))
In a pressure-resistant glass reactor with a nitrogen-substituted stirrer, 1,200 parts of 2-norbornene (NB; molecular weight = 94), 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene (MTHF; molecular weight) = 182) 1,160 parts, 5-methoxycarbonyl-2-norbornene (NBMA; molecular weight = 152) 970 parts 521 parts of styrene as molecular weight regulator and 7,700 parts of toluene as polymerization solvent were used and used in Example 1. The same catalyst solution was added to initiate polymerization. After reacting at 60 ° C. for 2 hours, the polymerization reaction solution is poured into a large amount of methanol to completely precipitate the polymer, washed by filtration, dried under reduced pressure at 50 ° C. for 18 hours, and then copolymer (D) 3,020. Got a part.
The obtained copolymer (D) was soluble in toluene, chloroform and the like. Copolymer (D) has Mn of 179,000, Mw of 409,000, and the composition ratio of NB unit / MTHF unit / NBMA unit in copolymer (D) is 58/25/17 (mol / mol / mol). )Met. The evaluation results of the properties of the copolymer (D) are shown in Table 1.
A film having a thickness of 100 μm was obtained from this copolymer (D) in the same manner as in Example 1.
Table 1 shows the results of measuring the glass transition temperature, the water absorption rate, and the linear expansion coefficient of the obtained film piece.

(Comparative Example 1)
(Synthesis of norbornene compound addition polymer (E))
To a nitrogen-replaced glass reactor, 8.2 parts of N, N′-bis- (2-methylphenyl) benzamidinate nickel (triphenylphosphine) chloride and toluene of methylaluminoxane having an aluminum content of 9.0% 825 parts of the solution was added, and subsequently 500 parts of toluene was added to prepare a catalyst solution.
Subsequently, 2,360 parts of 2-norbornene and 4,000 parts of toluene as a polymerization solvent were charged into a pressure-resistant glass reactor equipped with a nitrogen-substituted stirrer, and the polymerization was started by adding the above catalyst solution. When the reaction was performed for a time, the polymer was precipitated and the polymerization solution was solidified. The solidified polymerization reaction liquid was put in a large amount of methanol, finely pulverized, filtered and washed, and then dried under reduced pressure at 50 ° C. for 18 hours to obtain 2,300 parts of polymer (E). Since the obtained polymer (E) was insoluble in toluene, chloroform, etc., the molecular weight could not be measured. The evaluation results of the properties of the polymer (E) are shown in Table 1.
Moreover, since the polymer (E) did not melt | dissolve in a solvent, the film was not able to be created.

(Comparative Example 2)
(Synthesis of norbornene compound addition polymer (F))
Polymerization of norbornene compound in the same manner as in Example 1 except that the monomer amount was changed to 550 parts of 2-norbornene (NB; molecular weight = 94) and 900 parts of 5-acetoxy-2-norbornene (NBOAc; molecular weight = 152). And 360 parts of copolymer (F) was obtained. The obtained copolymer (F) was soluble in toluene and chloroform. The Mn of the copolymer (F) was 86,000, the Mw was 255,000, and the NB unit / NBOAc unit composition ratio in the copolymer (F) was 66/34 (mol / mol). The evaluation results of the properties of the copolymer (F) are shown in Table 1.
A film having a thickness of 100 μm was obtained from this copolymer (F) in the same manner as in Example 1.
Table 1 shows the results of measuring the glass transition temperature, the water absorption rate, and the linear expansion coefficient of the obtained film piece.

(Comparative Example 3)
(Synthesis of norbornene compound addition polymer (G))
In a pressure-resistant glass reactor equipped with a nitrogen-replaced stirrer, 2,400 parts of 2-norbornene (NB; molecular weight = 94), 1,280 parts of 5-triethoxysilyl-2-norbornene (NBSET, molecular weight = 256), molecular weight adjustment 521 parts of styrene as an agent and 8,600 parts of toluene as a polymerization solvent were added, and the same catalyst solution as used in Example 1 was added to initiate polymerization. After reacting at 60 ° C. for 3 hours, the polymerization reaction solution is poured into a large amount of methanol to completely precipitate the polymer, washed by filtration, dried under reduced pressure at 50 ° C. for 18 hours, and then copolymer (G) 3,100. Got a part.
The obtained copolymer (G) was soluble in toluene, chloroform and the like. Mn of the copolymer (G) was 211,000, Mw was 514,000, and the NB unit / NBSET unit composition ratio in the copolymer (G) was 85/15 (mol / mol). The evaluation results of the properties of the copolymer (G) are shown in Table 1.
A film having a thickness of 100 μm was obtained from this copolymer (G) in the same manner as in Example 1.
Table 1 shows the results of measuring the glass transition temperature, the water absorption rate, and the linear expansion coefficient of the obtained film piece.

(Comparative Example 4)
(Synthesis of norbornene compound addition polymer (H))
The norbornene compound was polymerized in the same manner as in Example 1 except that the amount of styrene was 200 parts to obtain 1,900 parts of copolymer (H).
The obtained copolymer (H) swelled in toluene and chloroform, but was not completely dissolved. Mn of the soluble part of the copolymer (H) is 433,000, Mw is 1,210,000, and the composition ratio of NB unit / NBOAc unit in the copolymer (H) is 91/9 (mol / mol). Met. The evaluation results of the properties of the copolymer (H) are shown in Table 1.
Moreover, since the polymer (H) swells only in a solvent and does not dissolve, a film could not be formed.

(Comparative Example 5)
(Synthesis of norbornene compound addition polymer (I))
The norbornene compound was polymerized in the same manner as in Example 1 except that the amount of styrene was changed to 1,200 parts to obtain 1,080 parts of copolymer (I).
The obtained copolymer (I) was soluble in toluene and chloroform. Copolymer (I) had Mn of 48,000, Mw of 121,000, and the composition ratio of NB units / NBOAc units in copolymer (I) was 94/6 (mol / mol). The evaluation results of the properties of the copolymer (I) are shown in Table 1.
A 100 μm-thick film was obtained from this copolymer (I) in the same manner as in Example 1.
Table 1 shows the results of measuring the glass transition temperature, the water absorption rate, and the linear expansion coefficient of the obtained film piece.

Footnotes in Table 1 * 1: 2-norbornene * 2: 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene * 3: 5-acetoxy-2-norbornene * 4: 9-methoxycarbonyltetra Cyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene * 5: 5-methyl-5-methoxycarbonyl-2-norbornene * 6: 5-methoxycarbonyl-2-norbornene * 7: 5-triethoxysilyl-2-norbornene

From the results of Table 1, a film is formed from polynorbornene consisting only of repeating repeating units (a): only norbornene compound monomers composed of only carbon and hydrogen, and all carbons are involved in the structure of the condensed ring skeleton. (Comparative Example 1).
Moreover, when the ratio of a repeating unit (a) is lower than the range prescribed | regulated by this invention, it turns out that a water absorption becomes high (comparative example 2).
In addition, the norbornene compound addition copolymer having a repeating unit of a norbornene compound monomer having a functional group having more than 2 carbon atoms instead of the repeating unit (b) has a high water absorption and a high linear expansion coefficient. It can be seen that this is only obtained (Comparative Example 3).
Furthermore, when the molecular weight of the norbornene compound addition polymer deviates from the range specified in the present invention, a film cannot be formed (Comparative Example 4), and when deviated below, the film strength is inferior (Comparative Example). 5) I understand.
In contrast, a film made of a norbornene compound addition polymer that satisfies the requirements of the present invention has a high glass transition temperature, a low water absorption, a low coefficient of linear expansion, and an excellent film strength. (Examples 1-4).

Claims (8)

It consists only of the following repeating unit (a) and repeating unit (b), and the molar ratio [(a) / (b)] of repeating unit (a) to repeating unit (b) is in the range of 70/30 to 98/2. A film comprising a norbornene compound addition polymer having a weight average molecular weight of 300,000 to 700,000 and a number average molecular weight of 80,000 to 350,000.
Repeating unit (a): A repeating unit of a norbornene compound monomer that is composed of only carbon and hydrogen and in which all the carbons are involved in the structure of the condensed ring skeleton.
Repeating unit (b): a part of hydrogen of a norbornene compound monomer composed only of carbon and hydrogen, and all the carbons are involved in the structure of the condensed ring skeleton, only with an acetoxy group or a methoxycarbonyl group or A repeating unit of a norbornene compound monomer having a structure in which only an acetoxy group or a methoxycarbonyl group and a hydrocarbon group having 2 or less carbon atoms are substituted.
The norbornene compound addition polymer is a 2-norbornene monomer or tetracyclo [6.2.1.1 ^3,6 . The film according to claim 1, which is a norbornene addition polymer having a repeating unit of 0 ^2,7 ] dodec-4-ene monomer.   The film according to claim 1 or 2, wherein the linear expansion coefficient is 70 ppm / ° C or less.   The film according to any one of claims 1 to 3, which has a water absorption of 0.1% by weight or less.   The film according to claim 1, wherein a transparent conductive film is laminated.   The film according to any one of claims 1 to 5, wherein a gas barrier film is laminated.   It is an optical film, The film in any one of Claims 1-6.   The film according to claim 7, which is a display element member.