WO2007122932A1 - ノルボルネン化合物付加重合体フィルム、その製造方法及びその用途 - Google Patents
ノルボルネン化合物付加重合体フィルム、その製造方法及びその用途 Download PDFInfo
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- WO2007122932A1 WO2007122932A1 PCT/JP2007/055463 JP2007055463W WO2007122932A1 WO 2007122932 A1 WO2007122932 A1 WO 2007122932A1 JP 2007055463 W JP2007055463 W JP 2007055463W WO 2007122932 A1 WO2007122932 A1 WO 2007122932A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/02—Wrappers or flexible covers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
- G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
- G11B7/2533—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins
- G11B7/2538—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins polycycloolefins [PCO]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon
Definitions
- the present invention relates to a norbornene compound addition polymer film excellent in dimensional stability, which is suitably used for optical parts and electrical insulating parts. More specifically, there is almost no dimensional change due to fluctuations in the use environment temperature or humidity, or treatment with chemicals.
- Non-Patent Document 1 proposes an electrical insulating component using a norbornene compound addition polymer film
- Patent Document 1 discloses a liquid crystal display group using a norbornene compound addition polymer film. Board materials are disclosed.
- Patent Document 2 discloses that a cyclic polyolefin-based addition polymer is dissolved in a solvent (1) that can be dissolved at 25 ° C and solution casted. The amount of residual solvent is not affected by thermal degradation by contacting with a solvent (2) having a boiling point of 150 ° C or less under atmospheric pressure, which does not dissolve the cyclic olefin-based addition polymer but is uniformly mixed with the solvent (1). Optical material with excellent optical properties, fracture strength, heat resistance and dimensional stability It has been reported that a film for use can be obtained.
- this method requires a complicated operation in which the formed film is immersed in the solvent (1) or brought into contact with the saturated vapor of the solvent (1) and then dried in a vacuum under heating. It is important.
- a vacuum drying treatment is performed at a high temperature as shown in a comparative example of the same document. Even if it is carried out, the residual solvent amount of the film obtained is from 2 to 5% compared to before the treatment, and at most it is about half, and the rupture strength is reduced and the dimensional change is not improved but remains very large. In addition, the total light transmittance is greatly reduced, which makes the optical material useless at all.
- Patent Document 1 Japanese Patent Application Laid-Open No. 5-61026
- Patent Document 2 JP 2004-59639 A
- Non-Patent Document 1 Journal of Polymer Science Part B: Polymer Physics (Part B: Polymer Pnysics, 1999, Brother 3 / ⁇ , pp3003-3010
- an object of the present invention is to provide a norbornene compound addition polymer film excellent in heat resistance, chemical resistance, dimensional stability, and the like, which can be suitably used in the production process of optical components and electrical insulating components, and its It is an object of the present invention to provide a manufacturing method, and an optical component, an electrical insulating component, an electrical / electronic component, an electronic component sealing material, a medical device, and a packaging material such as a norbornene compound addition polymer film.
- the present inventors have found that the norbornene compound addition polymer film can be obtained without performing a complicated treatment such as immersing the film of the norbornene compound addition polymer in a solvent.
- the glass transition temperature of the polymer polymer is slightly lower than this, and it can be warped or deformed even if it is exposed to high temperatures or in contact with chemicals by a simple operation of heat treatment at a temperature.
- a product that hardly changes with respect to the original dimension is obtained, and the present invention has been completed based on this finding.
- the norbornene compound addition polymer film of the present invention preferably has a dimensional change rate of lOOppm or less before and after being immersed in water at 25 ° C for 1 hour.
- the norbornene compound addition polymer film of the present invention preferably has a solvent content of 1,000 ppm or less.
- the norbornene compound addition polymer film of the present invention comprises at least one antioxidant selected from the group consisting of a phenolic antioxidant, a rataton antioxidant and a phosphorus antioxidant, and a norbornene compound addition polymer film.
- the content is preferably 0.01 to 10% by weight based on the weight.
- a film having a residual solvent amount of not more than 5, OOOppm is obtained at (T-150) ° C or 180 ° C. !, From the above high temperature to T ° C (where T is the glass transition temperature of the norbornene compound addition polymer).
- T is the glass transition temperature of the norbornene compound addition polymer.
- a cast film of a copolymer with a norbornene compound having a residual solvent amount of 5, OOOppm or less (T 150) ° C or 180 ° Heat treatment is preferably performed at a temperature in the range from C to!
- the process for preparing the norbornene compound addition polymer film directly from the norbornene compound addition polymer without passing through the form of a cast film is performed.
- the norbornene compound addition polymer film of the present invention In the production of the norbornene compound addition polymer film of the present invention, In preparing a film having a residual solvent amount of 5, OOOppm or less, it is preferable to use a plasticizer in combination.
- the norbornene compound addition polymer film of the present invention may be obtained by further laminating a transparent conductive film.
- an optical component an electrical insulating component, an electrical / electronic component, an electronic component sealing material, a medical device, and a packaging material that also have the norbornene compound addition polymer film power of the present invention.
- an optical component obtained by laminating the norbornene compound addition polymer film of the present invention and a transparent substrate having a light transmittance of 80% or more and a linear expansion coefficient of 50 ppmZ ° C or less. Provided.
- the solvent treatment of the film is not required, and the dimensional change is hardly caused by heating, solvent immersion and water immersion with a simple operation.
- a norbornene compound addition polymer film that is excellent in color and little colored can be obtained. Therefore, the norbornene compound addition polymer film of the present invention is useful for optical parts, electrical insulating parts, electrical and electronic parts, electronic parts sealing materials, medical equipment and packaging materials.
- the norbornene compound addition polymer used for the norbornene compound addition polymer film of the present invention is composed of a repeating structural unit represented by the general formula (1).
- I ⁇ to R 4 independently of each other have a hydrogen atom; a functional group containing a hetero atom or a silicon atom in Groups 15 to 16 of the periodic table; or However, it is a hydrocarbon group having 1 to 20 carbon atoms. Further, I ⁇ to R 4 may be bonded to each other to form a ring. m is 0 or an integer of 1 or more.
- I ⁇ ⁇ R periodic table 15-16 Group heteroatoms of which are included in the functional group represented by 4 is not particularly limited constant, it can be exemplified an oxygen atom, a nitrogen atom and a sulfur atom .
- functional groups include hydroxy, alkoxy, aryloxy, carbonyl, hydroxy carbo yl, alkoxy carbo yl, aryl carbo yl, functional groups containing oxygen atoms such as acid anhydride groups; Functional groups containing nitrogen atoms, such as arylamidocyano; functional groups containing oxygen atoms and nitrogen atoms, such as aminoamino, alkylaminocarbol, and arylaminocarbonyl; mercapto, alkylthio, arylthio, thiocarbo Functional groups containing sulfur atoms, such as thiol; functional groups containing key atoms such as silyl, alkylsilyl, arylsilyl, etc .; functional groups containing oxygen and key atoms such as alkoxysilyl, aryloxysilyl, etc. And the like.
- the hydrocarbon group represented by I ⁇ to R 4 may be any one having from 1 to 20 carbon atoms is not particularly limited. It may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a saturated group, or an unsaturated group. Furthermore, the aliphatic hydrocarbon group may be linear, branched or cyclic.
- hydrocarbon group represents a part of carbon which may have the above functional group.
- It may be substituted with a ⁇ 16 group hetero atom or a key atom.
- the ring formed by the bonding I ⁇ to R 4 are each other, be saturated be unsaturated, also provides a condensed ring may be a single ring It doesn't matter.
- the norbornene compound addition polymer used in the present invention can be obtained by addition polymerization of a norbornene compound represented by the general formula (2).
- the norbornene compound includes bicyclo [2. 2. 1] hept-2-enes in which m is 0 in the general formula (2) and tetracyclo [6. 2. 1. I 3 'in which m is 1. 6.0 2 '7] de de force one 4-E emission are preferred.
- bicyclo [2.2.1] hept-2-enes used in the synthesis of the norbornene compound addition polymer used in the present invention are not particularly limited, but specific examples thereof are as follows. Can be mentioned.
- Heptou 2 enes
- Alkoxycarbon groups such as methyl 5 norbornene 2 carboxylate, ethyl 5 norbornene 2 carboxylate, 2-methyl-5 norbornene 2—methyl methyl sulfonate, 2-methyl-5 norbornene 2—ethyl ethyl sulfonate Bicyclo [2.2.1] hept-2-enes having
- Bicyclone having a hydrocarbol group such as 5 norbornene-2 carbaldehyde [2.
- Bisque mouths having functional groups containing nitrogen atoms such as 5 norbornene-2 carbo-tolyl, 5 norbornene 2 carboxamide, 5-norbornene-2, 3 dicarboxylic imide [2.2.1] hept-2-enes;
- tetracyclo used for the synthesis of norbornene I ⁇ product addition polymer used in the present invention [6 2. 1. I 3 '6 0 2.' 7.] De de force - 4 E emissions such is particularly limited Specific examples thereof include the following.
- Tetracyclo [6.2.1. I 3 ' 6 .0 2 ' 7 ] Dede 1 9-4-carboxylic acid, tetracyclo [6.2.1. I 3 ' 6 .0 2 ' 7 ] Dede 9 tetracyclo having group or acid anhydride group - E down one 4, 5-dicarboxylic acid, tetracyclo [. 6.2.1 I 3,6 .0 2 ' 7] Dodeka 9 En 4, 5-hydroxy such as dicarboxylic acid anhydride-carbonitrile [6.2.1. I 3 ' 6 .0 2 ' 7 ] Dode force—4 hens; Tetracyclo [6.2.1.
- These norbornene compound addition polymers may be homopolymers or copolymers of two or more types of monomers.
- it may be a copolymer with cyclic olefin and other monomers other than norbornene compound.
- Examples of the cyclic olefin capable of copolymerization with the norbornene compound include monocyclic (di) olefins such as cyclobutene, cyclopentene, cyclohexene, cyclootaten, and 1,5 cyclooctagen.
- ⁇ -olefins such as ethylene, propylene, 1-butene, 1-hexene, and 1-octene
- styrene ⁇ -methylolene styrene
- ⁇ -methylstyrene ⁇ -methylstyrene
- ⁇ —Aromatic butyl compounds such as methoxystyrene
- Conjugates such as butadiene and isoprene
- (meta) attalate means attalate and Z or metatarate.
- the norbornene compound-added polymer used in the norbornene compound-added polymer film of the present invention is a bicyclo [2.2.1] hepto having an unsubstituted or hydrocarbon substituent from the viewpoint of dimensional stability and solubility.
- 2-E down such, or tetracyclo having an unsubstituted or hydrocarbon substituent [6. 2. 1. I 3 '6 0 2.' 7] de de force - 4 structure units of from E down such that all Those that occupy 70% or more of the repeating structural units are preferred and those that occupy 80% or more Those that occupy more than 85% are more preferable, and those that occupy more than 95% are particularly preferable.
- the hydrocarbon substituent is preferably one having 1 to 3 carbon atoms.
- the norbornene compound-added polymer used in the norbornene compound-added polymer film of the present invention particularly preferably comprises only the structural unit represented by the general formula (1).
- the norbornene compound addition polymer composed only of the structural unit represented by the general formula (1) has high heat resistance, preferably 200 ° C or higher, more preferably 220 ° C or higher, and particularly preferably 240 ° C. It has the above glass transition temperature (Tg).
- the glass transition temperature is lower than 200 ° C, heat resistance may be insufficient when used for some optical components and electrical insulation components.
- the upper limit of the glass transition temperature is not particularly limited, but if it is higher than 400 ° C, the polymer may be decomposed, and it may be difficult to measure Tg.
- the molecular weight of the norbornene compound-added polymer used in the norbornene compound-added polymer film of the present invention is such that the number average molecular weight (Mn) in terms of polystyrene is 10,000 to 500,000. It is more preferable that it is ⁇ 450,000 than force S, and it is particularly preferable that it is 50,000 to 400,000. If the number average molecular weight is too small, the mechanical properties may be low and it may be difficult to form a film. If it is too large, the solution viscosity may be too high to make the production difficult.
- the method for producing the norbornene compound addition polymer used in the present invention is not particularly limited.
- the polymerization catalyst is not particularly limited as long as it is a catalyst for addition polymerization of a norbornene compound.
- 11-505880 publication, WO00Z20472 pamphlet, Japanese Unexamined Patent Publication No. 20 01-98035 publication, a polymerization comprising a combination of a group 10 transition metal catalyst such as nickel or palladium and a promoter such as an aluminum compound or boron compound A catalyst can be mentioned.
- a norbornene compound-added polymer polymerized using a polymerization catalyst having a palladium atom is preferable because it has excellent mechanical properties.
- the norbornene compound addition polymer used in the present invention has an olefinic unsaturated bond in the norbornene compound addition polymer obtained by the above-described method.
- the bond may be hydrogenated.
- the hydrogenation reaction is carried out by a generally known method, that is, a method in which a norbornene compound addition polymer is brought into contact with hydrogen in the presence of a hydrogenation catalyst.
- hydrogenation catalysts include Group 8-10 transition metals such as nickel, rhodium, platinum, cobalt, ruthenium, rhodium or their compounds on porous carriers such as carbon, alumina, silica, silica alumina, and diatomaceous earth.
- a homogeneous catalyst such as a complex of
- the polymer after the polymerization or after the hydrogenation reaction contains a transition metal or a halogen atom as a residue of the polymerization catalyst, the hydrogenation catalyst and their co-catalyst. , Aluminum atoms, io atoms and the like.
- catalyst residues may remain in the norbornene compound-added polymer film for use in the norbornene compound addition polymer film of the present invention.
- a total mass force S of transition metal atoms, phosphorus atoms, aluminum atoms, ion atoms and halogen atoms contained in the polymer and is preferably 50 ppm or less by weight with respect to the polymer. It is more preferable that it is 30 ppm or less.
- the amount of transition metal atoms, phosphorus atoms and aluminum atoms contained in the polymer can be determined by atomic absorption spectrometry (ICP-AES).
- the amounts of xio atoms and halogen atoms can be determined using column chromatography using a sulfate ion or halogen ion aqueous solution after burning the polymer.
- the polymer is selected from at least one selected from the group consisting of clay, clay mineral and ion-exchangeable layered inorganic compound.
- a method of contacting with two inorganic compounds is preferred.
- Clay is usually composed mainly of clay minerals. Most clay minerals are ion-exchangeable layered inorganic compounds.
- the ion-exchangeable layered inorganic compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with a weak bond force, and the ions contained therein are exchangeable.
- clays, clay minerals and ion-exchangeable layered inorganic compounds Is not limited to natural products, and artificially synthesized products can also be suitably used.
- Examples thereof include an ion-binding compound having a structure
- the norbornene compound-added polymer film of the present invention has (1) dimensional change rate between before and after heating when it is heated from 25 ° C to 200 ° C and then cooled again to 25 ° C. Satisfy at least either SlOOppm or less (2) The rate of dimensional change between before and after immersion in propylene glycol monomethyl ether acetate for 1 hour at 25 ° C is less than lOOppm To do.
- dimensional change rates are preferably 80 ppm or less, more preferably 70 ppm or less.
- the dimensional change rate is a temperature at 25 ° C. before heating the film to 200 ° C.
- the distance between any two points on the film (referred to as Y) and the distance between the two points when heated to 200 ° C and then cooled back to 25 ° C (referred to as Y 1 )
- the force that is a value obtained from IY ° —Y 1 I ⁇ °, specifically, a value obtained in the same manner as in the examples described later.
- I ⁇ ° - ⁇ 2 I is a value obtained from I ⁇ , specifically, a value obtained in the same manner as in the examples described later.
- the norbornene compound addition polymer film of the present invention is excellent in heat resistance, even if it is heated to 200 ° C. or more and the glass transition temperature or less, the dimensional change rate is lOOppm or less. Whether the film is heated in an air atmosphere, an inert gas such as a nitrogen atmosphere, or under reduced pressure, the above-mentioned good low dimensional change rate is exhibited.
- the copolymer film with norbornene compound of the present invention preferably has a dimensional change rate of lOOppm or less before and after being immersed in water at 25 ° C for 1 hour.
- This dimensional change rate is more preferably 80 ppm or less, particularly preferably 70 ppm or less.
- the dimensional change rate is obtained by the method described in the examples.
- the norbornene compound addition polymer film of the present invention preferably has a solvent content of 1, OOOppm or less, more preferably 500 ppm or less.
- the thickness of the norbornene compound addition polymer film of the present invention is usually 1 to 1,000 m, preferably 2 to 500 ⁇ m. If it is less than 1 ⁇ m, the strength of the film is weak and it takes time to evaporate and remove the casting solvent in order to prepare a film of 1,000 m or more as soon as defects occur.
- film and sheet are distinguished by their thickness, but in the present invention, “film” is a concept including both “film” and “sheet”. It is.
- the norbornene compound-added polymer film of the present invention is a film having a residual solvent amount of not more than 5, OOOppm in the preparation process of the norbornene compound-added polymer film, either at (T-150) ° C or 180 ° C. It can be obtained by maintaining the temperature within a range from high temperature to T ° C (where T is the glass transition temperature of the norbornene compound addition polymer).
- a norbornene compound-attached polymer polymer cast film having a residual solvent amount of 5, OOOppm or less is (T 150) ° C or 180 ° C! Heat treatment at a temperature within the range of temperature to T ° C.
- the norbornene compound addition polymer film is directly prepared from the norbornene compound addition polymer without going through the cast film form! Give the film a (T 150) ° C or 180 ° C !, high or low, temperature history in the temperature to T ° C range.
- a cast film is obtained by a cast molding method.
- the cast molding method uses a solution obtained by dissolving or dispersing a norbornene compound addition polymer in an organic solvent (cast solution) using a die coater, metal drum, steel belt, polyethylene terephthalate (PET). And polyethylene naphthalate (PEN)
- the film is coated on a support such as a tellurium film or a polytetrafluoroethylene belt, then the solvent is removed, the polymer is dried, and the film is peeled off from the support.
- the solution can be applied to the support by spraying, brushing, roll spin coating, dating, etc., and then the solvent is dried to peel the film from the support.
- the thickness, surface smoothness, etc. can be controlled by repeatedly applying.
- the solvent used for cast molding may be any solvent as long as it dissolves or disperses the norbornene compound addition polymer.
- aliphatic hydrocarbon solvents such as pentane, hexane and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethyl cyclohexane, decahydronaphthalene, bicycloheptane, tri Cyclodecane, hexahydride Alicyclic hydrocarbon solvents such as indene and cyclooctane; Aromatic hydrocarbon solvents such as benzene, toluene and xylene; Halogen-containing aliphatic carbonization such as dichloromethane, chloroform, 1,2-dichloroethane Hydrogen solvents; halogen-containing aromatic hydrocarbon solvents such as black benzene and dichlorobenzene; nitrogen-containing solvents such as nitromethane, nitrobenzene, and acetonitrile; aliphatic or alicyclic ether solvents such as pent
- aromatic hydrocarbon solvents aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, ether solvents and halogen-containing hydrocarbon solvents are preferred.
- solvents such as cellosolve solvents such as methyl cellosolve, ethinoreserosonoleb, and 1-methoxy-2-propanol; diacetone alcohol, acetone, cyclohexanone, methyl ethyl ketone, 4-methyl-2- Examples thereof include ketone solvents such as pentanone; ester solvents such as methyl lactate and ethyl lactate; 1 alcohol solvents such as pentanol and 1-butanol.
- cellosolve solvents such as methyl cellosolve, ethinoreserosonoleb, and 1-methoxy-2-propanol
- polymer concentration ⁇ at the time of norbornene compound addition polymer is dissolved or dispersed in a solvent or, from 0.1 to 50 weight 0/0 force S Preferably, preferably from 0.2 to 45 weight 0/0 power S , 0.5 to 40 weight 0/0 are particularly preferred U,.
- the polymer concentration is less than the above lower limit, it becomes difficult to ensure the thickness of the film, and the surface smoothness of the film is obtained by foaming due to solvent evaporation, etc. The problem of becoming may arise.
- concentration exceeds the above upper limit the solution viscosity becomes too high, and the thickness and surface of the resulting film are difficult to become uniform.
- the viscosity of the above solution at room temperature is usually 1 to 1,000,000 mPa-s, preferably 10 to 100,000 mPa-s, more preferably 100 to 50,000 mPa-s, particularly preferably 1,000. ⁇ 40,000mPa, s.
- the film is usually formed at room temperature.
- the polymer solution is formed. It may be preheated.
- the temperature to be heated is a force depending on the boiling point of the solvent used. C, preferably 40. C ⁇ 200. C.
- a cast film of a norbornene compound-attached caropolymer having a residual solvent amount of 5, OOOppm or less (T — 150) ° C or 180 ° C !, high or low! Heat treatment at a temperature in the range from the temperature to just the temperature, but during the film preparation process, the residual solvent in the film state
- the amount is more than 5, OOOppm, it is preferable that there is no thermal history within the above temperature range.
- the drying step in the cast molding method is not particularly limited and can be carried out by a generally used method, for example, a method of passing through a drying furnace through a large number of rollers, but the evaporation of the solvent in the drying step.
- a generally used method for example, a method of passing through a drying furnace through a large number of rollers, but the evaporation of the solvent in the drying step.
- air bubbles are generated, the film characteristics are remarkably deteriorated. Therefore, in order to avoid this, it is preferable to make the drying process into two or more steps, and to control the temperature or the air volume appropriately in each step. .
- the amount of residual solvent in the cast film obtained by the above cast molding method (hereinafter simply referred to as “cast film”! /, Which has a wrinkling power) is 5, OOOppm or less, preferably 4, OOOppm or less. More preferably, it is 3, OOOppm or less, particularly preferably 2, OOOppm or less.
- the amount of residual solvent in the cast film exceeds the above upper limit, the dimensional change rate of the norbornene compound addition polymer film of the present invention obtained by heat-treating it in a predetermined temperature range increases.
- the residual solvent lowers the glass transition temperature of the norbornene compound addition polymer, lowers the heat resistance, deteriorates in the heat treatment step, and tends to be colored.
- the method for setting the amount of residual solvent in cast film to 5, OOOppm or less is not particularly limited. However, specific methods include vacuum drying and drying under an air stream such as air or nitrogen.
- the obtained norbornene compound addition polymer film (cast film) is obtained at (T 150) ° C or 180 ° C !, deviation high !, at a temperature within the range of temperature to T ° C.
- Heat treatment is preferably (T—120) ° C or 180 ° C !, or slightly higher !, preferably within the range of temperature to T ° C (T-100) ° C or 180 ° C. It is more preferable that the higher temperature force is within the range of T ° C.
- the heat treatment time is set in the range of 1 second to 100 hours, preferably in the range of 1 minute to 10 hours, depending on the film production conditions and thickness.
- the heating atmosphere may be an air atmosphere, an inert gas such as a nitrogen atmosphere, or a reduced pressure! /, But an inert gas atmosphere or a reduced pressure is preferred.
- the direct film forming method may be, for example, an extrusion molding method or a press molding method.
- a plasticizer in combination. Since the film contains a plasticizer, the residual solvent can be easily removed, and the residual solvent in the film can be easily reduced to 5,000 Oppm or less even in a short time and at a relatively low temperature.
- the plasticizer refers to an organic compound having a boiling point exceeding 200 ° C., preferably liquid at normal temperature
- the solvent refers to an organic compound having a boiling point of 200 ° C. or less, preferably liquid at normal temperature.
- the method of using the plasticizer in combination can be suitably employed in the “cast molding method” because the plasticizer is easily dispersed uniformly in the film.
- a plasticizer is added and dissolved in a solution (cast solution) in which a norbornene compound addition polymer is dissolved or dispersed in an organic solvent.
- a solution cast solution
- the solvent is removed, the polymer is dried, and the film is peeled off from the support to obtain a cast film in which the plasticizer is uniformly dispersed.
- the residual solvent in it can be easily removed compared to the case where it does not contain a plasticizer.
- a plasticizer may be added from an inlet of a raw material (such as a norbornene compound addition polymer) of an extruder.
- the amount of the plasticizer used is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, particularly preferably 2 to L0 with respect to 100 parts by weight of the norbornene compound addition polymer. Parts by weight. If the amount of the plasticizer is too small, removal of the residual solvent may not be easy, and if the amount of the plasticizer is too large, bleeding may occur.
- plasticizer examples include dibutyl malonate, diisopropyl malonate, dimethyl adipate, dibutyl adipate, diisopropyl adipate, diisobutyl adipate, bis (2-ethylhexyl) adipate, diisonol adipate, dioctyl adipate, diisodecyl adipate, Bis (butyldiglycol) adipate, bis (2-ethylhexyl) azelate, dimethyl sebacate, dibutyl sebacate, bis (2-ethylhexyl) sebacate, dioctyl sebacate, jetyl succinate, diisopropyl Aliphatic dibasic acid ester plasticizers such as succinate and dibutyl succinate; dimethyl phthalate, jetyl phthalate, diisopropyl phthalate, dibutino phthalate, bis (2-e
- aliphatic dibasic acid ester plasticizers and phthalic acid ester plasticizers are preferred because of their compatibility with norbornene compound addition polymers! If the compatibility with the norbornene compound addition polymer is low, the light transmittance of the film and the haze increase may occur, and the optical properties may deteriorate.
- the norbornene compound addition polymer film of the present invention thus obtained has an excellent total light transmittance with a solvent content of preferably 1, OOOppm or less, and particularly preferably 500ppm or less. Excellent mechanical strength and small dimensional change rate.
- the norbornene compound-added polymer film of the present invention has a small rate of dimensional change is that it is close to the glass transition temperature of the polymer, and the film is prepared at the above high temperature. It is presumed that the residual stress is relaxed without causing deterioration.
- the norbornene compound addition polymer film of the present invention preferably contains an antioxidant.
- the use of antioxidants can improve the stability at high temperatures.
- the antioxidants are not particularly limited, but are phenolic antioxidants, ratatonic antioxidants and phosphoric acids. It is preferable to use at least one selected group force that also has anti-wrinkle agent power. It is more preferable to use two or more of these in combination in order to enhance the anti-acid wrinkle-preventing effect.
- phenolic antioxidants include 2, 6-di-tert-butyl-4-methylphenol, 4, 4, -thiobis (6-tri-butyl-3-methylphenol), 1, 1, -bis (4 — Hydroxyphenyl) cyclohexane, 2,2,1-methylenebis (4 ethyl 6-t butylphenol), pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Octadecyl 3— (3,5-Di-tert-butyl 4-hydroxyphenol) propionate 3, 3 ', 3 ", 5, 5', 5" —Hexar t-Butyl a, a ', a,- (Mesitylene-2,4,6 triyl) tri-p-cresol, 1,3,5 tris (3,5 di-tert-butyl 4-hydroxybenzyl) 1,3,5 triazine 1,2,4,6 (1H, 3
- phosphorus antioxidants include tris (4-methoxy-1,3,5 diphenyl) phosphite, tris (noulefel) phosphite, tris (2,4 di-t-butylphenol). Phosphite, tris [2— [[2, 4, 8, 10-tetra-tert-butyldibenzo [d, f] [l, 3, 2] dioxaphosphephine 1-yl] oxy] ethyl] amine, etc. Can be mentioned.
- Specific examples of the rataton-based antioxidation agent include a reaction product of 3-hydroxy-5,7-di-butyl-furan-2-one and o-xylene.
- the addition amount of these anti-oxidation agents is not particularly limited, but is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, based on the caropolymer with a norbornene compound.
- heat-resistant cage stabilizers examples include hydroxylamine-based heat-resistant cage stabilizers; Zio-type heat-resistant such as didodecyl 3, 3, monothiodipropionate, dioctadecyl 3, 3, monothiodipropionate, etc. Processing stabilizers; and the like.
- UV absorbers examples include benzotriazole UV absorbers, triazine UV absorbers, and benzophenone UV absorbers.
- light stabilizers examples include benzoate light stabilizers, hindered amine light stabilizers, and the like.
- additives examples include inorganic fillers, organic fillers, processing stabilizers, antistatic agents, near infrared absorbers, colorants such as dyes and pigments, phosphors, lubricants, flame retardants, and crosslinking agents. I can get lost.
- the method for adding the acid inhibitor and other additives to the norbornene compound addition polymer film is such that the acid inhibitor and other additives can be uniformly dissolved or dispersed in the film of the present invention. Any method may be used. A method of preparing a cast film after dissolving or dispersing an acid / antioxidant and other additives in a casting solution of a norbornene compound addition polymer is simple and preferred.
- the norbornene compound addition polymer film of the present invention has a total light transmittance of 70% or more, preferably 80% or more, more preferably 85% or more. Therefore, the optical material and the display element are used. It can be suitably used as a member for use.
- the norbornene compound addition polymer film may be a composite film with a woven fabric or a non-woven fabric. This composite film is obtained by impregnating a woven or non-woven fabric such as glass cloth with a solution of a norbornene compound addition polymer, followed by drying, and then at a temperature of (T-150) ° C or 180 ° C.
- the norbornene compound addition polymer film may be obtained by blending with other thermoplastic resin.
- a film of such a blend can be obtained by mixing other thermoplastic resin in the cast solution and then by a casting method or a melt extrusion method using a melt extruder or the like. Then, heat treatment is performed at a temperature within the range from (T-150) ° C or 180 ° C, whichever is higher to T ° C.
- the norbornene compound addition polymer film of the present invention may be a laminate of transparent conductive films (hereinafter sometimes referred to as “transparent conductive film laminate film”).
- the transparent conductive film layer As a material for forming the transparent conductive film layer (transparent conductive film), metals such as Sn, In, Ti, Pb, Au, Pt, Ag, or oxides thereof such as indium oxide Tin (ITO), aluminum oxide, silicon oxide, titanium oxide, zinc oxide, tungsten oxide, aluminum nitride, silicon nitride, titanium nitride, sodium cadmium sulfate, zinc sulfide, zinc selenide, etc. Generally used. These single metal films can be formed on a substrate, and the single metal film can be oxidized as necessary to form a transparent conductive film layer.
- ITO indium oxide Tin
- a metal oxide layer is deposited from the beginning of the film formation, but at the beginning of the film formation, the film is formed in the form of a simple metal or a lower oxide, and then heat oxidation, anodization, or liquid phase oxidation. It can also be made transparent by subjecting it to oxidation treatment.
- These transparent conductive film layers may be formed by adhering a sheet, film or the like having another transparent conductive film layer to a norbornene compound addition polymer film, or a plasma polymerization method or a sputtering method. , Vacuum deposition, plating, ion plating, spraying, electrolytic deposition It may be formed directly on the norbornene compound addition polymer film by, for example.
- the thickness of these transparent conductive film layers is appropriately determined depending on desired characteristics and is not particularly limited, but is usually 10 to: LO, 000 angstrom, preferably 50 to 5,000 angstrom. is there.
- an adhesive layer and an anchor coat layer may be formed.
- the adhesive layer can be formed using a heat-resistant resin such as epoxy resin, polyimide, polybutadiene, phenol resin, or polyetheretherketone.
- the anchor coat layer is cured by a known curing method such as UV curing or heat curing using an anchor coating agent containing an acrylic prepolymer such as epoxy ditalylate, urethane ditalylate or polyester ditalylate. Can be formed.
- adhesion is performed between the norbornene compound addition polymer film and the transparent conductive film for the purpose of improving the smoothness of the film and the adhesion to the transparent conductive film.
- a layer may be provided.
- the adhesive layer can be obtained by applying a varnish varnish and removing the solvent by drying. At this time, a resin having film-forming properties after removal of the solvent, that is, a varnish to which a solid resin is added is preferable from the viewpoint of uniform coating.
- the resin used for this purpose include photocurable resins such as epoxy ditalylate, urethane diatalylate, polyester diatalylate, and the like; o Cresolol novolac type, bisphenol type Examples include epoxy-based, urethane-based, acrylic-based, urea-based, melamine-based and unsaturated polyester-based thermosetting resins; electron beam-curable resins. Of these, photocurable resin is preferable in terms of productivity and cost.
- any method for forming the cured resin coating any method having a gravure coating method, a reverse roll coating method, a kiss roll coating method, or the like may be used.
- the transparent conductive film laminated film of the present invention may have a gas noble layer on the side opposite to the transparent conductive film.
- the gas noble layer may be formed of an inorganic material or an organic material.
- the inorganic material that can be used include silicon oxide, aluminum oxide, indium oxide, and the like
- examples of the organic material that can be used include polybutyl alcohol, ethylene butyl alcohol copolymer, and polymer. Examples include lyamide and the like.
- the film thickness of the gas layer is 100-2, OOOA for inorganic materials and 500 for organic materials.
- inorganic materials can be formed by known means such as sputtering, ion plating, resistance heating, and CDV.
- a film 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 noble layer.
- a protective coat layer may be laminated on the gas barrier layer to protect it.
- the protective coating layer is preferably formed by the same method as the adhesive layer.
- the norbornene compound addition polymer film of the present invention is used for a color filter substrate, such as a light guide plate, a protective film, a polarizing film, a retardation film, a touch panel, a transparent electrode substrate, an optical recording substrate such as a CD, MD, and 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, or an optical element sealing material.
- 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.
- a color filter can be obtained by laminating one color filter layer on the norbornene compound addition polymer film of the present invention or the color filter substrate having the transparent conductive film laminate film force of the present invention.
- a lamination method a known pigment dispersion method, dyeing method, electrodeposition method, printing method, transfer method, or the like can be used.
- a sputtering method or vacuum deposition method is used to form a metallic light shielding film such as metallic chromium, acid chromium, chromium nitride, or a nickel Z tungsten alloy on a color filter substrate.
- a photosensitive resin composition (color resist) in which a black matrix is formed and then a red pigment is dispersed is applied by spin coating, wire It is applied to the entire surface by the bar method, flow coating method, die coating method, roll coating method, spray coating method, etc., exposed through a mask, developed after exposure, and red pixels are formed. In the same way, blue, green pixels are coated, exposed and developed to form three color pixels.
- the order in which the three color pixels are formed is arbitrarily selected. If the black matrix between pixels is concave, the surface is covered with a transparent resin such as epoxy resin or acrylic resin to form a protective film for smoothing. Also good. 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.
- Constituent components of the color resist and black resist compositions and methods of coating, exposure and imaging are described in, for example, JP-A-2004-56151, JP-A-2004-347831, and the like. Ingredients and methods can be used.
- the printing method a known method can be used. 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! / I can.
- the norbornene compound addition polymer film of the present invention has high resistance to chemicals such as resist, ink, developer, etc., the substrate may be deformed or cracks may be generated in one color filter lamination process. There is nothing to do.
- the film thickness is usually in the range of 0.01 to 10 / ⁇ ⁇ , preferably 0.05 to 5 m.
- the above-described color filter can be used as a color filter for 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.
- the optical component of the present invention preferably has a light transmittance of 80% or more, preferably 85% or more, and a linear expansion coefficient of 50ppmZ ° C or less, on the norbornene compound-added polymer film of the present invention.
- it may be a laminate of 40ppmZ ° C or less transparent substrate! / ⁇ .
- Any transparent substrate may be used as long as it has a light transmittance of 80% or more and a linear expansion coefficient of 50 ppmZ ° C or less.
- Specific examples thereof include glass substrates such as optical white glass, soda glass and thin film glass; resin substrates such as polyethylene terephthalate, polyethylene naphthalate and polyimide; Among these, glass substrates such as optical white glass and thin film glass are particularly preferable.
- both surfaces may be subjected to corona discharge treatment, ozone treatment or plasma treatment as necessary.
- a thin film of various resins such as a silane coupling agent and urethane-based resin may be formed.
- the film thickness is usually in the range of 0.01 to 10 m, preferably 0.05 to 5 ⁇ m.
- an adhesive layer may be provided between the two. Adhesion is achieved by applying a varnish varnish and removing the solvent by drying.
- a resin having film-forming properties after removing the solvent that is, a varnish to which solid resin is added is preferable from the viewpoint of uniform application.
- Such a resin include photo-curable resins such as epoxy dipolymers such as epoxy ditalylate, urethane ditalylate, and polyester ditalylate; o-cresol novolac type, bisphenol type Epoxy-based, urethane-based, acrylic-based, urea-based, melamine-based, unsaturated polyester-based thermosetting resins; electron beam curable resins; cyclic olefin fin resins or modified products thereof; cyclized polyisoprene resins Fat or a modified product thereof, and the like.
- photo-curable resins such as epoxy dipolymers such as epoxy ditalylate, urethane ditalylate, and polyester ditalylate
- o-cresol novolac type bisphenol type Epoxy-based, urethane-based, acrylic-based, urea-based, melamine-based, unsaturated polyester-based thermosetting resins
- electron beam curable resins cyclic olefin fin resin
- Examples of the method for forming the rosin thin film include a gravure coating method, a reverse roll coating method, and a kiss roll coating method, and any method may be used.
- the norbornene compound addition polymer film of the present invention can be used not only for optical parts but also for electrical insulation parts, electrical / electronic parts, electronic parts sealants, medical equipment, and packaging materials. it can. [Electrical insulation parts]
- the norbornene compound-added polymer film of the present invention is excellent in heat resistance and electrical characteristics, and has a small dimensional change even when subjected to high-temperature treatment or chemical treatment, and is therefore optimal as an electrical insulation component.
- Examples of electrical insulation parts include power cables and cable coating materials, insulation materials for office automation equipment such as computers, printers, and copiers, and insulation parts for flexible printed circuit boards. Particularly suitable for use as flexible printed circuit boards. It is done.
- Example 1 As medical equipment, it is used for chemical containers, infusion bags, sample containers, sterilization containers, tubes, etc.
- test and evaluation in an Example and a comparative example were performed with the following method.
- DMS6100 manufactured by Seiko Instruments Inc.
- the measurement frequency was 10 Hz
- the heating rate was 5 ° CZ
- the excitation mode was a single waveform
- the excitation amplitude was 5.
- the amount of residual solvent in the film before heat treatment is determined by gas chromatography after dissolving the non-heat treated film with a solvent other than the solvent used for the preparation of the film before heat treatment.
- the norbornene compound addition polymer film is dissolved in a solvent other than the solvent used for the preparation of the norbornene compound addition polymer film, and then quantified using gas chromatography.
- a plurality of markers are attached on a film having a thickness of 100 m and a length and width of 100 mm, immersed in propylene glycol monomethyl ether acetate (PGMEA) at 25 ° C for 1 hour, and then vacuum-dried at 100 ° C for 1 hour. The PGMEA adhering to the film was removed. Average the distance between each marker at 25 ° C before and after immersion in PGME A to obtain the dimensional change rate.
- PGMEA propylene glycol monomethyl ether acetate
- a plurality of markers are placed on a polymer film with a norbornene compound with a thickness of 100 m and length and width of 100 mm, immersed in water at 25 ° C for 1 hour, and then vacuum-dried at 100 ° C for 1 hour. Then, water adhering to the norbornene compound addition polymer film was removed. Average the difference in distance between each marker at 25 ° C before and after immersion in water to obtain the dimensional change rate.
- a nitrogen-substituted glass reactor was charged with 0.77 parts of (aryl) palladium (tricyclohexylphosphine) chloride and 14 parts of lithium tetrakis (pentafluorophenyl) borate, followed by 2 parts of toluene. was added to prepare a catalyst solution.
- 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 polymer (a) 2, 462 parts were obtained.
- the number average molecular weight (hereinafter sometimes abbreviated as “Mn”) of the polymer (a) is 140,000, and the weight average molecular weight (hereinafter sometimes abbreviated as “Mw”) is 502,000.
- the NB unit ZEtNB unit composition ratio in the polymer (a) is 71Z29 (mol Z mol), and the glass transition temperature (Tg) is 281. . Met.
- the polymer) was 117,000, Mw was 377,000, the composition ratio of NB unit ZDM NB unit in the polymer (b) was 52/48 (mol / mol), and Tg was 301 ° C.
- Polymer (c) had Mn of 105,000, Mw of 278,000, NB unit ZTCD MC unit composition in polymer (c) was 85/15 (mol / mol), and Tg was 335 ° C. It was.
- a 10% toluene solution of polymer (a) was prepared, and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) propionate as an antioxidant was 0.5% based on polymer (a).
- the reaction product was dissolved by adding 0.3% to the polymer (a).
- This solution (a) was cast on a flat polytetrafluoroethylene sheet, and the toluene was removed by evaporation in an air stream at room temperature for 24 hours, then at 80 ° C for 24 hours and at 150 ° C. It was vacuum-dried for 24 hours to obtain a cast film (A) having a residual solvent amount of less than 500 ppm and a film thickness of 100 ⁇ m.
- cast films (B) and (C) having a film thickness of 100 m were obtained from the polymers (b) and (c), respectively.
- Table 1 shows the amount of residual solvent in the obtained cast films (A) to (C).
- the cast films (A) and (B) were heat-treated at 250 ° C for 1 hour in a nitrogen atmosphere, and the cast film (C) was heat-treated at 280 ° C for 1 hour in a nitrogen atmosphere. In each case, a norbornene compound polymer film was obtained.
- This solution is cast on a flat polytetrafluoroethylene sheet, and after evaporating and removing toluene under an air stream at room temperature for 24 hours, it is vacuumed at 80 ° C for 1 hour and 150 ° C for 1 hour. Dried to obtain a cast film (D) with a residual solvent content of less than 500 ppm and a film thickness of 100 ⁇ m Next, the cast film (D) was heat-treated in the same manner as in Example 1 to obtain a norbornene compound polymer film. Table 1 shows the results of measurements similar to those of Example 1 for this film.
- the cast film (C) was heat-treated at 160 ° C for 1 hour in a nitrogen atmosphere.
- the dimensional change rate, the amount of solvent contained, and the total light transmittance of this film were measured.
- the measurement results are summarized in Table 1.
- a 10% toluene solution of polymer (a) was prepared, and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) propionate as an antioxidant was 0.5% based on polymer (a).
- the reaction product was dissolved by adding 0.3% to the polymer (a).
- Example 1 Example 2 Example 3 Example 4 Polymer composition (mol%) (* 1) (a) (b) (c) (a)
- T-glass transition temperature (° c) 281 301 335 260 Residual solvent (ppm) ⁇ 500 to 500 to 500 ⁇ 500 Heat treatment Yes Yes Yes Yes Yes Yes
- T Glass transition temperature (° C) 281 301 335 260
- T1 Heat treatment temperature (° C) 250 250 280 250
- T2 (T—150) and 180 0 C
- EtNB 5—Ethylbicyclo [2. 2. 1.] Heptou 2—Yen
- TCDMC tetracyclo [6. 2. 1. I 3 '. 6 0 2' 7] de de force one 9-E down one 4-carboxylate
- the rate is also large (Comparative Example 4). If the amount of residual solvent in the cast film before heat treatment exceeds the range specified in the present invention, even if it is heat-treated in the above temperature range specified in the present invention, it is still before and after heating at 200 ° C. It can be seen that the dimensional change rate before and after immersion in PGMEA is large, and in this case, the total light transmittance is reduced (Comparative Example 5). On the other hand, in the preparation process, the residual solvent amount is less than 5, OOOppm. A cast film is heated at a temperature within the range of (T—150) ° C or 180 ° C, whichever is higher, to T ° C (where T is the glass transition temperature of the norbornene compound addition polymer). It can be seen that after the process of maintaining, the dimensional change rate before and after 200 ° C heating, before and after PGMEA immersion, and before and after water immersion is small and the total light transmittance is high (Examples 1 to 4).
- the residual solvent can be reduced to 5, OOOppm or less in a short time compared to the case without a plasticizer (Examples 1 to 3). I can speak as much as I can.
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Abstract
Description
Claims
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JP2008512029A JPWO2007122932A1 (ja) | 2006-03-23 | 2007-03-19 | ノルボルネン化合物付加重合体フィルム、その製造方法及びその用途 |
EP07738908A EP1997848A4 (en) | 2006-03-23 | 2007-03-19 | POLYMER FILM WITH ADDITION OF NORBORNENE COMPOUND, PROCESS FOR PRODUCTION THEREOF AND USE THEREOF |
US12/225,408 US20090297870A1 (en) | 2006-03-23 | 2007-03-19 | Norbornene Compound Addition Polymer Film, Process for Production Thereof, and Use Thereof |
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- 2007-03-16 TW TW096109069A patent/TW200738765A/zh unknown
- 2007-03-19 EP EP07738908A patent/EP1997848A4/en not_active Withdrawn
- 2007-03-19 KR KR1020087025775A patent/KR20080114810A/ko not_active Application Discontinuation
- 2007-03-19 WO PCT/JP2007/055463 patent/WO2007122932A1/ja active Application Filing
- 2007-03-19 JP JP2008512029A patent/JPWO2007122932A1/ja not_active Withdrawn
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JP2015063087A (ja) * | 2013-09-25 | 2015-04-09 | 日本ゼオン株式会社 | 積層フィルム及び製造方法 |
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WO2016067893A1 (ja) * | 2014-10-28 | 2016-05-06 | 日本ゼオン株式会社 | 樹脂フィルム、バリアフィルム及び導電性フィルム、並びに、これらの製造方法 |
WO2016129145A1 (ja) * | 2015-02-10 | 2016-08-18 | コニカミノルタ株式会社 | 導電性フィルム、タッチパネル、および導電性フィルムの製造方法 |
JP2017042989A (ja) * | 2015-08-26 | 2017-03-02 | 日東電工株式会社 | 光学積層体 |
JP2017088715A (ja) * | 2015-11-09 | 2017-05-25 | コニカミノルタ株式会社 | 光学フィルム |
Also Published As
Publication number | Publication date |
---|---|
KR20080114810A (ko) | 2008-12-31 |
JPWO2007122932A1 (ja) | 2009-09-03 |
US20090297870A1 (en) | 2009-12-03 |
EP1997848A4 (en) | 2010-09-15 |
EP1997848A1 (en) | 2008-12-03 |
TW200738765A (en) | 2007-10-16 |
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