JP2006348115A - Saturated norbornene resin film and its manufacturing process, polarizing plate, optical compensation film, antireflection film, and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a saturated norbornene resin film which has an excellent surface improved in vertical streaks and lateral streaks often caused by a melt film fabrication process. <P>SOLUTION: Melt film fabrication is made to a saturated norbornene resin to which 0.01-5 mass% of a polymer obtained by polymerizing an ethylenic unsaturated monomer containing a fluorinated alkyl group expressed by general formula; CH2=C(R1)-COO-(X)<SB>n</SB>-Rf. Wherein, Rf is a 1-20C perfluoroalkyl group or a partially fluorinated alkyl group, may be straight-chained or branched and have a functional group containing an oxygen atom and/or a nitrogen atom in the main chain; R1 is a hydrogen atom, alkyl group optionally fluorinated, chlorine atom or fluorine atom; X is a bivalent linking group; n is an integer of 1-10. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a saturated norbornene resin film having good optical uniformity and a method for producing the same. The present invention also relates to a polarizing plate, an optical compensation film, an antireflection film and a liquid crystal display device using the saturated norbornene resin film.

  Since saturated norbornene resin films have low water absorption and moisture permeability, they have been developed as substrate films for optical materials. Furthermore, in recent years, it has been studied to develop in-plane retardation (Re) and retardation in the thickness direction (Rth) and use it as an optical compensation film for liquid crystal display elements to increase the viewing angle.

Such a saturated norbornene resin film may be used as it is in a melt-extruded state, but it is also used after stretching the extruded raw film. As a method of stretching a saturated norbornene resin film, a method of stretching in the casting direction (longitudinal or longitudinal direction) (longitudinal stretching) and a method of stretching in the lateral (width) direction (transverse stretching), or simultaneously in the longitudinal and lateral directions. A method of stretching (simultaneous stretching) can be mentioned. Of these, longitudinal stretching has been conventionally used because of its compact equipment. Usually, the longitudinal stretching is performed by heating the film to a glass transition temperature (Tg) or more between two or more pairs of nip rolls and increasing the conveyance speed on the outlet side from the conveyance speed of the nip roll on the inlet side. Various improvements have been attempted for the conditions of the longitudinal stretching method using this mechanism. For example, Patent Document 1 discloses that the variation in Re is reduced by reducing temperature unevenness during stretching of a saturated norbornene resin film. It is described. Further, Patent Document 2 and Patent Document 3 describe the surface shape and the preferred region of the die line.
JP 2001-42130 A JP 2005-55575 A JP 2005-55619 A

  However, the stretched film obtained by the method described in Patent Document 1 is a streak formed in the casting direction during casting extrusion (referred to as a die streak) or a stepped streak formed in the lateral direction ( This was a problem. In particular, when the stretched film obtained by the method described in Patent Document 1 is used as an optical compensation film, fine surface unevenness is expressed, and a liquid crystal display device incorporating the same causes fine display unevenness. Improvement was desired. Further, the specific solutions described in Patent Document 2 and Patent Document 3 are not sufficient. Furthermore, when a saturated norbornene resin is melt-formed, a dirt substance adheres to the extrusion roll and the transport roll. However, it is difficult to reduce the amount of such a dirt substance attached.

  An object of this invention is to provide the saturated norbornene resin film which has the favorable surface shape which improved the vertical stripe and danmura seen when manufacturing with the conventional melt film-forming method. Another object of the present invention is to provide a saturated norbornene resin film having a small change in optical properties due to environmental conditions. Furthermore, the present invention aims to provide a method for easily producing a saturated norbornene resin film having such properties, particularly a production method for reducing dirt substances adhering to an extrusion roll or a conveyance roll during melt film formation. . It is another object of the present invention to provide a polarizing plate, an optical compensation film, an antireflection film, and a liquid crystal display device having a small change in optical characteristics due to environmental conditions, particularly a liquid crystal display device with improved fine display unevenness on an image.

The above object of the present invention is achieved by the present invention having the following configuration.
[1] A saturated norbornene resin film comprising a polymer having a fluorine atom in an amount of 0.01 to 5% by mass with respect to the solid content of the film and a residual solvent amount of 0.01% by mass or less.
[2] The saturated norbornene according to [1], wherein the polymer having a fluorine atom is a polymer obtained by polymerizing a monomer containing a fluorinated alkyl group-containing ethylenically unsaturated monomer. Resin film.
[3] The saturated norbornene resin film according to [2], wherein the fluorinated alkyl group-containing ethylenically unsaturated monomer is represented by the following general formula (FM-1).
Formula _{(FM-1) CH 2 =} C (R 1) -COO- (X) n-Rf
(In the formula, Rf is a perfluoroalkyl group having 1 to 20 carbon atoms or a partially fluorinated alkyl group, Rf may be linear or branched, and an oxygen atom and / or It may have a functional group containing a nitrogen atom in the main chain, R ¹ represents a hydrogen atom, an alkyl group which may be fluorinated, a chlorine atom or a fluorine atom, and X is a divalent linking group. And n represents an integer of 1 to 10.)
[4] The saturated norbornene resin film according to any one of [1] to [3], containing 0.005 to 2% by mass of fine particles having an average primary particle size of 0.005 to 2 μm.
[5] In any one of [1] to [4], 0.05 to 5 g / m ^{2 of} at least one selected from the group consisting of a plasticizer, an ultraviolet absorber and a stabilizer is contained. The saturated norbornene resin film described.
[6] The in-plane retardation (Re) is 0 nm to 500 nm, and the thickness direction retardation (Rth) is −300 nm to 700 nm. Any one of [1] to [5] The saturated norbornene resin film described in 1.
[7] Both the slow axis direction of Re and the variation in the direction perpendicular to the slow axis are 5% or less, and the variation of Rth in the slow axis direction and the direction perpendicular to the slow axis are both 5%. The saturated norbornene resin film according to any one of [1] to [6], which is the following.

[8] A saturated norbornene resin film comprising a step of melt-forming a mixture of a saturated norbornene resin and a polymer having 0.01 to 5% by mass of fluorine atoms based on the solid content of the saturated norbornene resin. Manufacturing method.
[9] The method for producing a saturated norbornene resin film according to [8], further comprising a step of stretching the melt-formed film at 0.90 to 5 times in at least one of the casting direction or the width direction.
[10] A saturated norbornene resin film produced by the production method according to [8] or [9].

[11] A polarizing plate obtained by laminating at least one layer of the saturated norbornene resin film according to any one of [1] to [7] and [10] on a polarizing film.
[12] An optical compensation film using the saturated norbornene resin film according to any one of [1] to [7] and [10] as a base material.
[13] An antireflection film using the saturated norbornene resin film according to any one of [1] to [7] and [10] as a base material.
[14] A liquid crystal display device using the saturated norbornene resin film according to any one of [1] to [7] and [10].

  The saturated norbornene resin film of the present invention has a good surface shape with reduced vertical lines and dangling irregularities observed when produced by a conventional melt film-forming method. In addition, since the change in optical characteristics due to environmental conditions is small, stable optical characteristics can be maintained for a long time. According to the production method of the present invention, it is possible to easily produce a saturated norbornene resin film having such properties, and it is possible to reduce dirt substances adhering to the extrusion roll and the transport roll during melt film formation. . The polarizing plate, the optical compensation film, the antireflection film, and the liquid crystal display device of the present invention have a small change in optical characteristics due to environmental conditions. In particular, the liquid crystal display device of the present invention has improved fine display unevenness on an image.

Detailed Description of the Invention

  Hereinafter, the saturated norbornene resin film of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

<Saturated norbornene resin film>
"Characteristic"
The saturated norbornene resin film of the present invention is characterized by containing a polymer having fluorine atoms in an amount of 0.01 to 5% by mass with respect to the solid content of the film and having a residual solvent amount of 0.01% by mass or less.

《Saturated norbornene resin》
Saturated norbornene resins-A and saturated norbornene resins-B described below are preferable examples of the saturated norbornene resins used as the raw material for the saturated norbornene resin film of the present invention. In particular, saturated norbornene resin-A is preferable because it is suitable for melt film formation.

(Saturated norbornene resin-A)
As the saturated norbornene resin-A, (1) a ring-opening (co) polymer of a norbornene monomer is subjected to polymer modification such as maleic acid addition or cyclopentadiene addition as necessary, and then further hydrogenated. Obtained resin, (2) resin obtained by addition polymerization of norbornene monomer, and (3) obtained by addition copolymerization of norbornene monomer and olefin monomer such as ethylene and α-olefin. Resins etc. can be mentioned. The polymerization method and the hydrogenation method can be performed by conventional methods.

  Examples of the norbornene-based monomer include norbornene and alkyl and / or alkylidene substituted products thereof (for example, 5-methyl-2-norbornene, 5-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl- 2-norbornene, 5-ethylidene-2-norbornene, etc.), polar substituents such as halogens thereof; dicyclopentadiene, 2,3-dihydrodicyclopentadiene, etc .; dimethanooctahydronaphthalene, its alkyl and / or alkylidene Substituents and polar group substituents such as halogen (for example, 6-methyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6- Ethyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octa Dronaphthalene, 6-ethylidene-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-chloro-1,4: 5,8-dimethano -1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-cyano-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a -Octahydronaphthalene, 6-pyridyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-methoxycarbonyl-1,4: 5 8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, etc.); adducts of cyclopentadiene and tetrahydroindene, etc .; 3-pentamers of cyclopentadiene (for example, 4, 9: 5,8-dimethano-3a, 4,4a, , 8,8a, 9,9a-octahydro-1H-benzoindene, 4,11: 5,10: 6,9-trimethano-3a, 4,4a, 5,5a, 6,9,9a, 10,10a, 11, 11a-dodecahydro-1H-cyclopentanthracene) and the like. These norbornene monomers may be used alone or in combination of two or more.

(Saturated norbornene resin-B)
Examples of the saturated norbornene resin-B include those represented by the following general formulas (1) to (4). Among these, those represented by the following general formula (1) are particularly preferable.

In general formulas (1) to (4), R ^{1 to} R ¹² each independently represent a hydrogen atom or a monovalent substituent (preferably an organic group), and at least one of them is a polar group. Is preferred. The mass average molecular weight of these saturated norbornene resins is usually preferably from 5,000 to 1,000,000, more preferably from 8,000 to 200,000.

   Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms such as a methyl group, an ethyl group, and iso- A propyl group, a tert-butyl group, an n-octyl group, an n-decyl group, an n-hexadecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, etc.), an alkenyl group (having 1 to 20 carbon atoms, preferably 1 to 10 alkenyl groups such as vinyl group, allyl group, 2-butenyl group and 3-pentenyl group), alkynyl group (C1-C20, preferably 1-10 alkynyl group, For example, a propargyl group, a 3-pentynyl group, etc.), an aryl group (an aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, A phenyl group, a p-methylphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, etc.), an amino group (an amino group having 0 to 20 carbon atoms, preferably 0 to 10 carbon atoms, such as an amino group). , Methylamino group, dimethylamino group, diethylamino group, dibenzylamino group, etc.), alkoxy group (C1-C20, preferably 1-10 alkoxy group such as methoxy group, ethoxy group, butoxy group) Groups), aryloxy groups (C6-C20, preferably 6-15 aryloxy groups such as phenyloxy group and 2-naphthyloxy group), heterocyclic oxy groups (C1-C20, preferably C1-10 heterocyclic oxy group, for example, pyridyloxy group, pyrimidinyloxy group A pyridazinyloxy group, a benzimidazolyloxy group, etc.), a silyloxy group (a silyloxy group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, such as a trimethylsilyloxy group, a t-butyldimethylsilyloxy group, etc. ), Acyl groups (acyl groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as acetyl group, benzoyl group, formyl group, and pivaloyl group), alkoxycarbonyl groups (carbon number). An alkoxycarbonyl group having 2 to 20, preferably 2 to 10, such as a methoxycarbonyl group and an ethoxycarbonyl group), an aryloxycarbonyl group (C7-20, preferably 7-15 aryloxycarbonyl). Group, for example, a phenyloxycarbonyl group). An acyloxy group (acyloxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as an acetoxy group and a benzoyloxy group); ), An acylamino group (acylamino group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms such as acetylamino group and benzoylamino group), an alkoxycarbonylamino group (2 to 20 carbon atoms, preferably 2 carbon atoms). 10 to 10 alkoxycarbonylamino groups such as methoxycarbonylamino group), aryloxycarbonylamino groups (7 to 20 carbon atoms, preferably 7 to 15 aryloxycarbonylamino groups such as phenyloxycarbonyl Amino group, etc.), alkyl or arylsulfonylamino group (C1-C20, preferably 1-10 alkyl or arylsulfonylamino groups such as methanesulfonylamino group, benzenesulfonylamino group, etc.). .), Sul Amoyl group (sulfamoyl group having 0 to 20, preferably 0 to 10 carbon atoms, such as sulfamoyl group, N-methylsulfamoyl group, N, N-dimethylsulfamoyl group, N-phenylsulfamoyl group, etc.) ), A carbamoyl group (a carbamoyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as a carbamoyl group, an N-methylcarbamoyl group, an N, N-diethylcarbamoyl group, an N-phenylcarbamoyl group). ), Alkylthio groups (C1-C20, preferably C1-C10 alkylthio groups such as methylthio and ethylthio groups), arylthio groups (C6-C20, preferably C6-C15). An arylthio group such as a phenylthio group), a heterocyclic thio group (having 1 to 3 carbon atoms). 0, preferably 1 to 10 heterocyclic thio groups such as pyridinylthio group, pyrimidinylthio group, pyridazinylthio group, benzimidazolylthio group, thiadiazolylthio group, etc., alkyl or arylsulfonyl group (carbon number) 1-20, preferably 1-10 alkyl or arylsulfonyl groups, such as mesyl, tosyl, etc.), alkyl or arylsulfinyl groups (C1-C20, preferably 1-10 alkyl or Arylsulfonyl groups such as methanesulfinyl group, benzenesulfinyl group, etc.), hydroxy group, mercapto group, cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group , Heterocyclic groups (charcoal A heterocyclic group having a prime number of 1 to 20, preferably 1 to 10, for example, a nitrogen atom, an oxygen atom, a sulfur atom, specifically an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a thienyl group, a piperidyl group, a morpholino Group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, carbazolyl group, azepinyl group and the like. ), A silyl group (a silyl group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, such as a trimethylsilyl group or a triphenylsilyl group). The hydrogen atom of these substituents may be further substituted. Moreover, when there are two or more substituents in one molecule, these substituents may be the same or different. If possible, they may be linked together to form a ring. As the substituent, a halogen atom, an alkyl group, a silyl group, an aryl group, an alkoxy group and an aryloxy group are preferable, and a methyl group, a trimethylsilyl group, a phenyl group and a methoxy group are particularly preferable.

  The polar group refers to an organic group that is polarized by atoms having high electronegativity such as oxygen, sulfur, nitrogen, and halogen. Specifically, an amino group (an amino group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as an amino group, a methylamino group, a dimethylamino group, a diethylamino group, and a dibenzylamino group). Alkoxy groups (C1-C20, preferably 1-10 alkoxy groups such as methoxy, ethoxy and butoxy groups), aryloxy groups (C6-20, preferably 6-15). An aryloxy group such as a phenyloxy group and a 2-naphthyloxy group), a heterocyclic oxy group (a heterocyclic oxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms such as a pyridinyloxy group, Pyrimidinyloxy group, pyridazinyloxy group, benzimidazolyloxy group, etc.), silyloxy group (3 to 2 carbon atoms) A silyloxy group having 3 to 10 carbon atoms, such as a trimethylsilyloxy group and a t-butyldimethylsilyloxy group.), An acyl group (acyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, An acetyl group, a benzoyl group, a formyl group, a pivaloyl group, etc.), an alkoxycarbonyl group (a C2-C20, preferably a C2-C10 alkoxycarbonyl group, such as a methoxycarbonyl group, an ethoxycarbonyl group, etc.). An aryloxycarbonyl group (C6-C20, preferably a C6-C15 aryloxycarbonyl group such as a phenyloxycarbonyl group), an acyloxy group (C1-C20, preferably 1-10 acyloxy groups such as acetoxy group, benzoy An oxy group, etc.), an acylamino group (acylamino group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms such as an acetylamino group and a benzoylamino group), an alkoxycarbonylamino group (carbon number). An alkoxycarbonylamino group having 2 to 20, preferably 2 to 10, such as a methoxycarbonylamino group), an aryloxycarbonylamino group (having 6 to 20 carbon atoms, preferably 6 to 15 aryloxycarbonylamino groups) For example, a phenyloxycarbonylamino group), an alkyl or arylsulfonylamino group (an alkyl or arylsulfonylamino group having 1 to 20, preferably 1 to 10 carbon atoms, such as a methanesulfonylamino group, benzenesulfonyl Amino group And so on. ), A sulfamoyl group (a sulfamoyl group having 0 to 20, preferably 0 to 10 carbon atoms, such as a sulfamoyl group, an N-methylsulfamoyl group, an N, N-dimethylsulfamoyl group, an N-phenylsulfamoyl group). ), A carbamoyl group (a carbamoyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as a carbamoyl group, an N-methylcarbamoyl group, an N, N-diethylcarbamoyl group, an N-phenylcarbamoyl group, etc. Ureido group (C1-C20, preferably 1-10 ureido groups such as ureido group, methylureido group, phenylureido group, etc.), hydroxy group, halogen atom (for example, Fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, Toromoto, hydroxamic acid group, sulfino group, a hydrazino group, an imino group, a heterocyclic group. These substituents may be directly connected to the norbornene ring, may be connected by an alkylene group or the like, and may be further substituted. Moreover, when there are two or more substituents in one molecule, these substituents may be the same or different. If possible, they may be linked together to form a ring. Preferred as the polar group are amino group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, and aryl. An oxycarbonylamino group, more preferably an alkoxycarbonyl group, an acyloxy group, an acylamino group, and an alkoxycarbonylamino group, and particularly preferably an alkoxycarbonyl group.

Examples of saturated norbornene resins that can be used in the present invention include, for example, JP-A-60-168708, JP-A-62-252406, JP-A-62-2252407, JP-A-2-133413, Examples thereof include resins described in JP-A-63-145324, JP-A-63-264626, JP-A-1-240517, and JP-B-57-8815.
Among these resins, a hydrogenated polymer obtained by hydrogenating a ring-opening polymer of a norbornene monomer is particularly preferable.
The glass transition temperature (Tg) of these saturated norbornene resins is preferably 100 ° C. to 250 ° C., more preferably 110 ° C. to 200 ° C., and further preferably 120 ° C. to 180 ° C. The saturated water absorption is preferably 1% by mass or less, and more preferably 0.8% by mass or less. The glass transition temperature (Tg) and saturated water absorption of the saturated norbornene resins represented by the general formulas (1) to (4) can be controlled by selecting the type of R ^{1 to} R ¹² .

  In the present invention, as the saturated norbornene resin, at least one tetracyclododecene derivative represented by the following general formula (5) is used alone, or the unsaturated compound capable of copolymerizing with the tetracyclododecene derivative. A hydrogenated polymer obtained by hydrogenating a polymer obtained by metathesis polymerization with a cyclic compound can also be used.

In General Formula (5), R ^{13 to} R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent (preferably an organic group), and at least one of these is preferably a polar group. Specific examples and preferred ranges of the substituents and polar groups herein are the same as those described for the general formulas (1) to (4).
In the tetracyclododecene derivative represented by the above general formula (5), when at least one of R ^{13 to} R ¹⁶ is a polar group, a polarizing film having excellent adhesion to other materials, heat resistance, etc. Obtainable. Further, the polar group is a group represented by — (CH ₂ ) _n COOR (where R is a hydrocarbon group having 1 to 20 carbon atoms, and n is an integer of 0 to 10). The resulting hydrogenated polymer (polarizing film substrate) is preferred because it has a high glass transition temperature. In particular, the polar substituent represented by — (CH ₂ ) _n COOR is preferably contained in one molecule of the tetracyclododecene derivative of the general formula (5) from the viewpoint of reducing the water absorption rate. In the above polar substituent, it is preferable in that the hygroscopicity of the obtained hydrogenated polymer decreases as the number of carbon atoms of the hydrocarbon group represented by R increases, but the balance with the glass transition temperature of the obtained hydrogenated polymer is good. From this point, the hydrocarbon group is preferably a chain alkyl group having 1 to 4 carbon atoms or a (poly) cyclic alkyl group having 5 or more carbon atoms, and particularly preferably a methyl group, an ethyl group, or a cyclohexyl group. preferable.

Furthermore, the tetracyclododecene derivative of the general formula (5) in which a hydrocarbon group having 1 to 10 carbon atoms is bonded as a substituent to a carbon atom to which a group represented by — (CH ₂ ) _n COOR is bonded, This is preferable because the resulting hydrogenated polymer has low hygroscopicity. In particular, the tetracyclododecene derivative of the general formula (5) in which the substituent is a methyl group or an ethyl group is preferable in terms of easy synthesis. Specifically, 8-methyl-8-methoxycarbonyltetracyclo [4,4,0,1 ^2.5, 1 ^7.10] dodeca-3-ene are preferred. These tetracyclododecene derivatives and mixtures of unsaturated cyclic compounds copolymerizable therewith are described, for example, in JP-A-4-77520, page 4, upper right column, line 12 to page 6, lower right column, line 6. Metathesis polymerization and hydrogenation can be carried out by the prepared method.
These norbornene resins preferably have an intrinsic viscosity (η _inh ) measured at 30 ° C. in chloroform of 0.1 to 1.5 dl / g, more preferably 0.4 to 1.2 dl / g. g. Further, the hydrogenation rate of the hydrogenated polymer is preferably 50% or more, more preferably 90% or more, and still more preferably 98% or more, as measured by 60 MHz and ¹ H-NMR. The higher the hydrogenation rate, the more the obtained saturated norbornene resin film has better stability to heat and light. The gel content contained in the hydrogenated polymer is preferably 5% by mass or less, more preferably 1% by mass or less.

(Other ring-opening polymerizable cycloolefins)
In the present invention, other cycloolefins capable of ring-opening polymerization can be used in combination as long as the object of the present invention is not impaired. Specific examples of such cycloolefins include compounds having one reactive double bond such as cyclopentene, cyclooctene, and 5,6-dihydrodicyclopentadiene. The content of these ring-opening polymerizable cycloolefins is preferably 0 mol% to 50 mol%, more preferably 0.1 mol% to 30 mol%, based on the norbornene-based monomer. And 0.3 mol% to 10 mol% is particularly preferable.

(Polymer having fluorine atom)
Next, a polymer having a fluorine atom contained in the saturated norbornene resin of the present invention will be described. As a polymer which has a fluorine atom, the polymer described in Unexamined-Japanese-Patent No. 2001-269564 can be mentioned, for example. What is preferable as the polymer having a fluorine atom is a polymer obtained by polymerizing a monomer containing a fluorinated alkyl group-containing ethylenically unsaturated monomer (monomer A) as an essential component. . The fluorinated alkyl group-containing ethylenically unsaturated monomer (monomer A) is not particularly limited as long as it is a compound having an ethylenically unsaturated group and a fluorinated alkyl group in the molecule. Preferably it contains an acrylic ester group and its related groups, and specific examples thereof include fluorinated (meth) acrylates represented by the general formula (FM-1). In addition, (meth) acrylate here is a general term for methacrylate, acrylate, fluoroacrylate, and chlorinated acrylate.

Formula _{(FM-1) CH 2 =} C (R 2) -COO- (X) n2 -Rf
In the formula, Rf is a perfluoroalkyl group having 1 to 20 carbon atoms or a partially fluorinated alkyl group, Rf may be linear or branched, and may be an oxygen atom and / or nitrogen. It may have a functional group containing an atom in the main chain. R ² represents a hydrogen atom, an optionally fluorinated alkyl group, a chlorine atom or a fluorine atom, X represents a divalent linking group, and n 2 represents an integer of 1 to 10.

The carbon number of the perfluoroalkyl group or the partially fluorinated alkyl group of Rf is preferably 1 to 18, more preferably 4 to 18, still more preferably 6 to 14, and most preferably 6 to 12. . The partially fluorinated alkyl group preferably has a perfluoroalkyl group in a part thereof, and the preferred range of the carbon number of the perfluoroalkyl group is the same as described above. The functional group containing an oxygen atom that may be present in the main chain is —SO ₂ —, —C (═O) —, and the functional group containing a nitrogen atom is —NH—, —N ( CH ₃ ) —, —N (C ₂ H ₅ ) —, —N (C ₃ H ₇ ) — and the like can be mentioned. The alkyl group which may be fluorinated which R ² may take may be any of an unsubstituted alkyl group, a perfluoroalkyl group and a partially fluorinated alkyl group. Preference is given to unsubstituted alkyl groups and partially fluorinated alkyl groups. A methyl group is preferred as the unsubstituted alkyl group.

Preferred as the divalent linking group that X can take is — (CH ₂ ) _m —, —CH ₂ CH (OH) — (CH ₂ ) _m —, — (CH ₂ ) _m N (R ³ ) —SO ₂ —, — (CH ₂ ) _m N (R ³ ) —CO—, —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ) ₂ —, —CH (CF _{3 ) -, - C (CH 3} ) (CF 3) -, - C (CF 3) 2 - and the like. m is an integer of 1 to 10, preferably 1 to 8, and more preferably 1 to 6. When m is 2 or more, the linking groups represented by each X may be the same or different. R ³ is hydrogen or an alkyl group having 1 to 6 carbon atoms. Moreover, the raw material represented by General formula (6) is also preferable as a fluorinated alkyl group containing ethylenically unsaturated monomer (A).

   In General formula (6), k represents the integer of 1-20, k becomes like this. More preferably, it is 2-18, More preferably, it is 4-14, Most preferably, it is 6-12.

   Specific examples of the fluorinated alkyl group-containing (meth) acrylate, which is a preferred monomer, are shown below, but the fluorinated alkyl group-containing (meth) acrylate that can be used in the present invention is limited to these. It is not something.

  Only one type of fluorinated alkyl group-containing ethylenically unsaturated monomer (monomer A) may be used, or two or more types may be used in combination. From the viewpoint of releasability (peelability), the fluorinated alkyl group in the fluorinated alkyl group-containing ethylenically unsaturated monomer (monomer A) preferably has 6 to 18 carbon atoms. Furthermore, what is 6-14 is more preferable, and what is 6-12 is especially preferable. In the present invention, the amount of the fluorinated alkyl group-containing ethylenically unsaturated monomer (monomer A) introduced into the polymer (I) is not particularly limited, but it is preferably 10% by mass or more, 15 mass% or more is more preferable, and 20 mass% or more is especially preferable.

  Furthermore, in this invention, it is also possible to contain the polyoxyalkylene group containing unsaturated monomer (monomer B) in the polymer which has a fluorine atom. The polyoxyalkylene group-containing ethylenically unsaturated monomer (monomer B) is not particularly limited as long as it is a compound having a polyoxyalkylene group and an ethylenically unsaturated group in one molecule. The oxyalkylene group is preferably an ethylene oxide group and / or a propylene oxide group. Moreover, the polymerization degree is 1-100 normally, and 5-50 are preferable. The ethylenically unsaturated group is a (meth) acrylic ester from the viewpoints of availability of raw materials, compatibility with blends in various coating compositions, ease of controlling such compatibility, or polymerization reactivity. Those containing groups and their analogous groups are suitable.

  Specific examples of the polyoxyalkylene group-containing ethylenically unsaturated monomer (monomer B) include polyethylene glycol, polypropylene glycol, and a copolymer of ethylene oxide and propylene oxide having a polymerization degree of 1 to 100. A poly (alkylene glycol) mono (meth) acrylic acid ester (hereinafter, this expression is a generic term for both alkyl acrylates and alkyl methacrylates), or a terminal with an alkyl group having 1 to 6 carbon atoms. And a mono (meth) acrylic acid ester of polyalkylene glycol such as polyethylene glycol, polypropylene glycol, and a copolymer of ethylene oxide and propylene oxide. Moreover, as a commercial item, NK ester M-20G, M-40G, M-90G, M-230G, AM-90G, AMP-10G, AMP-20G, AMP-60G made by Shin-Nakamura Chemical Co., Ltd. Blenmer PE-90, PE-200, PE-350, PME-100, PME-200, PME-400, PME-4000, PP-1000, PP-500, PP-800, 70PEP- 350B, 55PET-800, 50POEP-800B, NKH-5050, AP-400, AE-350, etc. are mentioned. Only one type of polyoxyalkylene group-containing ethylenically unsaturated monomer (monomer B) may be used, or two or more types may be used simultaneously.

  Furthermore, it is also possible to contain an ethylenically unsaturated monomer (monomer C) having two or more unsaturated bonds in one molecule. There is no restriction | limiting in particular as an ethylenically unsaturated monomer (monomer C) which has a 2 or more unsaturated bond in 1 molecule, According to composition of the matrix resin in a target compound, a solvent, etc. suitably Selected. The ethylenically unsaturated group includes (meth) acrylic ester groups from the viewpoint of availability of raw materials, compatibility with formulations in various coating compositions, ease of controlling such compatibility, or polymerization reactivity. Those containing such analogs are suitable.

  Specific examples of the ethylenically unsaturated monomer (monomer C) having two or more unsaturated bonds in one molecule include polyethylene glycol having a polymerization degree of 1 to 100, polypropylene glycol, and ethylene oxide and propylene oxide. Di (meth) acrylic acid esters of polyalkylene glycols such as copolymers, polyethylene glycols having a degree of polymerization of 1 to 100, capped with alkyl groups having 1 to 6 carbon atoms, polypropylene glycol, and ethylene oxide and propylene oxide (Poly) alkylene glycol di (meth) acrylic acid ester, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane tri (meth) acrylate and its ethylene oxide ( O) modified product, tetramethylolpropane tri (meth) acrylate and its EO modified product, bisphenol A diacrylate and its EO modified product, tetramethylolmethane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, etc. .

  Moreover, as a commercial item, NK ester 1G, 2G, 3G, 4G, 9G, 14G, 23G, BG, HD, NPG, A-200, A-400, A-600, manufactured by Shin-Nakamura Chemical Co., Ltd. A-HD, A-NPG, APG-200, APG-400, APG-700, A-BPE-4, 701A, Nippon Oil & Fats Co., Ltd. Bremer PDE-50, PDE-100, PDE-150, PDE-200 , PDE-400, PDE-600, ADE-200, ADE-400 and the like.

  The compounds that can be used in the present invention are not limited by the above specific examples. As an ethylenically unsaturated monomer (monomer C) having two or more unsaturated bonds in one molecule, the degree of polymerization is 1 to 100 in terms of compatibility with each compound and control of polymerization reaction. Poly (ethylene glycol), polypropylene glycol, and poly (alkylene glycol) such as a copolymer of ethylene oxide and propylene oxide, or a degree of polymerization of 1 to 100 having a terminal capped with an alkyl group having 1 to 6 carbon atoms Particularly preferred are poly (alkylene glycols) such as polyethylene glycol, polypropylene glycol, and polyalkylene glycols such as copolymers of ethylene oxide and propylene oxide. Only one type of ethylenically unsaturated monomer (monomer C) having two or more unsaturated bonds in one molecule may be used, or two or more types may be used simultaneously.

  Although there is no restriction | limiting in particular in the polymerization composition of the polymer concerning this invention which has been described above, (A) / (B) / (C) = 10-90 / 0-40 / 0-30 in mass ratio. The preferred range is (A) / (B) / (C) = 15 to 70/5 to 30/0 to 10, and the particularly preferred range is (A) / (B). / (C) = 15-65 / 5-5-20 / 1-7. In addition to the monomers (A), (B), and (C), the polymer having a fluorine atom used in the present invention is compatible with the blends in various coating compositions, polymerization reactivity, and cost. In view of the above, it is possible to introduce an ethylenically unsaturated monomer (monomer D) other than these as a copolymerization component. Such an ethylenically unsaturated monomer (monomer D) is not particularly limited, and any known and publicly used compound can be used.

  Specific examples include styrene, nucleus-substituted styrene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl pyridine, N-vinyl pyrrolidone, vinyl sulfonic acid, vinyl acetate, and other fatty acid vinyls, and α, β-ethylenically unsaturated carboxylic acids. That is, as a derivative of a monovalent or divalent carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, or an α, β-ethylenically unsaturated carboxylic acid, the alkyl group has 1 to 1 carbon atoms. 18 (meth) acrylic acid alkyl esters, that is, methyl, ethyl, propyl, butyl, octyl, 2-ethylhexyl, decyl, dodecyl, stearyl esters of (meth) acrylic acid, and (meth) acrylic acid having 1 to 1 carbon atoms 18 hydroxyalkyl esters, ie 2-hydroxyethyl ester, hydroxy Propyl ester, hydroxybutyl ester, and the like.

  Also, (meth) acrylic acid aminoalkyl ester having 1 to 18 carbon atoms, that is, dimethylaminoethyl ester, diethylaminoethyl ester, diethylaminopropyl ester, etc., and (meth) acrylic acid containing 3 to 18 carbon atoms in ether oxygen Alkyl esters such as methoxyethyl ester, ethoxyethyl ester, methoxypropyl ester, methyl carbyl ester, ethyl carbyl ester, butyl carbyl ester and the like, and further as a bridged bond-containing monomer, for example, dicyclopentanyloxyl ethyl (meth) acrylate, Isobornyloxylethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, dicyclopentanyl (Meth) acrylate, dicyclopentenyl (meth) acrylate and the like, and alkyl vinyl ethers having 1 to 18 alkyl carbon atoms such as methyl vinyl ether, propyl vinyl ether, dodecyl vinyl ether, glycidyl ester of (meth) acrylic acid, that is, glycidyl methacrylate, glycidyl Examples thereof include acrylates, and various macromonomers such as Sartomer styrene macromonomer 4500, Toa Gosei Co., Ltd. AA-6 and AN-6. Moreover, Kyoeisha Chemical Co., Ltd. product HOA-MS, HOA-MPL, HOA-MPE, HOA-HH, Toagosei Co., Ltd. product Aronix M-5300, M-5400, M-5500, M- 5600, M-5700 and the like.

  Further, γ-methacryloxypropylmethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropylmethyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, vinyltrimethoxy Silane coupling group-containing monomers such as silane, and monomers containing polar groups, particularly anionic groups and hydroxyl groups, in the molecule include acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2 -Acrylamido-2-methylpropane sulfonic acid, partially sulfonated styrene, mono (acryloyloxyethyl) acid phosphate, mono (methacryloxyethyl) acid phosphate, 2-hydroxyethyl (meth) acrylate, Examples include 2-hydroxypropyl (meth) acrylate. The ethylenically unsaturated monomer (monomer D) may be used alone or in combination of two or more.

  When the monomer (monomer D) is introduced, the introduction ratio is not particularly limited, but is determined by the composition in the composition in which the polymer is blended, the level of the desired physical properties, the coating method, and the like. Is done. A preferable introduction amount is a mass ratio, and is within a range of [(monomer A) + (monomer B) + (monomer C)] / (monomer D) = 20 to 100/0 to 80. As a more preferable range, [(monomer A) + (monomer B) + (monomer C)] / (monomer D) = 50 to 97/3 to 50, and particularly preferable range is [ (Monomer A) + (Monomer B) + (Monomer C)] / (Monomer D) = 60 to 95/5 to 40.

  The method for producing the polymer having a fluorine atom used in the present invention is not limited at all, and a solution polymerization method or a bulk polymerization method based on a polymerization mechanism such as a publicly known method, that is, a radical polymerization method, a cation polymerization method, an anion polymerization method or the like. It can be produced by suspension polymerization, emulsion polymerization or the like. There is also no particular limitation on the structure of the polymer, and random, alternating, block copolymers based on the above polymerization mechanism, various living polymerization methods or block reaction, molecular weight distribution controlled by polymer reaction, graft, star type A polymer or the like can be freely selected. Furthermore, after obtaining such a polymer, it is also possible to modify the polymer by a method using various polymer reactions, energy rays such as radiation, electron beam, and ultraviolet rays. Among these methods, the radical polymerization method is convenient and preferred industrially. In this case, as the polymerization initiator, those known in the art can be used, for example, peroxides such as benzoyl peroxide and diacyl peroxide, and azo compounds such as azobisisobutyronitrile and phenylazotriphenylmethane. And metal chelate compounds such as Mn (acac) 3.

  If necessary, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, ethylthioglycolic acid, octylthioglycolic acid, and coupling group-containing thiol compounds such as γ-mercaptopropyltrimethoxysilane Can be used in combination with a chain transfer agent. In addition, the fluoropolymer can be obtained by photopolymerization in the presence of a photosensitizer or a photoinitiator, or by polymerization using radiation or heat as an energy source. The polymerization can be carried out in the presence or absence of a solvent, but is preferably in the presence of a solvent from the viewpoint of workability.

  Examples of the solvent include alcohols such as ethanol, isopropyl alcohol, n-butanol, isobutanol, tert-butanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone, methyl acetate, ethyl acetate, butyl acetate, Esters such as methyl lactate, ethyl lactate and butyl lactate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, 2- Monocarboxylic acid esters such as ethyl methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, methyl cello Ethers such as rurub, cellosolve, butyl cellosolve, butyl carbitol, ethyl cellosolve acetate, propylene glycol such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate And their esters, halogen solvents such as 1,1,1-trichloroethane and chloroform, ethers such as tetrahydrofuran and dioxane, aromatics such as benzene, toluene and xylene, perfluorooctane and perfluorotriene Any of the fluorinated inerts such as -n-butylamine can be used.

The amount of the polymer having a fluorine atom used in the present invention is 0.01 to 5% by mass, preferably 0.02 to 3% by mass, and more preferably 0.005% by mass with respect to the solid content of the saturated norbornene resin. It is 05-2 mass%. Especially preferably, it is 0.05-1 mass%.
Specific examples of the polymer having a fluorine atom preferably used in the present invention are shown below, but the polymer having a fluorine atom that can be used in the present invention is not limited thereto.

PF-1: A-9 / butyl acrylate = 30/70 (molar ratio, molecular weight 3000)
PF-2: A-9 / 2-ethylhexyl acrylate = 25/75 (molar ratio, molecular weight 5000)
PF-3: A-8 / butyl acrylate = 20/80 (molar ratio, molecular weight 8000)
PF-4: A-8 / butyl methacrylate = 15/85 (molar ratio, molecular weight 5000)
PF-5: A-2 / butyl acrylate = 25/75 (molar ratio, molecular weight 8000)
PF-6: A-2 / butyl methacrylate = 20/70 (molar ratio, molecular weight 5000)
PF-7: A-9 / butyl acrylate = 25/75 (molar ratio, molecular weight 5000)
PF-8: A-9 / poly (average polymerization degree 5) oxyethylene methacrylate / butyl acrylate = 30/20/50 (molar ratio, molecular weight 9000)
PF-9: A-1 / poly (average polymerization degree 5) oxyethylene methacrylate / 2-ethylhexyl acrylate / methyl acrylate / triethylene glycol dimethacrylate = 30/20/30/15/5 (molar ratio, molecular weight 3000)

PF-10: A-8 / poly (average polymerization degree 5) oxyethylene acrylate / 2-butyl acrylate / methyl methacrylate / tetraethylene glycol dimethacrylate = 30/25/25/15/5 (molar ratio, molecular weight 3500)
PF-11: A-12 / poly (average polymerization degree 5) oxyethylene methacrylate / 2-hexyl acrylate / methyl methacrylate / tetraethylene glycol dimethacrylate = 30/25/25/5/5 (molar ratio, molecular weight 6000)
PF-12: A-34 / poly (average polymerization degree 5) oxyethylene methacrylate / 2-hexyl acrylate / methyl methacrylate = 30/25/25/20 (molar ratio, molecular weight 6000)
PF-13: A-47 / poly (average polymerization degree 5) oxyethylene methacrylate / 2-hexyl acrylate / methyl methacrylate = 25/25/30/20 (molar ratio, molecular weight 8000)
PF-14: A-34 / poly (average polymerization degree 5) oxyethylene methacrylate / 2-hexyl acrylate / styrene = 30/25/35/10 (molar ratio, molecular weight 9000)

(Additive)
Next, the saturated norbornene resin film of the present invention preferably contains fine particles. In addition, if necessary, various additives may be added at any stage from the preparation to the preparation of the melt pelletization. Examples of additives other than the fine particles of the present invention include ultraviolet absorbers, (thermal) stabilizers such as group 2 metal salts such as calcium and magnesium, antistatic agents, flame retardants, lubricants, and oils.

(Fine particles)
First, in the saturated norbornene resin film in the present invention, fine particles having an average primary particle size of 0.005 to 2 μm with respect to the saturated norbornene resin are 0. 005-2. It is preferable to contain 0% by mass. Examples of the fine particles include fine particles of inorganic compounds and fine particles of organic compounds.

As the inorganic _{compound, SiO 2, ZnO, TiO 2} , SnO 2, Al 2 O 3, ZrO 2, In 2 O 3, MgO, BaO, MoO 2, V 2 O 5, talc, clay, calcined kaolin, calcined silica Examples include calcium hydrate, hydrated calcium silicate, aluminum silicate, magnesium silicate, and calcium phosphate. _Preferably, SiO _{2, ZnO,} is _{TiO 2, SnO 2, Al 2} O 3, ZrO 2, In 2 O 3, MgO, BaO, MoO 2, V 2 O 5, more preferably SiO _2, TiO _2, SnO _2, Al ₂ O _3, a ZrO _2. As the SiO ₂ fine particles, for example, commercially available products such as Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (above Nippon Aerosil Co., Ltd.) can be used. As the fine particles of ZrO ₂ , commercially available products such as Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) can be used.

  Next, as the fine particles of the organic compound that can be used in the present invention, for example, polymers such as silicone resins, fluororesins, and acrylic resins are preferable, and silicone resins are also preferably used. The silicone resin preferably has a three-dimensional network structure, such as Tospearl 103, 105, 108, 120, 145, 3120, and 240 (above, manufactured by Toshiba Silicone Co., Ltd.). Commercial products with names can be used. The average primary particle size of the fine particles according to the present invention is preferably from 0.005 to 2 μm, more preferably from 0.005 to 0.5 μm, from the viewpoint of keeping haze low. The average primary particle size is particularly preferably 0.005 to 0.1 μm. Here, the average primary particle size of the fine particles is measured by observing particles of a saturated norbornene resin film with a transmission electron microscope (magnification of 500,000 to 1,000,000 times), observing 100 particles, and averaging the average values. The primary particle size was used.

  The addition of these fine particles can be carried out by a method such as kneading by a conventional method, but particularly preferably, the fine particles dispersed in a solvent in advance and a saturated norbornene resin are mixed and dispersed, and then the solvent is volatilized solid, It is preferable that a melt of the obtained saturated norbornene resin mixture is used in the production process in that a uniform melt can be obtained. In order to obtain fine particles that are uniformly dispersed in the film, the powder is finely divided and finely dispersed by a share in a kneader or a die (preferably a T-die) during film formation. It is preferable to include a process. In addition to the fine particles, other functional materials (for example, a plasticizer and / or an ultraviolet absorber) may be simultaneously dissolved and dispersed in a solvent and mixed for use. At this time, the average secondary particle size of the fine particles finally in the saturated norbornene resin film is preferably 0.01 to 5 μm, more preferably the average secondary particle size is 0.02 to 3 μm, and particularly the average secondary particle size. A particle size of 0.02-1 μm is preferred. Here, the average secondary particle size of the fine particles is measured by observing particles with a transmission electron microscope (magnification 100,000 to 1,000,000 times) in a saturated norbornene resin film, observing 100 particles, and averaging the average values. The secondary particle size was used.

Furthermore, when fine particles (inorganic fine particles) made of an inorganic compound are used in the present invention, the inorganic fine particles are preferably surface-treated in order to stably exist in the saturated norbornene resin film. The inorganic fine particles are preferably used after being subjected to a surface treatment. The surface treatment method includes chemical surface treatment using a coupling agent and physical surface treatment such as plasma discharge treatment and corona discharge treatment, and the use of a coupling agent is preferred. As the coupling agent, an organoalkoxy metal compound (for example, a silane coupling agent, a titanium coupling agent, etc.) is preferably used. For inorganic fine particles (particularly SiO ₂ ), treatment with a silane coupling agent is particularly effective. As the silane coupling agent, an organosilane compound represented by the general formula (11) can be used. Although the usage-amount of a coupling agent is not specifically limited, It is recommended to use it with 0.005-5 mass% preferably with respect to inorganic fine particles, Furthermore, 0.01-3 mass% is preferable.

Formula _{(11) R x Si (OR} ') (4-x)
(In the formula, R and R ′ are the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, an allyl group or a fluoroalkyl group. The alkyl group is an epoxy group, amino group, acrylic group as a functional group. And may have a group, an isocyanate group, and / or a mercapto group, x is an integer of 0 to 3, preferably an integer of 0 to 2.)

Specific examples of the organosilane represented by the general formula (11) include the following, but the organosilane that can be used in the present invention is not limited to these examples. Specific examples of x = 0 include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, and tetra-n-butoxysilane. Specific examples of x = 1 include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropyltrimethoxy Examples include silane, γ-trimethoxysilylpropyl isocyanate, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-acryloxypropyltrimethoxysilane. Specific examples of x = 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-methacryloxypropylmethyl. Examples include dimethoxysilane. Also, two or more different organosilanes can be used in combination for the purpose of adjusting the hardness and brittleness of the cured film and introducing functional groups.

  The coupling agent is processed by a direct processing method for fine particles and an integral blend method. The direct method is roughly classified into a dry method and a slurry method spray method. The fine particles obtained by the direct treatment method are excellent in that they can be added to the binder and the coupling agent can be reliably modified on the surface of the fine particles. Among them, the dry method is generally carried out by uniformly dispersing fine particles in an alcohol aqueous solution, an organic solvent or an aqueous solution of a silane coupling agent and then drying. It is preferable to use a stirrer such as a Henschel mixer, a super mixer, a ready mixer, a V-type blender or an open kneader. Among these agitators, an open kneader is particularly preferable. It is preferable that fine particles and a small amount of water, or an organic solvent containing water and a coupling agent are mixed, stirred with an open kneader to remove water, and then finely dispersed.

  The slurry method has an advantage that a coupling agent is added to the slurry when there is a step of slurrying the fine particles in the production of the fine particles. The spray method is to add a coupling agent to the fine particles in the fine particle drying step, and has an advantage that it can be treated in the production step, but has a problem in the uniformity of the treatment. Describing the integral blend method, it is a method of adding a coupling agent into fine particles and a binder, which requires simple kneading and is simple. In the present invention, the fine particles are preferably contained in an amount of 0.005 to 2.0 mass% with respect to the saturated norbornene resin. More preferably, it is 0.005-1.0 mass%, More preferably, it is 0.01-0.8 mass%, Most preferably, it is 0.02-1. 0% by mass.

(Other additives to saturated norbornene resin)
To the saturated norbornene resin film of the present invention, various additives other than fine particles (for example, plasticizers, ultraviolet inhibitors, deterioration inhibitors, optical property modifiers, etc.) other than fine particles can be added in each preparation step. . Moreover, the addition time may be added at any stage of the melt (dope) production process, or may be performed by adding a process of adding an additive at the end of the dope preparation process.

(Plasticizer)
As the plasticizer preferably added to the saturated norbornene resin film of the present invention, phosphate ester or carboxylic acid ester is used. Examples of phosphate esters include triphenyl phosphate (TPP) and tricresyl phosphate (TCP), cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate.

  Representative examples of the carboxylic acid ester include phthalic acid esters and citric acid esters. Examples of phthalic acid esters include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl phthalate (DPP) and diethyl hexyl phthalate (DEHP). Examples of citrate esters include triethyl O-acetylcitrate (OACTE) and tributyl O-acetylcitrate (OACTB), acetyltriethyl citrate, and acetyltributyl citrate.

  Examples of other carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters. Examples of glycolic acid esters include triacetin, tributyrin, butyl phthalyl butyl glycolate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, and butyl phthalyl butyl glycolate. Further trimethylolpropane tribenzoate, pentaerythritol tetrabenzoate, ditrimethylolpropane tetraacetate, ditrimethylolpropane tetrapropionate, pentaerythritol tetraacetate, sorbitol hexaacetate, sorbitol hexapropionate, sorbitol triacetate tripropionate, inositol pentaacetate Sorbitan tetrabutyrate is also preferably used.

  Among them, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, tributyl phosphate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diethyl hexyl phthalate, triacetin, ethyl phthalyl ethyl glycolate, trimethylol propane tribenzoate, Pentaerythritol tetrabenzoate, ditrimethylolpropane tetraacetate, pentaerythritol tetraacetate, sorbitol hexaacetate, sorbitol hexapropionate, sorbitol triacetate tripropionate and the like are preferable.

  Particularly preferred are triphenyl phosphate, diethyl phthalate, ethyl phthalyl ethyl glycolate, trimethylolpropane tribenzoate, pentaerythritol tetrabenzoate, ditrimethylolpropane tetraacetate, sorbitol hexaacetate, sorbitol hexapropionate, and sorbitol triacetate tripropionate. . These plasticizers may be used alone or in combination of two or more. The addition amount of the plasticizer is preferably 2 to 30% by mass, particularly 3 to 16% by mass, based on the saturated norbornene resin. Examples of the plasticizer include (di) pentaerythritol esters described in JP-A No. 11-124445, glycerol esters described in JP-A No. 11-246704, diglycerol esters described in JP-A No. 2000-63560, and the like. Examples thereof include citric acid esters described in Kaihei 11-92574 and substituted phenyl phosphates described in JP-A-11-90946.

(UV absorber)
The saturated norbornene resin film of the present invention preferably contains one or more ultraviolet absorbers. From the viewpoint of preventing deterioration of the liquid crystal, the ultraviolet absorbent for liquid crystal is preferably excellent in the ability to absorb ultraviolet light having a wavelength of 380 nm or less, and has little absorption of visible light having a wavelength of 400 nm or more from the viewpoint of liquid crystal display properties. Examples include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like. Particularly preferred ultraviolet absorbers are benzotriazole compounds and benzophenone compounds. Among these, a benzotriazole-based compound is preferable because unnecessary coloring with respect to the saturated norbornene resin is small.

  Preferred UV inhibitors include 2,6-di-tert-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol -Bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di tert-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 1,3,5-trimethyl-2,4,6 -Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate and the like can be mentioned.

  In particular, 2,6-di-tert-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] is most preferred. Further, for example, hydrazine-based metal deactivators such as N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine and tris (2,4-di-tert A phosphorus processing stabilizer such as -butylphenyl) phosphite may be used in combination. The amount of these compounds added is preferably 1 ppm to 3.0%, more preferably 10 ppm to 2% in terms of mass ratio with respect to the saturated norbornene resin.

  Commercially available products of these ultraviolet absorbers include the following, which can be used in the present invention. Benzotriazoles include TINUBIN P (Ciba Specialty Chemicals), TINUBIN 234 (Ciba Specialty Chemicals), TINUBIN 320 (Ciba Specialty Chemicals), TINUBIN 326 (Ciba Specialty Chemicals), TINUBIN 327 (Ciba Specialty Chemicals) Specialty Chemicals), TINUBIN 328 (Ciba Specialty Chemicals), Sumisorb 340 (Sumitomo Chemical), etc. Also, as benzophenone ultraviolet absorbers, Seasorb 100 (Cipro Kasei), Seasorb 101 (Cipro Kasei), Seasorb 101S (Cipro Kasei), Seasorb 102 (Cipro Kasei), Seasorb 103 (Cipro Kasei), Adekas Type LA-51 ( Asahi Denka), Chemisorp 111 (Chemipro Kasei), UVINUL D-49 (BASF), etc. Oxalic acid anilide UV absorbers include TINUBIN 312 (Ciba Specialty Chemicals) and TINUBIN 315 (Ciba Specialty Chemicals). In addition, SeaSorb 201 (Cipro Kasei) and Seasorb 202 (Cipro Kasei) are marketed as salicylic acid UV absorbers, and Seasorb 501 (Cipro Kasei) and UVINUL N-539 (BASF) as cyanoacrylate UV absorbers There is.

  A retardation adjusting agent for controlling optical anisotropy is optionally added to the saturated norbornene resin film of the present invention. In order to adjust the retardation of the saturated norbornene resin film, it is preferable to use an aromatic compound having at least two aromatic rings as a retardation increasing agent. An aromatic compound is used in 0.01-20 mass parts with respect to 100 mass parts of saturated norbornene resins. The aromatic compound is preferably used in the range of 0.05 to 15 parts by mass, and more preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the saturated norbornene resin. Two or more aromatic compounds may be used in combination. The aromatic ring of the aromatic compound includes an aromatic hetero ring in addition to the aromatic hydrocarbon ring. The aromatic hydrocarbon ring is particularly preferably a 6-membered ring (that is, a benzene ring). The aromatic heterocycle is generally an unsaturated heterocycle. The aromatic heterocycle is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring. Aromatic heterocycles generally have the most double bonds. As the hetero atom, a nitrogen atom, an oxygen atom and a sulfur atom are preferable, and a nitrogen atom is particularly preferable. Examples of aromatic heterocycles include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, pyridine ring , Pyridazine ring, pyrimidine ring, pyrazine ring and 1,3,5-triazine ring.

(Stabilizer)
The saturated norbornene resin film of the present invention preferably contains a stabilizer, and comprises a phenol stabilizer, a phosphorus (phosphite) stabilizer, a thioether stabilizer, a tin stabilizer and an amine stabilizer. Mention may be made of one or more stabilizers selected from the group. In the present invention, as a specific example of the phosphorus stabilizer, the compounds described in [0023] to [0039] of JP-A No. 2004-182979 are more preferable as long as the required performance is not impaired. It can be preferably used. Specific examples of the phosphite ester stabilizer include JP-A No. 51-70316, JP-A No. 10-306175, JP-A No. 57-78431, JP-A No. 54-157159, and JP-A No. 54-157159. The compounds described in JP-A-55-13765 can be used. Furthermore, as other stabilizers, the materials described in detail on pages 17 to 22 of the Japan Society for Invention and Technology (Public Technical Number 2001-1745, issued on March 15, 2001, Japan Society of Invention) are preferably used. Can do.

  Any known phenolic stabilizer may be used as the phenolic stabilizer. Preferable phenolic stabilizers include hindered phenolic stabilizers. Examples of hindered phenol stabilizers include, for example, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -s-tridian-2,4,6- (1H, 3H, 5H) trione, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydro Nannamate)] methane, and 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8 , 10-tetraoxaspiro [5,5] undecane, 2,6-di-t-butyl-p-cresol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'- Methylene bi (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), tetrakis [ Methylene (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butyl-phenyl) propionate, tris- 3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate, 2,6-di-tert-butyl-4-methylphenol, n-octadecyl 3- (3 ′, 5′-di-tert-butyl-4) '-Hydroxyphenyl) propionate, tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethi ] Methane, Tris [N- (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, Butylidene-1,1-bis- (2-methyl-4-hydroxy-5-t-butylphenyl) , Triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate]. High molecular weight polycyclic hindered phenol antioxidants are more preferred. More preferred is 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane.

  These are commercially available from Sumitomo Chemical as Sumilizer BHT, Sumilizer BP-76, Sumilizer BBM-S, Sumilizer GA-80, and from Ciba Specialty Chemicals as Irganox 1076, Irganox 1000, Irganox 3114, Irganox 245.

  As the phosphorus stabilizer, any conventionally known phosphorus stabilizer can be used in the present invention. Examples of preferred phosphorus stabilizers include bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol di-phosphite and tris (2,4-di-t-butylphenyl) phos Phyto, distearyl pentaerythritol diphosphite, trioctadecyl phosphite, trinonylphenyl phosphite, triphenyl phosphite, 9,10-dihydro-9-oxa · 10-phospha phenanthrene-10-oxide, tetrakis (2 , 4-di-t-butylphenyl) -4,4 ′ biphenylene diphosphite. A phosphite antioxidant is more preferred. More preferred is bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite. These are commercially available from Asahi Denka as Adeka Tab 1178, 2112, PEP-8, PEP-24G, PEP-36G, HP-10, and Sandostab P-EPQ from Clariant.

  As the thioether stabilizer, any known thioether stabilizer can be used in the present invention. Examples of preferred thioether stabilizers include tetrakis [methylene-3- (dodecylthio) propionate] methane, 3,3′-thiodipropionic acid, dilauryl thiodipropionate, distearyl thiodipropionate. . These are commercially available from Sumitomo Chemical as Sumilizer TPL, TPM, TPS, TDP. As the tin-based stabilizer, any known tin-based stabilizer can be used in the present invention. Examples of preferred tin stabilizers include octyl tin maleate polymer, monostearyl tin tris (isooctyl thioglycolate), and dibutyl tin dilaurate.

  As the amine stabilizer, any known amine stabilizer can be used in the present invention. Examples of preferred amine stabilizers include 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-[(2H-benzotriazol-2-yl) phenol]], Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, phenyl-β-naphthylamine, N, N′-di-sec-butyl-p-phenylene Diamine, N-N'-diphenyl-p-phenylenediamine, N-phenyl-N'-cyclohexyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, 4-benzoyloxy-2,2 , 6,6-tetramethylpiperazine, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate, bis [(1,2,2,6,6, -penta Til-4-piperidinyl) 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butyl malonate, tetrakis (2,2,6,6-tetramethyl-4-piperidinyl) 1 2,3,4-butane-tetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidinyl) 1,2,3,4-butane-tetracarboxylate and the like. These are commercially available from Asahi Denka as ADK STAB LA-57, LA-52, LA-67, LA-62 and LA-77, and from Ciba Specialty Chemicals as TINUVIN 765 and 144.

  Furthermore, the stabilizer used in the present invention is preferably a combination of a high molecular weight polycyclic hindered phenol antioxidant and a phosphate ester antioxidant. More preferably, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol- Combination with di-phosphite. The amount of the (C) stabilizer added in the present invention is preferably 0.01 to 3% by mass based on the saturated norbornene resin. More preferably, it is 0.03 to 2 mass%. More preferably, it is 0.05-1.5 mass%. When the added amount of the stabilizer is 0.01% by mass or more, the effect of the stabilizer can be easily obtained and coloring can be easily suppressed. Moreover, if the addition amount of a stabilizer is 3 mass% or less, a favorable surface shape is easy to be obtained.

<Properties of saturated norbornene resin film>
(Re and Rth)
When the saturated norbornene resin film of the present invention is used for optical applications, it is preferable that the in-plane retardation (Re) is from 0 nm to 500 nm and the retardation in the thickness direction (Rth) is from -300 nm to 700 nm. The Re of the saturated norbornene resin film of the present invention is more preferably 0 nm to 300 nm, further preferably 20 nm to 200 nm, and particularly preferably 40 nm to 150 nm. Furthermore, Rth is more preferably 30 nm to 500 nm, still more preferably 50 nm to 400 nm, and particularly preferably 100 nm to 300 nm. Further, those satisfying Re ≦ Rth are more preferable, and those satisfying Re × 2 ≦ Rth are more preferable.
Further, both the slow axis direction of Re and the fluctuation in the direction perpendicular to the slow axis are preferably 5% or less, and both the fluctuation of Rth in the slow axis direction and the direction perpendicular to the slow axis are both 5%. % Or less is preferable.

  In this specification, Re and Rth respectively represent in-plane retardation and retardation in the thickness direction at a wavelength λ. Re is measured with KOBRA 21ADH (manufactured by Oji Scientific Instruments Co., Ltd.) by making light having a wavelength of λ nm incident in the normal direction of the film. Rth was measured by making light having a wavelength λ nm incident from a direction inclined + 40 ° with respect to the film normal direction with the Re, in-plane slow axis (determined by KOBRA 21ADH) as the tilt axis (rotation axis). Retardation value and retardation value measured by making light of wavelength λ nm incident from a direction inclined by −40 ° with respect to the film normal direction with the in-plane slow axis as the tilt axis (rotation axis) 3 in total KOBRA 21ADH is calculated based on retardation values measured in two or more directions. Here, as the assumed value of the average refractive index, the values in the polymer handbook (JOHN WILEY & SONS, INC) and catalogs of various optical films can be used. Those whose average refractive index is not known can be measured with an Abbe refractometer. The average refractive index values of main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), Polystyrene (1.59). KOBRA 21ADH calculates nx, ny, and nz by inputting these assumed values of average refractive index and film thickness.

  In actuality, the film was conditioned at 25 ° C. and 60% relative humidity for 24 hours, and then measured using an automatic birefringence meter (KOBRA-21ADH: manufactured by Oji Scientific Instruments) at 25 ° C./relative At a humidity of 60%, the phase difference at a wavelength of 590 nm was measured from a direction inclined in increments of 10 ° from + 50 ° to −50 ° from the normal to the film surface with the direction perpendicular to the film surface and the slow axis as the rotation axis. The inner retardation value (Re) and the retardation value (Rth) in the film thickness direction were calculated. Unless otherwise specified, Re and Rth refer to this value.

(Thickness)
The thickness of the saturated norbornene resin film of the present invention is preferably 10 to 300 μm, more preferably 20 to 250 μm, still more preferably 30 to 200 μm, and the thickness distribution is preferably within ± 8% of the average value, More preferably, it is within ± 5%, and further preferably within ± 3%. The variation in thickness per cm is usually 5% or less, preferably 3% or less, more preferably 1% or less, and particularly preferably 0.5% or less.

(Residual solvent amount)
The residual solvent amount of the saturated norbornene resin film of the present invention is 0.01% by mass or less (0% by mass to 0.01% by mass). The amount of residual solvent is preferably 0% by mass to 0.005% by mass, more preferably 0% by mass to 0.001% by mass.
The type of the residual solvent is not particularly limited as long as it is a general organic solvent. For example, halogen-containing organic solvents having 1 to 10 carbon atoms (for example, dichloromethane, chloroform, etc.), esters having 3 to 12 carbon atoms (for example, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, and Pentyl acetate, etc.), ketones having 3 to 12 carbon atoms (for example, acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and methylcyclohexanone), ethers having 3 to 12 carbon atoms ( For example, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole and phenetole), an organic solvent having two or more kinds of functional groups (for example, 2-ethoxyethyl acetate) , 2-methoxyethanol and 2-butoxyethanol), alcohols (for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butyl alcohol, 1-pentanol, 2- Methyl-2-butanol, cyclohexanol, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol, etc.), saturated or unsaturated hydrocarbons (eg , Cyclohexane, hexane, benzene, toluene and xylene).

<Method for producing saturated norbornene resin film>
"Characteristic"
The method for producing a saturated norbornene resin film of the present invention includes a step of melt-forming a mixture of a saturated norbornene resin and a polymer having 0.01 to 5% by mass of fluorine atoms based on the solid content of the saturated norbornene resin. It is characterized by that.

<Melting film formation>
(1) Melting The saturated norbornene resin and additive are preferably mixed and pelletized prior to melt film formation. By pelletizing, surging in the hopper of the melt extruder is suppressed and stable supply becomes possible. Preferably, the pellet size is such cross-sectional area is 1 mm ² to 300 mm ^2, a length 1Mm～30mm, and more preferably the cross-sectional area of 2 mm ² 100 mm ^2, length 1.5Mm～10mm.
The saturated norbornene resin pellets are put into a melt extruder, dehydrated at 100 ° C. to 200 ° C. for 1 minute to 10 hours, and then kneaded and extruded. Kneading can be performed using a single-screw or twin-screw extruder.

  The saturated norbornene resin is supplied into the cylinder through the supply port of the extruder. FIG. 1 shows a schematic diagram of a typical extruder 22 that can be used in the present invention. In the cylinder 32, in order from the supply port 40 side, a supply unit (region A) for quantitatively transporting the saturated norbornene resin supplied from the supply port, a compression unit (region B) for melt-kneading and compressing the saturated norbornene resin, and melt-kneading -It is comprised with the measurement part (area | region C) which measures the saturated saturated norbornene resin. In order to prevent the melted resin from being oxidized by the remaining oxygen, it is more preferable to carry out the inside of the extruder in an inert (nitrogen or the like) air flow or while evacuating it using a vented extruder. The screw compression ratio of the extruder is preferably set to 2.5 to 4.5, and L / D is set to 20 to 70. Here, the screw compression ratio is represented by the volume ratio between the supply unit A and the metering unit C, that is, the volume per unit length of the supply unit A ÷ the volume per unit length of the metering unit C. It is calculated using the outer diameter d1 of the shaft, the outer diameter d2 of the screw shaft of the measuring part C, the groove part diameter a1 of the supply part A, and the groove part diameter a2 of the measuring part C. L / D is the ratio of the cylinder length to the cylinder inner diameter. The extrusion temperature is preferably set to 240 to 320 ° C, more preferably 250 to 310 ° C, and still more preferably 260 ° C to 300 ° C.

As the type of the extruder, a single-screw extruder having a relatively low equipment cost is generally used, and there are screw types such as full flight, mudock, and dalmage, but the full flight type is preferable. In addition, although the equipment cost is effective, it is possible to use a twin-screw extruder that can be extruded while volatilizing unnecessary volatile components by providing a vent port in the middle by changing the screw segment. There are two types of shaft extruders, the same direction and the different direction, which can be used. However, the type of the same direction rotation with high self-cleaning performance is preferred because a stagnant portion is hardly generated. The twin-screw extruder is effective, but it is suitable for forming a saturated norbornene resin because it has high kneadability and high resin supply performance and can be extruded at a low temperature. By properly arranging the vent port, it is possible to use the saturated norbornene pellets and powder in an undried state as they are. Also, film smears produced during film formation can be reused as they are without drying.
In addition, although the diameter of a preferable screw changes with target extrusion rates per unit time, it is 10 mm-300 mm, More preferably, it is 20 mm-250 mm, More preferably, it is 30 mm-150 mm.

(2) Filtration In order to filter foreign matters in the resin and avoid damage to the gear pump due to foreign matters, it is preferable to perform so-called breaker plate type filtration in which a filter medium is provided at the outlet of the extruder. In order to filter foreign matter with higher accuracy, it is preferable to provide a filtration device incorporating a so-called leaf type disk filter after passing through the gear pump. Filtration can be performed by providing one filtration section, or multistage filtration performed by providing a plurality of places. The filtration accuracy of the filter medium is preferably higher, but the filtration accuracy is preferably 15 μm to 3 μm, more preferably 10 μm to 3 μm, because of the pressure resistance of the filter medium and the increase in the filtration pressure due to clogging of the filter medium. In particular, when using a leaf-type disk filter device that finally filters foreign matter, it is preferable to use a filter medium with high filtration accuracy in terms of quality, and it is adjusted by the number of loaded sheets to ensure the suitability of pressure resistance and filter life. Is possible. The type of filter medium is preferably a steel material because it is used under high temperature and high pressure. Among steel materials, stainless steel, steel, etc. are particularly preferable, and stainless steel is particularly preferable in terms of corrosion. . As a configuration of the filter medium, for example, a sintered filter medium formed by sintering metal long fibers or metal powder can be used in addition to a knitted wire, and a sintered filter medium is preferable in terms of filtration accuracy and filter life.

(3) Gear pump To improve the thickness accuracy, it is important to reduce the fluctuation of the discharge amount. A gear pump is provided between the extruder and the die to supply a certain amount of saturated norbornene resin from the gear pump. It is effective to do. A gear pump is accommodated in a state where a pair of gears consisting of a drive gear and a driven gear are engaged with each other, and the drive gear is driven to engage and rotate the two gears so that a melted state is generated from the suction port formed in the housing. Resin is sucked into the cavity, and a certain amount of the resin is discharged from a discharge port formed in the housing. Even if there is a slight fluctuation in the resin pressure at the front end of the extruder, the fluctuation is absorbed by using a gear pump, the fluctuation in the resin pressure downstream of the film forming apparatus becomes very small, and the thickness fluctuation is improved. By using a gear pump, it is possible to keep the fluctuation range of the resin pressure in the die portion within ± 1%.
In order to improve the quantitative supply performance by the gear pump, a method of controlling the pressure before the gear pump to be constant by changing the number of rotations of the screw can also be used. In addition, a high-precision gear pump using three or more gears that eliminate the gear pump gear variation is also effective.

Other advantages of using a gear pump are that the pressure at the screw tip can be reduced to form a film, reducing energy consumption, preventing rise in resin temperature, improving transport efficiency, shortening the residence time in the extruder, L / D can be expected to be shortened. Also, when using a filter to remove foreign matter, if there is no gear pump, the amount of resin supplied from the screw may fluctuate as the filtration pressure rises. It can be resolved. On the other hand, the disadvantages of gear pumps are that the length of the equipment will be longer depending on the equipment selection method, the resin residence time will be longer, and the shearing stress of the gear pump may cause the molecular chain to break. is required.
The preferred residence time of the resin from the supply port through the extruder until it exits the die is 2 minutes to 60 minutes, more preferably 3 minutes to 40 minutes, and even more preferably 4 minutes to 30 minutes. is there.

  Since the flow of the polymer for bearing circulation of the gear pump is deteriorated, the sealing by the polymer in the drive part and the bearing part is deteriorated, and there is a problem that the fluctuation of the metering and liquid feeding extrusion pressure becomes large. A gear pump design (especially clearance) that matches the melt viscosity is required. Moreover, since the stay part of a gear pump causes deterioration of saturated norbornene resin, a structure with as little stay as possible is preferable. The polymer pipe and adapter that connect the extruder and gear pump or the gear pump and die also need to be designed with as little stagnation as possible. To stabilize the extrusion pressure, it is preferable to make the temperature fluctuation as small as possible. Generally, a band heater having a low equipment cost is often used for heating the polymer tube, but it is more preferable to use an aluminum cast heater with less temperature fluctuation.

(4) Die The saturated norbornene resin is melted by the extruder configured as described above, and the molten resin is continuously fed to the die via a filter and a gear pump as necessary. As long as the die is designed so that the molten resin stays in the die, any type of commonly used T die, fishtail die, and hanger coat die may be used. Moreover, there is no problem in placing a static mixer for improving the uniformity of the resin temperature immediately before the die. The clearance at the die outlet is generally 1.0 to 5.0 times the film thickness, preferably 1.2 to 3 times, more preferably 1.3 to 2 times. A lip clearance of 1.0 times or more of the film thickness is preferable because a sheet having a good surface shape can be easily obtained by film formation. Moreover, it is preferable if the lip clearance is 5.0 times or less of the film thickness because the thickness accuracy of the sheet can be easily increased. The die is a very important facility for determining the thickness accuracy of the film, and a die capable of strictly controlling the thickness adjustment is preferable. Normally, the thickness can be adjusted at intervals of 40 to 50 mm, but preferably a type capable of adjusting the film thickness at intervals of 35 mm or less, more preferably at intervals of 25 mm or less. In addition, it is important to have a design that minimizes the temperature unevenness of the die and the flow velocity unevenness in the width direction. An automatic thickness adjustment die that measures the downstream film thickness, calculates the thickness deviation, and feeds back the result to the die thickness adjustment is also effective in reducing the thickness fluctuation in long-term continuous production.
A single-layer film forming apparatus with a low equipment cost is generally used for manufacturing the film, but in some cases, a film having two or more types of structures can also be manufactured using a multilayer film forming apparatus in order to provide a functional layer on the outer layer. Is possible. In general, the functional layer is preferably thinly laminated on the surface layer, but the layer ratio is not particularly limited.

(5) Casting By the above method, the molten resin extruded from the die onto the sheet is cooled and solidified on a casting drum to obtain a film. At this time, it is preferable to use a method such as an electrostatic application method, an air knife method, an air chamber method, a vacuum nozzle method, or a touch roll method to increase the adhesion between the casting drum and the melt-extruded sheet. Such an adhesion improving method may be performed on the entire surface of the melt-extruded sheet or a part thereof. In particular, a method called “edge pinning”, in which only both ends of the film are brought into close contact with each other, is often used, but is not limited thereto.
More preferably, a plurality of casting drums are used for slow cooling. In particular, it is relatively common to use three cooling rolls, but this is not a limitation. The diameter of the roll is preferably 50 mm to 5000 mm, more preferably 100 mm to 2000 mm, and still more preferably 150 mm to 1000 mm. The interval between the plural rolls is preferably 0.3 mm to 300 mm, more preferably 1 mm to 100 mm, and still more preferably 3 mm to 30 mm.
The melting temperature is preferably 200 to 320 ° C, more preferably 230 to 310 ° C, still more preferably 250 to 300 ° C, and the temperature of the casting drum is preferably 80 to 170 ° C, more preferably 90 ° C to 160 ° C, still more preferably. Is cast at 100 ° C to 150 ° C.
Then, it peels off from a casting drum, winds up after passing through a nip roll. The winding speed is preferably 10 m / min to 100 m / min, more preferably 15 m / min to 80 m / min, still more preferably 20 m / min to 70 m / min.

The film forming width is preferably 0.7 m to 5 m, more preferably 1 m to 4 m, and still more preferably 1.3 m to 3 m. The thickness of the unstretched film thus obtained is preferably 30 μm to 400 μm, more preferably 40 μm to 300 μm, and still more preferably 50 μm to 200 μm.
The thickness unevenness of the formed saturated norbornene resin film is preferably 0% to 2% in both the longitudinal direction and the width direction, more preferably 0% to 1.5%, still more preferably 0% to 1%. The saturated norbornene resin film of the present invention can be obtained by stretching by the above-described method.
When the so-called touch roll method is used, the touch roll surface may be a resin such as rubber or Teflon (registered trademark) or a metal roll. Further, it is possible to use a roll called a flexible roll because the roll surface is slightly dented by the pressure when touched by reducing the thickness of the metal roll, and the crimping area is widened.
The touch roll temperature is preferably 60 ° C to 160 ° C, more preferably 70 ° C to 150 ° C, and still more preferably 80 ° C to 140 ° C.

(6) Winding The sheet thus obtained is preferably trimmed at both ends and wound. The trimmed portion is recycled as a film raw material of the same type or as a film raw material of a different type after being pulverized or after being subjected to a granulation process or a depolymerization / repolymerization process as necessary. May be used. As the trimming cutter, any type of rotary cutter, shear blade, knife, or the like may be used. As for the material, either carbon steel or stainless steel may be used. In general, it is preferable to use a cemented carbide blade or a ceramic blade because the life of the blade is long and the generation of chips is suppressed.
Moreover, it is also preferable from a viewpoint of scratch prevention to attach a lami film to at least one surface before winding. A preferable winding tension is 1 kg / m width to 50 kg / width, more preferably 2 kg / m width to 40 kg / width, and further preferably 3 kg / m width to 20 kg / width. A winding tension of 1 kg / m width or more is preferable because the film can be easily wound up uniformly. If the take-up tension is 50 kg / width or less, the film will not be tightly wound, the winding appearance will be beautiful, and the film's bump will be extended by the creep phenomenon, causing the film to wavy. Residual birefringence due to elongation of the film does not occur. It is preferable that the winding tension is detected by tension control in the middle of the line and wound while being controlled so as to have a constant winding tension. If there is a difference in film temperature depending on the location of the film production line, the length of the film may be slightly different due to thermal expansion. It is necessary to prevent tension.
The winding tension can be wound at a constant tension by controlling the tension control. However, it is more preferable that the winding tension is tapered according to the wound diameter to obtain an appropriate winding tension. Generally, the tension is gradually reduced as the winding diameter increases, but in some cases, it may be preferable to increase the tension as the winding diameter increases.

<Extension>
A film obtained by melt film formation can be stretched. When stretching, it is preferable to stretch at a high temperature. Stretching in the casting direction (longitudinal stretching) is usually carried out by changing the conveying speed between two or more pairs of nip rolls, and generally in a narrow roll interval (that is, the width of the saturated norbornene resin film ( Compared to W), the nip roll interval (L) used for stretching is small and the aspect ratio (L / W) is small). This is because the saturated norbornene resin film is also rapidly heated from the nip roll in order to stretch rapidly in a short time, and the nip roll also acts as a preheating roll.

By such stretching, Re and Rth can be expressed in the saturated norbornene resin film, but the relationship between Re and Rth preferably satisfies Re ≦ Rth, and more preferably satisfies Re × 2 ≦ Rth. preferable. In order to realize such a high Rth and low Re, it is preferable to stretch the film that has been longitudinally stretched as described above in the transverse (width) direction. In other words, the difference in orientation between the vertical direction and the horizontal direction becomes the difference in retardation (Re) in the plane, but by stretching in the horizontal direction, which is the orthogonal direction in addition to the vertical direction, the difference in vertical and horizontal orientation is reduced. It is possible to reduce the surface orientation (Re). On the other hand, since the area magnification increases by stretching in addition to the length, the thickness decreases. Along with this, the orientation in the thickness direction increases, and Rth can be increased. For stretching in the transverse direction, a method is generally used in which both ends are held by a chuck and widened by a tenter. The magnification of such transverse stretching is preferably more than 1 and 2.5 times or less, more preferably 1.05 to 2.2 times, and still more preferably 1.1 to 2 times. In addition, the draw ratio here is the value calculated | required by the following formula | equation.
Stretch ratio (times) = (Length after stretching) / (Length before stretching)
A preferable stretching temperature is Tg to (Tg + 100 ° C.), more preferably (Tg + 2 ° C.) to (Tg + 50 ° C.), and further preferably (Tg + 5 ° C.) to (Tg−30 ° C.). In the present invention, since stretching is performed on a saturated norbornene resin film having a property of expressing appropriate Re and Rth by stretching, stretching unevenness is hardly exhibited and desired Re and Rth are easily realized.

<Processing and use of saturated norbornene resin film>
The saturated norbornene resin film thus obtained may be used alone, or may be used in combination with a polarizing plate, and a liquid crystal layer or a layer with a controlled refractive index (low reflection layer) on these. ) Or a hard coat layer may be used. These can be achieved by the following steps.

"surface treatment"
The saturated norbornene resin film can be surface-treated to improve adhesion with each functional layer (for example, the undercoat layer and the back layer). For example, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment can be used. The glow discharge treatment here may be low-temperature plasma that occurs in a low-pressure gas of 10 ^{−3 to} 20 Torr, and plasma treatment under atmospheric pressure is also preferable. A plasma-excitable gas is a gas that is plasma-excited under the above-mentioned conditions, and examples thereof include chlorofluorocarbons such as argon, helium, neon, krypton, xenon, nitrogen, carbon dioxide, tetrafluoromethane, and mixtures thereof. It is done. Details of these are described in detail on pages 30 to 32 of the Japan Society of Invention Disclosure Technical Bulletin (Public Technical Number 2001-1745, published on March 15, 2001, Japan Society of Invention). In the plasma treatment at atmospheric pressure, which has been attracting attention in recent years, for example, irradiation energy of 20 to 500 kGy is used under 10 to 1000 keV, and more preferably irradiation energy of 20 to 300 kGy is used under 30 to 500 keV.
Of these, glow discharge treatment, corona treatment, and flame treatment are particularly preferred.
It is also preferable to provide an undercoat layer for adhesion to the functional layer. This layer may be applied after the above surface treatment or may be applied without the surface treatment. The details of the undercoat layer are described on page 32 of the Japan Society for Invention and Innovation (Public Technical Number 2001-1745, published on March 15, 2001, Japan Society of Invention). These surface treatment and undercoating processes can be incorporated at the end of the film forming process, can be performed alone, or can be performed in the functional layer application process described later.

《Granting functional layer》
The saturated norbornene resin film of the present invention is combined with the functional layer described in detail on pages 32 to 45 of the Japan Society for Invention and Technology (Publication No. 2001-1745, published on March 15, 2001, Japan Society of Invention). It is preferable. Among these, application of a polarizing film (polarizing plate), application of an optical compensation layer (optical compensation sheet), and application of an antireflection layer (antireflection film) are preferable. Hereinafter, these preferred embodiments will be described in order.

(A) Application of polarizing film (preparation of polarizing plate)
(E1) Material used Currently, a commercially available polarizing film is produced by immersing a stretched polymer in a solution of iodine or dichroic dye in a bath, and allowing the iodine or dichroic dye to penetrate into the binder. It is common to be done. As the polarizing film, a coating type polarizing film represented by Optiva Inc. can also be used. The iodine and the dichroic dye in the polarizing film develop polarizing performance by being oriented in the binder. As the dichroic dye, an azo dye, stilbene dye, pyrazolone dye, triphenylmethane dye, quinoline dye, oxazine dye, thiazine dye or anthraquinone dye is used. The dichroic dye is preferably water-soluble. The dichroic dye preferably has a hydrophilic substituent (for example, a sulfo group, an amino group, or a hydroxyl group). For example, the compounds described in page 58 of the Japan Society of Invention Disclosure Technique (Public Technical No. 2001-1745, published on March 15, 2001, Japan Society of Invention).

  As the binder for the polarizing film, either a polymer that can be crosslinked per se or a polymer that is crosslinked by a crosslinking agent can be used, and a plurality of combinations thereof can be used. Examples of the binder include methacrylate copolymer, styrene copolymer, polyolefin, polyvinyl alcohol and modified polyvinyl alcohol, poly (N-methylolacrylamide), polyester described in paragraph [0022] of JP-A-8-338913. , Polyimide, vinyl acetate copolymer, carboxymethyl cellulose, polycarbonate and the like. Silane coupling agents can be used as the polymer. Water-soluble polymers (for example, poly (N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol, and modified polyvinyl alcohol) are preferable, gelatin, polyvinyl alcohol, and modified polyvinyl alcohol are more preferable, and polyvinyl alcohol and modified polyvinyl alcohol are most preferable. . It is particularly preferable to use two types of polyvinyl alcohol or modified polyvinyl alcohol having different degrees of polymerization. The saponification degree of polyvinyl alcohol is preferably 70 to 100%, more preferably 80 to 100%. It is preferable that the polymerization degree of polyvinyl alcohol is 100-5000. The modified polyvinyl alcohol is described in JP-A-8-338913, JP-A-9-152509 and JP-A-9-316127. Two or more kinds of polyvinyl alcohol and modified polyvinyl alcohol may be used in combination.

The lower limit of the binder thickness is preferably 10 μm. The upper limit of the thickness is preferably as thin as possible from the viewpoint of light leakage of the liquid crystal display device. It is preferable that it is below the thickness (about 30 micrometers) of the commercially available polarizing plate now, it is preferable that it is 25 micrometers or less, and it is further more preferable that it is 20 micrometers or less.
The binder of the polarizing film may be cross-linked. A polymer or monomer having a crosslinkable functional group may be mixed in the binder, or a crosslinkable functional group may be imparted to the binder polymer itself. Crosslinking can be performed by light, heat, or pH change, and a binder having a crosslinked structure can be formed. The crosslinking agent is described in US Reissue Patent 23297. Boron compounds (for example, boric acid and borax) can also be used as a crosslinking agent. The addition amount of the crosslinking agent in the binder is preferably 0.1 to 20% by mass with respect to the binder. The orientation of the polarizing element and the moisture and heat resistance of the polarizing film are improved.
Even after the crosslinking reaction is completed, the amount of unreacted crosslinking agent is preferably 1.0% by mass or less, and more preferably 0.5% by mass or less. By doing in this way, a weather resistance improves.

(E2) Stretching of polarizing film The polarizing film is preferably dyed with iodine or a dichroic dye after the polarizing film is stretched (stretching method) or rubbed (rubbing method).
In the stretching method, the stretching ratio is preferably 2.5 to 30.0 times, and more preferably 3.0 to 10.0 times. Stretching can be performed by dry stretching in air. Moreover, you may implement wet extending | stretching in the state immersed in water. The stretch ratio of dry stretching is preferably 2.5 to 5.0 times, and the stretch ratio of wet stretching is preferably 3.0 to 10.0 times. Stretching may be performed in parallel to the MD direction (parallel stretching) or may be performed in an oblique direction (oblique stretching). These stretching operations may be performed once or divided into several times. By dividing into several times, it can be stretched more uniformly even at high magnification.

a) Parallel stretch method Prior to stretching, the PVA film is swollen. The swelling degree is preferably 1.2 to 2.0 times (mass ratio before swelling and after swelling). Thereafter, the film is stretched at a bath temperature of preferably 15 to 50 ° C., more preferably 17 to 40 ° C. in an aqueous medium bath or a dye bath for dissolving a dichroic substance while being continuously conveyed through a guide roll or the like. . Stretching can be achieved by gripping with two pairs of nip rolls and increasing the conveyance speed of the subsequent nip roll to be higher than that of the previous nip roll. The draw ratio is based on the length ratio after stretching / initial state (hereinafter the same), but the draw ratio is preferably 1.2 to 3.5 times, more preferably 1.5 to 3. 0 times. Thereafter, the film is dried at 50 ° C. to 90 ° C. to obtain a polarizing film.

b) Diagonal Stretching Method For this purpose, a method of stretching using a tenter projecting in an obliquely inclined direction as described in JP-A-2002-86554 can be used. Since this stretching is performed in the air, it is necessary to make it easy to stretch by adding water in advance. The preferred water content is 5% to 100%, more preferably 10% to 100%.
The temperature during stretching is preferably 40 ° C to 90 ° C, more preferably 50 ° C to 80 ° C. The relative humidity is preferably 50% to 100%, more preferably 70% to 100%, and still more preferably 80% to 100%. The traveling speed in the longitudinal direction is preferably 1 m / min or more, more preferably 3 m / min or more.
After the completion of stretching, the film is preferably dried at 50 ° C to 100 ° C, more preferably 60 ° C to 90 ° C, and preferably 0.5 minutes to 10 minutes. The drying time is more preferably 1 minute to 5 minutes.
The absorption axis of the polarizing film thus obtained is preferably 10 to 80 degrees, more preferably 30 to 60 degrees, and still more preferably 45 degrees (40 to 50 degrees).

(E3) Bonding The saturated norbornene resin film after the surface treatment and the polarizing film prepared by stretching are bonded to prepare a polarizing plate. The laminating direction is preferably such that the casting axis direction of the saturated norbornene resin film and the stretching axis direction of the polarizing plate are 45 degrees.
The bonding adhesive is not particularly limited, and examples include PVA resins (including modified PVA such as acetoacetyl group, sulfonic acid group, carboxyl group, oxyalkylene group), boron compound aqueous solution, epoxy adhesive, and the like. Of these, PVA resins and epoxy adhesives are preferred. The thickness of the adhesive layer is preferably 0.01 to 10 μm after drying, and particularly preferably 0.05 to 5 μm.
The polarizing plate thus obtained preferably has a higher light transmittance, and preferably has a higher degree of polarization. The transmittance of the polarizing plate is preferably in the range of 30 to 50%, more preferably in the range of 35 to 50%, and most preferably in the range of 40 to 50% in light having a wavelength of 550 nm. . The degree of polarization is preferably in the range of 90 to 100%, more preferably in the range of 95 to 100%, and most preferably in the range of 99 to 100% in light having a wavelength of 550 nm.
Furthermore, the polarizing plate thus obtained can be laminated with a λ / 4 plate to produce circularly polarized light. In this case, lamination is performed so that the slow axis of λ / 4 and the absorption axis of the polarizing plate are 45 degrees. At this time, λ / 4 is not particularly limited, but more preferably has a wavelength dependency such that the lower the wavelength, the smaller the retardation. Furthermore, it is preferable to use a polarizing film having an absorption axis inclined by 20 to 70 degrees with respect to the longitudinal direction and a λ / 4 plate made of an optically anisotropic layer made of a liquid crystalline compound.

(B) Application of optical compensation layer (creation of optical compensation sheet)
The optically anisotropic layer is for compensating the liquid crystal compound in the liquid crystal cell in the black display of the liquid crystal display device, and forms an alignment film on the saturated norbornene resin film, and further provides an optically anisotropic layer. It is formed by doing.

(Row 1) Alignment film An alignment film is provided on the surface-treated saturated norbornene resin film. This film has a function of defining the alignment direction of liquid crystalline molecules. However, if the alignment state is fixed after aligning the liquid crystalline compound, the alignment film plays the role, and thus is not necessarily an essential component of the present invention. That is, it is possible to produce the polarizing plate of the present invention by transferring only the optically anisotropic layer on the alignment film in which the alignment state is fixed onto the polarizer.
The alignment film is an organic compound (for example, ω-tricosanoic acid) formed by rubbing treatment of an organic compound (preferably polymer), oblique deposition of an inorganic compound, formation of a layer having a microgroove, or Langmuir-Blodgett method (LB film). , Dioctadecylmethylammonium chloride, methyl stearylate). Furthermore, an alignment film in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known.
The alignment film is preferably formed by polymer rubbing treatment. In principle, the polymer used for the alignment film has a molecular structure having a function of aligning liquid crystal molecules.
In the present invention, in addition to the function of aligning liquid crystalline molecules, a crosslink having a function of aligning a side chain having a crosslinkable functional group (for example, a double bond) to the main chain or aligning liquid crystalline molecules. It is preferable to introduce a functional functional group into the side chain.

  As the polymer used in the alignment film, either a polymer that can be crosslinked by itself or a polymer that is crosslinked by a crosslinking agent can be used, and a plurality of combinations thereof can be used. Examples of the polymer include methacrylate copolymers, styrene copolymers, polyolefins, polyvinyl alcohols and modified polyvinyl alcohols, poly (N-methylol acrylamide) described in paragraph No. [0022] of JP-A-8-338913, for example. , Polyester, polyimide, vinyl acetate copolymer, carboxymethyl cellulose, polycarbonate and the like. Silane coupling agents can be used as the polymer. Water-soluble polymers (for example, poly (N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol, and modified polyvinyl alcohol) are preferable, gelatin, polyvinyl alcohol, and modified polyvinyl alcohol are more preferable, and polyvinyl alcohol and modified polyvinyl alcohol are most preferable. . It is particularly preferable to use two types of polyvinyl alcohol or modified polyvinyl alcohol having different degrees of polymerization. The saponification degree of polyvinyl alcohol is preferably 70 to 100%, more preferably 80 to 100%. It is preferable that the polymerization degree of polyvinyl alcohol is 100-5000.

A side chain having a function of aligning liquid crystal molecules generally has a hydrophobic group as a functional group. The specific type of functional group is determined according to the type of liquid crystal molecule and the required alignment state. For example, the modifying group of the modified polyvinyl alcohol can be introduced by copolymerization modification, chain transfer modification or block polymerization modification. Examples of modifying groups include hydrophilic groups (carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, amino groups, ammonium groups, amide groups, thiol groups, etc.), hydrocarbon groups having 10 to 100 carbon atoms, fluorine atoms Examples include substituted hydrocarbon groups, thioether groups, polymerizable groups (unsaturated polymerizable groups, epoxy groups, azirinidyl groups, etc.), alkoxysilyl groups (trialkoxy, dialkoxy, monoalkoxy), and the like. Specific examples of these modified polyvinyl alcohol compounds include those described in, for example, paragraph numbers [0022] to [0145] of JP-A No. 2000-155216 and paragraph numbers [0018] to [0022] of JP-A No. 2002-62426. Etc.
When a side chain having a crosslinkable functional group is bonded to the main chain of the alignment film polymer, or a crosslinkable functional group is introduced into a side chain having a function of aligning liquid crystalline molecules, the alignment film polymer and the optically anisotropic film The polyfunctional monomer contained in the conductive layer can be copolymerized. As a result, not only between the polyfunctional monomer and the polyfunctional monomer, but also between the alignment film polymer and the alignment film polymer and between the polyfunctional monomer and the alignment film polymer is firmly bonded by a covalent bond. Therefore, the strength of the optical compensation sheet can be remarkably improved by introducing the crosslinkable functional group into the alignment film polymer.

The crosslinkable functional group of the alignment film polymer preferably contains a polymerizable group in the same manner as the polyfunctional monomer. Specific examples include those described in JP-A 2000-155216, paragraph numbers [0080] to [0100]. Apart from the crosslinkable functional group, the alignment film polymer can also be crosslinked using a crosslinking agent.
Examples of the crosslinking agent include aldehydes, N-methylol compounds, dioxane derivatives, compounds that act by activating carboxyl groups, active vinyl compounds, active halogen compounds, isoxazole, and dialdehyde starch. Two or more kinds of crosslinking agents may be used in combination. Specific examples include compounds described in paragraph numbers [0023] to [0024] of JP-A No. 2002-62426. Aldehydes having high reaction activity, particularly glutaraldehyde are preferred.

0.1-20 mass% is preferable with respect to a polymer, and, as for the addition amount of a crosslinking agent, 0.5-15 mass% is more preferable. The amount of the unreacted crosslinking agent remaining in the alignment film is preferably 1.0% by mass or less, and more preferably 0.5% by mass or less. By adjusting in this way, even if the alignment film is used for a long time in a liquid crystal display device or left in a high temperature and high humidity atmosphere for a long time, sufficient durability without reticulation can be obtained. May occur.
The alignment film can be basically formed by applying the polymer on the transparent support containing the alignment film forming material and the crosslinking agent, followed by drying by heating (crosslinking) and rubbing treatment. As described above, the crosslinking reaction may be carried out at any time after coating on the transparent support. When a water-soluble polymer such as polyvinyl alcohol is used as the alignment film forming material, the coating solution is preferably a mixed solvent of an organic solvent (for example, methanol) having a defoaming action and water. The ratio of water: methanol is preferably 0: 100 to 99: 1, and more preferably 0: 100 to 91: 9. Thereby, generation | occurrence | production of a bubble is suppressed and the defect of the layer surface of an alignment film and also an optically anisotropic layer reduces remarkably.

The alignment film is preferably applied by spin coating, dip coating, curtain coating, extrusion coating, rod coating, or roll coating. The rod coating method is particularly preferable. The film thickness after drying is preferably 0.1 to 10 μm. Heating and drying can be performed at 20 ° C to 110 ° C. In order to form a sufficient crosslink, 60 ° C to 100 ° C is preferable, and 80 ° C to 100 ° C is particularly preferable. The drying time can be 1 minute to 36 hours, preferably 1 minute to 30 minutes. The pH is also preferably set to an optimum value for the crosslinking agent to be used. When glutaraldehyde is used, the pH is 4.5 to 5.5, and 5 is particularly preferable.
The alignment film is provided on the transparent support or the undercoat layer. The alignment film can be obtained by rubbing the surface after crosslinking the polymer layer as described above.
For the rubbing treatment, a treatment method widely adopted as a liquid crystal alignment treatment process of LCD can be applied. That is, a method of obtaining the orientation by rubbing the surface of the orientation film in a certain direction using paper, gauze, felt, rubber, nylon, polyester fiber or the like can be used. Generally, it is carried out by rubbing several times using a cloth or the like in which fibers having a uniform length and thickness are planted on average.

In industrial implementation, this is achieved by bringing the rotating rubbing roll into contact with the film with the polarizing film being transported. Is preferably 30 μm or less. The film wrap angle on the rubbing roll is preferably 0.1 to 90 °. However, as described in JP-A-8-160430, a stable rubbing treatment can be obtained by winding 360 ° or more. As for the conveyance speed of a film, 1-100 m / min is preferable. It is preferable to select an appropriate rubbing angle in the range of 0 to 60 °. When used in a liquid crystal display device, 40 to 50 ° is preferable, and 45 ° is particularly preferable.
The thickness of the alignment film thus obtained is preferably in the range of 0.1 to 10 μm.

Next, the liquid crystalline molecules of the optically anisotropic layer are aligned on the alignment film. Thereafter, as necessary, the alignment film polymer and the polyfunctional monomer contained in the optically anisotropic layer are reacted, or the alignment film polymer is crosslinked using a crosslinking agent.
The liquid crystalline molecules used in the optically anisotropic layer include rod-like liquid crystalline molecules and discotic liquid crystalline molecules. The rod-like liquid crystal molecules and the disk-like liquid crystal molecules may be high-molecular liquid crystals or low-molecular liquid crystals, and further include those in which low-molecular liquid crystals are cross-linked and no longer exhibit liquid crystallinity.

(Ro 2) Rod-like liquid crystalline molecules As rod-like liquid crystalline molecules, azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenyl Pyrimidines, alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used.
The rod-like liquid crystalline molecule includes a metal complex. In addition, a liquid crystal polymer containing a rod-like liquid crystalline molecule in a repeating unit can also be used as the rod-like liquid crystalline molecule. In other words, the rod-like liquid crystal molecule may be bonded to a (liquid crystal) polymer.
For rod-like liquid crystalline molecules, see Chapter 4, Chapter 7 and Chapter 11 of the Chemical Chemistry of the Quarterly Chemical Review Vol. 22, Liquid Crystal Chemistry (1994), and the 142nd Committee of the Japan Society for the Promotion of Science. Described in Chapter 3.
The birefringence of the rod-like liquid crystal molecule is preferably in the range of 0.001 to 0.7.
The rod-like liquid crystalline molecule preferably has a polymerizable group in order to fix its alignment state. The polymerizable group is preferably a radical polymerizable unsaturated group or a cationic polymerizable group. Specifically, for example, the polymerizable group described in paragraphs [0064] to [0086] of JP-A No. 2002-62427 can be used. Liquid crystal compounds.

(Row 3) Discotic liquid crystalline molecules Discotic liquid crystalline molecules include C.I. Destrade et al., Mol. Cryst. 71, 111 (1981), benzene derivatives described in C.I. Destrade et al., Mol. Cryst. 122, 141 (1985), Physics lett, A, 78, 82 (1990); Kohne et al., Angew. Chem. 96, page 70 (1984) and the cyclohexane derivatives described in J. Am. M.M. Lehn et al. Chem. Commun. , 1794 (1985), J. Am. Zhang et al., J. Am. Chem. Soc. 116, 2655 (1994), azacrown type and phenylacetylene type macrocycles are included.

As a discotic liquid crystalline molecule, a compound having liquid crystallinity having a structure in which a linear alkyl group, an alkoxy group, and a substituted benzoyloxy group are radially substituted as a side chain of the mother nucleus with respect to the mother nucleus at the center of the molecule Is also included. The molecule or the assembly of molecules is preferably a compound that has rotational symmetry and can give a certain orientation. In the optically anisotropic layer formed from the discotic liquid crystalline molecules, the compound finally contained in the optically anisotropic layer does not need to be a discotic liquid crystalline molecule. Also included are compounds that have a group that reacts with heat or light, and that eventually polymerize or cross-link by reaction with heat or light to increase the molecular weight and lose liquid crystallinity. Preferred examples of the discotic liquid crystalline molecules are described in JP-A-8-50206. The polymerization of discotic liquid crystalline molecules is described in JP-A-8-27284.
In order to fix the discotic liquid crystalline molecules by polymerization, it is necessary to bond a polymerizable group as a substituent to the discotic core of the discotic liquid crystalline molecules. A compound in which the discotic core and the polymerizable group are bonded via a linking group is preferable, whereby the orientation state can be maintained even in the polymerization reaction. Examples thereof include compounds described in paragraph numbers [0151] to [0168] of JP-A No. 2000-155216.

It increases or decreases in the depth direction of the optically anisotropic layer and with increasing distance from the plane of the polarizing film. The angle preferably decreases with increasing distance. Further, the change in angle can be a continuous increase, a continuous decrease, an intermittent increase, an intermittent decrease, a change including a continuous increase and a continuous decrease, or an intermittent change including an increase and a decrease. The intermittent change includes a region where the inclination angle does not change in the middle of the thickness direction. Even if the angle includes a region where the angle does not change, the angle only needs to increase or decrease as a whole. Furthermore, it is preferable that the angle changes continuously.
The average direction of the major axis of the discotic liquid crystalline molecules on the polarizing film side can be generally adjusted by selecting a discotic liquid crystalline molecule or an alignment film material, or by selecting a rubbing treatment method. In addition, the major axis (disk surface) direction of the surface-side (air-side) discotic liquid crystalline molecules is generally adjusted by selecting the type of additive used together with the discotic liquid crystalline molecules or discotic liquid crystalline molecules. be able to. Examples of the additive used together with the discotic liquid crystalline molecule include a plasticizer, a surfactant, a polymerizable monomer and a polymer. The degree of change in the orientation direction of the major axis can also be adjusted by selecting liquid crystalline molecules and additives as described above.

(Raw 4) Other composition of optically anisotropic layer Along with the above liquid crystalline molecules, a plasticizer, a surfactant, a polymerizable monomer, etc. are used in combination to obtain coating film uniformity, film strength, and liquid crystal molecules. The orientation of the film can be improved. It is preferable that the compound has compatibility with the liquid crystal molecules and can change the tilt angle of the liquid crystal molecules or does not inhibit the alignment.
Examples of the polymerizable monomer include radically polymerizable or cationically polymerizable compounds. Preferably, it is a polyfunctional radically polymerizable monomer and is preferably copolymerizable with the above-described polymerizable group-containing liquid crystal compound. Examples thereof include those described in JP-A-2002-296423, paragraph numbers [0018] to [0020]. The amount of the compound added is generally in the range of 1 to 50% by mass and preferably in the range of 5 to 30% by mass with respect to the discotic liquid crystalline molecules.
Examples of the surfactant include conventionally known compounds, and fluorine compounds are particularly preferable. Specifically, for example, compounds described in JP-A-2001-330725, paragraph numbers [0028] to [0056] can be mentioned.

The polymer used together with the discotic liquid crystalline molecule is preferably capable of changing the tilt angle of the discotic liquid crystalline molecule.
A cellulose ester can be mentioned as an example of a polymer. Preferable examples of the cellulose ester include those described in paragraph No. [0178] of JP-A No. 2000-155216. The addition amount of the polymer is preferably in the range of 0.1 to 10% by mass, and preferably in the range of 0.1 to 8% by mass with respect to the liquid crystal molecule so as not to inhibit the alignment of the liquid crystal molecules. It is more preferable.
The discotic nematic liquid crystal phase-solid phase transition temperature of the discotic liquid crystalline molecules is preferably 70 to 300 ° C, more preferably 70 to 170 ° C.

(Raw 5) Formation of optically anisotropic layer The optically anisotropic layer is formed by applying a coating liquid containing liquid crystalline molecules and, if necessary, a polymerizable initiator and an optional component on the alignment film. Can be formed.
As a solvent used for preparing the coating solution, an organic solvent is preferably used. Examples of organic solvents include amides (eg N, N-dimethylformamide), sulfoxides (eg dimethyl sulfoxide), heterocyclic compounds (eg pyridine), hydrocarbons (eg benzene, hexane), alkyl halides (eg , Chloroform, dichloromethane, tetrachloroethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.
The coating liquid can be applied by a known method (for example, a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, or a die coating method).
The thickness of the optically anisotropic layer is preferably 0.1 to 20 μm, more preferably 0.5 to 15 μm, and most preferably 1 to 10 μm.

(Row 6) Fixation of alignment state of liquid crystalline molecules Aligned liquid crystalline molecules can be fixed while maintaining the alignment state. The immobilization is preferably performed by a polymerization reaction. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator. A photopolymerization reaction is preferred.
Examples of photopolymerization initiators include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ethers (US Pat. No. 2,448,828). No. description), α-hydrocarbon substituted aromatic acyloin compounds (U.S. Pat. No. 2,722,512), polynuclear quinone compounds (U.S. Pat. Nos. 3,046,127 and 2,951,758). ), Combinations of triarylimidazole dimers and p-aminophenyl ketones (described in US Pat. No. 3,549,367), acridine and phenazine compounds (Japanese Patent Laid-Open No. 60-105667), U.S. Pat. No. 4,239,850) and oxadiazole compounds (described in U.S. Pat. No. 4,212,970).

The amount of the photopolymerization initiator used is preferably in the range of 0.01 to 20% by mass, more preferably in the range of 0.5 to 5% by mass, based on the solid content of the coating solution.
It is preferable to use ultraviolet rays for light irradiation for polymerization of liquid crystalline molecules.
The irradiation energy is preferably in the range of ^{20mJ / cm 2 ~50J / cm 2} , more preferably in the range of 20~5000mJ / cm ^2, more preferably in the range of 100 to 800 mJ / cm ² . In order to accelerate the photopolymerization reaction, light irradiation may be performed under heating conditions.
A protective layer may be provided on the optically anisotropic layer.

It is also preferable to combine this optical compensation film and a polarizing film. Specifically, the optically anisotropic layer is formed by applying the coating liquid for the optically anisotropic layer as described above to the surface of the polarizing film. As a result, without using a polymer film between the polarizing film and the optically anisotropic layer, a thin polarizing plate with a small stress (strain × cross-sectional area × elastic modulus) associated with the dimensional change of the polarizing film is created. . When the polarizing plate according to the present invention is attached to a large liquid crystal display device, an image with high display quality can be displayed without causing problems such as light leakage.
The tilt angle of the polarizing film and the optical compensation layer may be stretched so as to match the angle formed by the transmission axis of the two polarizing plates bonded to both sides of the liquid crystal cell constituting the LCD and the vertical or horizontal direction of the liquid crystal cell. preferable. A normal inclination angle is 45 °. Recently, however, devices that are not necessarily 45 ° have been developed in transmissive, reflective, and transflective LCDs, and it is preferable that the stretching direction can be arbitrarily adjusted according to the design of the LCD.

(Row 7) Liquid crystal display device Each liquid crystal mode in which such an optical compensation film is used will be described.

(TN mode liquid crystal display)
It is most frequently used as a color TFT liquid crystal display device and is described in many documents. The alignment state in the liquid crystal cell in the TN mode black display is an alignment state in which the rod-like liquid crystalline molecules rise at the center of the cell and the rod-like liquid crystalline molecules lie in the vicinity of the cell substrate.

(OCB mode liquid crystal display)
This is a bend alignment mode liquid crystal cell in which rod-like liquid crystal molecules are aligned in a substantially opposite direction (symmetrically) between the upper and lower portions of the liquid crystal cell. A liquid crystal display device using a bend alignment mode liquid crystal cell is disclosed in US Pat. Nos. 4,583,825 and 5,410,422. Since the rod-like liquid crystal molecules are symmetrically aligned at the upper and lower portions of the liquid crystal cell, the bend alignment mode liquid crystal cell has a self-optical compensation function. Therefore, this liquid crystal mode is also called an OCB (Optically Compensated Bend) liquid crystal mode.
Similarly to the TN mode, the liquid crystal cell in the OCB mode is in a black display, and the alignment state in the liquid crystal cell is such that the rod-like liquid crystal molecules rise in the center of the cell and the rod-like liquid crystal molecules lie in the vicinity of the cell substrate. .

(VA mode liquid crystal display device)
The feature is that the rod-like liquid crystalline molecules are oriented substantially vertically when no voltage is applied. In the VA mode liquid crystal cell, (1) the rod-like liquid crystalline molecules are oriented substantially vertically when no voltage is applied. In addition to a narrowly defined VA mode liquid crystal cell (described in JP-A-2-176625) that is aligned substantially horizontally when a voltage is applied, (2) the VA mode is multi-domained to expand the viewing angle ( Liquid crystal cell (in MVA mode) (SID97, Digest of tech. Papers 28 (1997) 845), (3) Rod-like liquid crystal molecules are substantially vertically aligned when no voltage is applied, and twisted A liquid crystal cell in a domain alignment mode (n-ASM mode) (described in the proceedings 58-59 (1998) of the Japanese Liquid Crystal Society) and (4) a SURVAVAL mode liquid crystal cell (LCD interface) Announced at National 98).

(IPS mode liquid crystal display)
The feature is that the rod-like liquid crystalline molecules are aligned substantially horizontally in the plane when no voltage is applied, and this is characterized by switching by changing the orientation direction of the liquid crystal with or without voltage application. Specifically, as described in JP-A No. 2004-365941, JP-A No. 2004-12731, JP-A No. 2004-215620, JP-A No. 2002-221726, JP-A No. 2002-55341, and JP-A No. 2003-195333. Things can be used.

(Other liquid crystal display devices)
The ECB mode and STN mode liquid crystal display devices can be optically compensated in the same way as described above.

(C) Application of an antireflection layer (antireflection film)
The antireflection film generally comprises a low refractive index layer which is also an antifouling layer, and at least one layer having a higher refractive index than that of the low refractive index layer (ie, a high refractive index layer and a medium refractive index layer). It is provided above.
Colloidal metal by multilayer deposition of transparent thin films of inorganic compounds (metal oxides, etc.) with different refractive indexes by chemical vapor deposition (CVD) method, physical vapor deposition (PVD) method, sol-gel method of metal compounds such as metal alkoxides Examples include a method of forming a thin film by post-processing (ultraviolet irradiation: JP-A-9-157855, plasma processing: JP-A-2002-327310) after forming an oxide particle film.
On the other hand, various antireflection films formed by laminating and applying a thin film in which inorganic particles are dispersed in a matrix have been proposed as an antireflection film having high productivity.
The antireflection film which consists of the antireflection layer which provided the anti-glare property which the antireflection film by application | coating as mentioned above provided the surface of the uppermost layer with the shape of a fine unevenness | corrugation is also mentioned.
The saturated norbornene resin film of the present invention can be applied to any of the above methods, but the coating method (coating type) is particularly preferable.

(Her 1) Layer structure of coating type antireflection film An antireflection film comprising at least a medium refractive index layer, a high refractive index layer, and a low refractive index layer (outermost layer) in order on the substrate has the following relationship: Designed to have a satisfactory refractive index.
The refractive index of the high refractive index layer> The refractive index of the medium refractive index layer> The refractive index of the transparent support> The refractive index of the low refractive index layer. Also good. Furthermore, it may consist of a medium refractive index hard coat layer, a high refractive index layer and a low refractive index layer.
Examples thereof include JP-A Nos. 8-122504, 8-110401, 10-300902, JP-A 2002-243906, JP-A 2000-11706, and the like.
Other functions may be imparted to each layer, for example, an antifouling low refractive index layer or an antistatic high refractive index layer (for example, JP-A-10-206603, JP-A-2002). -243906 publication etc.) etc. are mentioned.
The haze of the antireflection film is preferably 5% or less, more preferably 3% or less. The strength of the film is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test according to JIS K5400.

(Her 2) High Refractive Index Layer and Medium Refractive Index Layer The antireflective coating layer having a high refractive index is formed from a curable film containing at least an inorganic compound ultrafine particle having a high refractive index with an average particle size of 100 nm or less and a matrix binder. Become.
Examples of the high refractive index inorganic compound fine particles include inorganic compounds having a refractive index of 1.65 or more, preferably those having a refractive index of 1.9 or more. Examples thereof include oxides such as Ti, Zn, Sb, Sn, Zr, Ce, Ta, La, and In, and composite oxides containing these metal atoms.
In order to obtain such ultrafine particles, the surface of the particles is treated with a surface treating agent (for example, silane coupling agents, etc .: JP-A Nos. 1-295503, 11-153703, 2000-9908). , Anionic compounds or organometallic coupling agents: Japanese Patent Application Laid-Open No. 2001-310432), a core-shell structure with high refractive index particles as a core (Japanese Patent Application Laid-Open No. 2001-166104, etc.), a specific dispersant Combined use (for example, Unexamined-Japanese-Patent No. 11-153703, US Patent 6,210,858B1, Unexamined-Japanese-Patent No. 2002-27776069 etc.) etc. are mentioned.
Examples of the material forming the matrix include conventionally known thermoplastic resins and curable resin films.

Further, the composition is selected from a polyfunctional compound-containing composition containing at least two radically polymerizable and / or cationically polymerizable groups, an organometallic compound containing a hydrolyzable group, and a partial condensate composition thereof. At least one composition is preferred. Examples thereof include compounds described in JP-A Nos. 2000-47004, 2001-315242, 2001-31871, and 2001-296401.
A curable film obtained from a colloidal metal oxide obtained from a hydrolyzed condensate of metal alkoxide and a metal alkoxide composition is also preferred. For example, it describes in Unexamined-Japanese-Patent No. 2001-293818.
The refractive index of the high refractive index layer is generally 1.70 to 2.20. The thickness of the high refractive index layer is preferably 5 nm to 10 μm, and more preferably 10 nm to 1 μm.
The refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.50 to 1.70.

(Her 3) Low Refractive Index Layer The low refractive index layer is formed by sequentially laminating on the high refractive index layer. The refractive index of the low refractive index layer is 1.20 to 1.55. Preferably it is 1.30-1.50.
It is preferable to construct as the outermost layer having scratch resistance and antifouling property. As means for greatly improving the scratch resistance, it is effective to impart slipperiness to the surface, and conventionally known thin film layer means such as introduction of silicone or introduction of fluorine can be applied.
The refractive index of the fluorine-containing compound is preferably 1.35 to 1.50. More preferably, it is 1.36-1.47. The fluorine-containing compound is preferably a compound containing a crosslinkable or polymerizable functional group containing fluorine atoms in the range of 35 to 80% by mass.
For example, paragraph numbers [0018] to [0026] in JP-A-9-222503, paragraph numbers [0019] to [0030] in JP-A-11-38202, and paragraph number [0027] in JP-A-2001-40284. To [0028], paragraph numbers [0012] to [0077] of JP 2000-284102 A, JP 2003-26732 A, paragraph numbers [0030] to [0047] of JP 2004-45462 A, and the like. And the compounds described.

The silicone compound is a compound having a polysiloxane structure, preferably containing a curable functional group or a polymerizable functional group in the polymer chain and having a crosslinked structure in the film. For example, reactive silicone (for example, Silaplane (manufactured by Chisso Corporation), silanol group-containing polysiloxane (Japanese Patent Laid-Open No. 11-258403, etc.) and the like can be mentioned.
The crosslinking or polymerization reaction of the fluorine-containing and / or siloxane polymer having a crosslinking or polymerizable group is performed simultaneously with or after the coating composition for forming the outermost layer containing a polymerization initiator, a sensitizer and the like is applied. It is preferable to carry out by light irradiation or heating.
Also preferred is a sol-gel cured film in which an organometallic compound such as a silane coupling agent and a specific fluorine-containing hydrocarbon group-containing silane coupling agent are cured by a condensation reaction in the presence of a catalyst.
For example, a polyfluoroalkyl group-containing silane compound or a partially hydrolyzed condensate thereof (Japanese Patent Laid-Open Nos. 58-142958, 58-147483, 58-147484, Japanese Patent Laid-Open No. 9-157582, Compounds described in JP-A-11-106704, etc.), silyl compounds containing a poly "perfluoroalkyl ether" group which is a fluorine-containing long chain group (JP 2000-117902 A, JP 2001-48590 A, Compounds described in JP 2002-53804 A) and the like.

The low refractive index layer has an average primary particle diameter of 1 to 150 nm such as a filler (for example, silicon dioxide (silica), fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride)) as an additive other than the above. A low refractive index inorganic compound, organic fine particles described in paragraphs [0020] to [0038] of JP-A-11-3820), silane coupling agents, slip agents, surfactants, and the like.
When the low refractive index layer is located below the outermost layer, the low refractive index layer may be formed by a vapor phase method (vacuum deposition method, sputtering method, ion plating method, plasma CVD method, etc.). The coating method is preferable because it can be manufactured at a low cost.
The film thickness of the low refractive index layer is preferably 30 to 200 nm, more preferably 50 to 150 nm, and most preferably 60 to 120 nm.

(Her 4) Hard coat layer The hard coat layer is provided on the surface of the transparent support in order to impart physical strength to the antireflection film. In particular, it is preferably provided between the transparent support and the high refractive index layer.
The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of a light and / or heat curable compound. The curable functional group is preferably a photopolymerizable functional group, and the hydrolyzable functional group-containing organometallic compound is preferably an organic alkoxysilyl compound.
Specific examples of these compounds are the same as those exemplified for the high refractive index layer.
Specific examples of the constituent composition of the hard coat layer include those described in JP-A Nos. 2002-144913, 2000-9908, and WO 00/46617.

The high refractive index layer can also serve as a hard coat layer. In such a case, it is preferable to form fine particles dispersed in the hard coat layer using the method described for the high refractive index layer.
The hard coat layer can also serve as an antiglare layer (described later) provided with particles having an average particle size of 0.2 to 10 μm to provide an antiglare function (antiglare function).
The film thickness of the hard coat layer can be appropriately designed depending on the application. The film thickness of the hard coat layer is preferably 0.2 to 10 μm, more preferably 0.5 to 7 μm.
The strength of the hard coat layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test according to JIS K5400. Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

(Her 5) Forward scattering layer The forward scattering layer is provided in order to give a viewing angle improvement effect when the viewing angle is inclined in the vertical and horizontal directions when applied to a liquid crystal display device. By dispersing fine particles having different refractive indexes in the hard coat layer, it can also serve as a hard coat function.
For example, Japanese Patent Application Laid-Open No. 11-38208 specifying a forward scattering coefficient, Japanese Patent Application Laid-Open No. 2000-199809 having a relative refractive index of a transparent resin and fine particles in a specific range, and Japanese Patent Application Laid-Open No. 2002 specifying a haze value of 40% or more. -107512 gazette etc. are mentioned.

(He 6) Other layers In addition to the above layers, a primer layer, an antistatic layer, an undercoat layer, a protective layer, and the like may be provided.

(He 7) Coating method Each layer of the anti-reflection film is formed by the dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating, micro gravure method and extrusion coating method (US Patent No. 1). 2, 681, 294 specification).

(He 8) Anti-glare function The antireflection film may have an anti-glare function that scatters external light. The antiglare function is obtained by forming irregularities on the surface of the antireflection film. When the antireflection film has an antiglare function, the haze of the antireflection film is preferably 3 to 30%, more preferably 5 to 20%, and most preferably 7 to 20%.
As a method for forming irregularities on the surface of the antireflection film, any method can be applied as long as these surface shapes can be sufficiently maintained. For example, a method of forming irregularities on the film surface using fine particles in the low refractive index layer (for example, JP 2000-271878 A), a lower refractive index layer (high refractive index layer, medium refractive index layer) Alternatively, a small amount (0.1 to 50% by mass) of relatively large particles (particle size 0.05 to 2 μm) is added to the hard coat layer to form a surface uneven film, and these shapes are maintained thereon. A method of providing a low refractive index layer (for example, JP 2000-281410 A, JP 2000-95893 A, JP 2001-100004 A, 2001-281407, etc.), an uppermost layer (antifouling layer) And a method of physically transferring the uneven shape onto the surface after coating (for example, as an embossing method, Japanese Patent Laid-Open Nos. 63-278839, 11-183710, 2000-275401) Include equal forth) and the like.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

Example 1
1-1) Saturated norbornene resin (1) Saturated norborn resin-AA (resin-AA)
6-methyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 10 parts by mass of a 15% cyclohexane solution of triethylaluminum as a polymerization catalyst, triethylamine 5 parts by mass and 10 parts by mass of a 20% cyclohexane solution of titanium tetrachloride were added to perform ring-opening polymerization in cyclohexane, and the resulting ring-opening polymer was hydrogenated with a nickel catalyst to obtain a polymer solution. This polymer solution was coagulated in isopropyl alcohol and dried to obtain a powdered resin-AA. The number average molecular weight of this resin was 40,000, the hydrogenation rate was 99.8% or more, and the Tg was 139 ° C. For Tg, 20 mg of a sample was put in a DSC measurement pan, and this was heated from 30 ° C. to 250 ° C. at 10 ° C./min in a nitrogen stream, then cooled to −30 ° C. at −10 ° C./min, and again 30 The temperature was determined by raising the temperature from 0 ° C. to 250 ° C. and setting Tg as the temperature at which the baseline starts to deviate from the low temperature side (the same applies hereinafter).

(2) Saturated norvol resin-BB (resin-BB)
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2.5, 1 ^7.10] -3- dodecene (specific monomer B) and 100 parts by mass, 5- (4-biphenyl carbonyl oxy) bicyclo [ 2.2.1] Charged 150 parts by mass of hept-2-ene (specific monomer A), 18 parts by mass of 1-hexene (molecular weight regulator), and 750 parts by mass of toluene into a nitrogen-substituted reaction vessel, This solution was heated to 60 ° C. Subsequently, 0.62 parts by mass of a toluene solution of triethylaluminum (1.5 mol / l) as a polymerization catalyst and tungsten hexachloride modified with t-butanol and methanol (t-butanol: methanol: By adding 3.7 parts by mass of a toluene solution (concentration 0.05 mol / l) of tungsten = 0.35 mol: 0.3 mol: 1 mol), the system is heated and stirred at 80 ° C. for 3 hours. A ring-opening polymer solution was obtained by a ring-opening polymerization reaction. The polymerization conversion rate in this polymerization reaction was 97%, and the intrinsic viscosity (η _inh ) of the obtained ring-opened polymer measured in chloroform at 30 ° C. was 0.65 dl / g.

The autoclave was charged with 4,000 parts by mass of the ring-opening polymer solution thus obtained, and 0.48 part by mass of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution. And a hydrogenation reaction was performed by heating and stirring for 3 hours under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C. After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover the coagulated product, and dried to obtain a hydrogenated polymer (specific cyclic polyolefin resin) (resin-BB). The hydrogenated polymer thus obtained was measured for hydrogenation rate of olefinically unsaturated bonds using 400 MHz, ¹ H-NMR, and found to be 99.9%. The Tg was 110 ° C., and when the number average molecular weight (Mn) and the mass average molecular weight (Mw) in terms of polystyrene were measured by the GPC method (solvent: tetrahydrofuran), the number average molecular weight (Mn) was 39,000 and the mass average The molecular weight (Mw) was 126,000, and the molecular weight distribution (Mw / Mn) was 3.23.

1-2) Melt film formation (1) Pelletization After the saturated norbornene resin-AA or saturated norbornene resin-BB is dried at 100 ° C. for 6 hours to have a water content of 0.07% by mass, the primary average particle size is 20 nm. 0.05% by mass of silica fine particles, 2% by mass of plasticizer biphenyldiphenyl phosphate, UV agent a {2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di- tert-butylanilino) -1,3,5-triazine}, 0.5% by mass, UV agent b {2 (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole } And 0.2 wt% of UV agent c {2 (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) -5-chlorobenzotriazole}, and As a stabilizer, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite 0.25% by mass, 2,2′-methylenebis [4- (1,1,3, 3-tetramethylbutyl) -6-[(2H-benzotriazol-2-yl) phenol]] 0.25% by weight and bis [(1,2,2,6,6-pentamethyl-4-piperidinyl) 2 -(3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate 0.25% by weight was added. Furthermore, the polymer which has a fluorine atom was added according to Table 1 (The addition amount of said each raw material shows the mass% with respect to saturated norbornene resin solid content).

(2) Melt film formation The saturated norbornene resin-AA or saturated norbornene resin-BB was molded into a cylindrical pellet having a diameter of 3 mm and a length of 5 mm. This was dried with a vacuum dryer at 110 ° C., the water content was adjusted to 0.1% or less, and then charged into a hopper adjusted to a temperature 10 ° C. lower than the Tg of the saturated norbornene resin. Next, the mixture was heated to 260 ° C. so that the melt viscosity was 5000 Pa · s (at this time, the melt viscosity was 5000 Pa · s or less), and further melted using a uniaxial kneader for 5 minutes, and then the melting temperature. The film was cast from a T-die set higher by 10 ° C. onto a casting drum set to (Tg-5 ° C.) and solidified to obtain a film. At this time, each level electrostatic application method (a 10 kV wire was placed 10 cm from the point where the melt was attached to the casting drum) was used. The solidified melt was peeled off and wound up. In addition, after trimming both ends (each 3% of the total width) just before winding, the both ends were subjected to a thicknessing process (knurling) having a width of 10 mm and a height of 50 μm. In each level, the width was 1.5 m, and 3000 m was wound at 30 m / min.

At this time, the distance between the T-die and the casting drum is 8 cm, the solidification speed is 30 ° C./second, the casting drum temperature is the first roll (upstream) (Tg-10 ° C.) and the second roll (upstream) (Tg-11 ° C.) The third roll (upstream) (Tg-12 ° C.) and the cooling rate was −15 ° C./second. The melt was melt extruded over 10 minutes. At this time, each level electrostatic application method (a 10 kV wire was placed 10 cm from the point where the melt was attached to the casting drum) was used. The solidified melt was peeled off and wound with a winding tension of 6 kg / cm ² via a nip roll. In addition, after trimming both ends (each 3% of the total width) immediately before winding, the both ends were subjected to thicknessing processing (knurling) having a width of 10 mm and a height of 50 μm, and then wound. For each level, the width was 1.5 m, and 500 m was wound at 30 m / min. The film thickness was prepared with a target of 80 μm.

1-3) Evaluation (1) Evaluation Method The measurement method and evaluation method for each saturated norbornene resin film thus obtained are described below.
(Daisy)
The evaluation of the die streak was carried out in accordance with the following by visually observing streaky unevenness seen in the casting direction under a reflected light source.
A: Dice lines were not seen.
B: Dice lines were slightly seen.
C: Dice lines were clearly recognized.
D: Dice lines were remarkably observed on the entire surface.

(Danmura)
The evaluation of danmura was carried out in accordance with the following by visually observing stepped irregularities seen in the width direction under a reflected light source.
A: Danmura was not seen.
B: Danmura was slightly observed.
C: Danmura was clearly recognized.
D: Danmura was remarkably observed on the entire surface.

(Re and Rth)
After conditioning the saturated norbornene resin film at 25 ° C. and 60% relative humidity for 24 hours, using an automatic birefringence meter (KOBRA-21ADH: manufactured by Oji Scientific Instruments) at 25 ° C. and 60% relative humidity, In-plane retardation is measured by measuring the phase difference at a wavelength of 590 nm from the direction tilted in increments of 10 ° from + 50 ° to −50 ° from the normal to the film surface with the slow axis as the rotation direction perpendicular to the film surface. The value (Re) and the retardation value (Rth) in the film thickness direction were calculated. Unless otherwise specified, Re and Rth refer to this value.

(Re unevenness, Rth unevenness)
In the MD direction sampling, sampling was performed at a size of 100 points and 1 cm square at 1 m intervals in the longitudinal direction. The sampling in the TD direction was sampled at an equal interval of 5 cm in a size of 1 cm square over the entire width of the film formation. The difference between the maximum value and the minimum value of each sample obtained was determined and used as Re unevenness and Rth unevenness.
(Thickness unevenness)
In the MD direction sampling, sampling was performed at a size of 100 points and 1 cm square at 1 m intervals in the longitudinal direction. The sampling in the TD direction was sampled at an equal interval of 5 cm in a size of 1 cm square over the entire width of the film formation. The thickness of each obtained sample was measured, and the difference between the maximum value and the minimum value of the thickness was determined and evaluated.

(Re humidity dependence and Rth humidity dependence)
Further, Re (10% RH) and Rth (10% RH) of these samples were determined at 25 ° C./relative humidity 10%. Further, these samples were similarly measured at 25 ° C. and a relative humidity of 80%, and Re (80% RH) and Rth (80% RH) were obtained. About each sample, the difference of Re and Rth was calculated | required, and Re humidity dependence and Rth humidity dependence were evaluated.

(Roll dirt)
When extruding from the T-die, the degree of contamination on the roll surface at the film end of the first roll was visually observed under a reflected light source and carried out as follows.
A: Dirt was not seen.
B: Dirt was slightly seen.
C: Dirt was clearly recognized.
D: Dirt was noticeable on the entire surface.

(Haze)
A sample of 40 mm × 80 mm was measured according to JIS K-6714 using a haze meter (HGM-2DP, Suga Test Instruments) at 25 ° C. and a relative humidity of 60%.

(Transparency)
The transparency of visible light (615 nm) was measured for a sample of 20 mm × 70 mm at 25 ° C. and a relative humidity of 60% using a transparency measuring device (AKA photoelectric tube colorimeter, KOTAKI Corporation).

(Molecular orientation axis)
Sample 70mm x 100mm was conditioned for 2 hours at 25 ° C and 65% relative humidity, and the phase difference when the incident angle at normal incidence was changed using an automatic birefringence meter (KOBRA21DH, Oji Scientific Co., Ltd.) The molecular orientation axis was calculated by measurement.

(Axis misalignment)
Using an automatic birefringence meter (KOBRA-21ADH, Oji Scientific Instruments Co., Ltd.), a sample misalignment angle of 70 mm × 100 mm was measured. Twenty points were measured at equal intervals over the entire width in the width direction, and the average absolute value was determined. The range of the slow axis angle (axis deviation) is the measurement of 20 points at equal intervals over the entire width direction, and the difference between the average of the absolute value of the axis deviation and the average of the four points from the smaller absolute value. Is taken.

(Kisimi)
Samples 100 mm × 200 mm and 75 mm × 100 mm were conditioned at 23 ° C. and 65% relative humidity for 2 hours, and a large film was placed on the table using a Tensilon tensile tester (RTA-100, Orientec Co., Ltd.). A small film with a 200 g weight was fixed. By pulling the weight in the horizontal direction, the force when moving and the force when moving were measured, and the coefficient of static friction was calculated according to the following equation.
F = μ × W (W: weight of weight (kgf))
Also, the dynamic friction (steel ball method) was conditioned for 2 hours at 23 ° C and 65% relative humidity on a 35 mm x 100 mm sample, and the sample was placed on the surface with the dynamic friction coefficient measuring instrument (Toyo Baldwin) The steel ball was lowered onto the sample and measured by sending a table.

(Curl value)
Sample 35mm x 3mm was conditioned for 24 hours at 25%, 55% and 85% relative humidity in a curl humidity chamber (HEIDON (No. YG53-168), Shinto Kagaku Co., Ltd.) And measured as a dry curl value. In addition, curling with wet was measured after standing for 30 minutes in water having a water temperature of 25 ° C.

(Moisture permeability coefficient)
A 70 mmφ sample was conditioned at 25 ° C./95% relative humidity and 40 ° C./95% relative humidity for 24 hours, respectively, with a moisture permeation tester (KK-70907, Toyo Seiki Co., Ltd.) according to JIS Z-0208. The amount of water (g / m ² ) per unit area was calculated. And the water vapor transmission rate was calculated | required by the mass before humidity-mass before humidity control. Further, as a compulsory evaluation, the moisture permeability coefficient was measured after conditioning for 24 hours at 60 ° C. and 95% relative humidity.

(Foreign substance inspection)
Reflected light was applied to a range of the entire width of the sample × 1 m to visually detect foreign matter in the film, and then the foreign matter (lint) was confirmed and evaluated with a polarizing microscope.

(Dimensional stability)
The dimensional stability was evaluated by the heat shrinkage rate. Three test pieces each having a width of 30 mm and a length of 120 mm were collected from the vertical and horizontal directions of the sample. Holes of 6 mmφ were punched at both ends of the test piece at 100 mm intervals. This was conditioned for 3 hours or more in a room at 23 ± 3 ° C. and a relative temperature of 65 ± 5%. Using an automatic pin gauge (manufactured by Shinto Kagaku Co., Ltd.), the original size (L1) of the punch interval was measured to the minimum scale / 1000 mm. Next, the test piece was suspended in a thermostat at 80 ° C. ± 1 ° C. and heat-treated for 3 hours, adjusted to a humidity of 23 ± 3 ° C. and a relative humidity of 65 ± 5% for 3 hours or more, and then subjected to heat treatment with an automatic pin gauge. The dimension (L2) of the punch interval was measured. And the thermal contraction rate was computed by the following formula | equation.
Thermal contraction rate = (L1-L2 / L1) × 100

(Measurement of bright spot foreign matter)
Two polarizing plates were placed in an orthogonal state (crossed Nicols) to block transmitted light, and each sample was placed between the two polarizing plates. The polarizing plate used was a glass protective plate. Light was irradiated from one side, and the number of bright spots having a diameter of 0.01 mm or more per 1 cm ² was counted with an optical microscope (50 times) from the opposite side.

(2) Evaluation results Table 1 summarizes the evaluation results of die saturation, dangling unevenness, Re unevenness, Rth unevenness, unevenness in thickness, Re humidity dependency, Rth humidity dependency, and roll soil of each saturated norbornene resin film.

  Comparative Sample 1-1 that does not contain a polymer having fluorine atoms, or Comparative Sample 1-2 that contains a small amount of polymer having fluorine atoms, has die lines, dangling, Re unevenness, Rth unevenness, uneven thickness, and roll stains. It was bad. In contrast, the saturated norbornene resin film samples 1-3 to 1-11 of the present invention containing a polymer having a fluorine atom in the saturated norbornene resin have greatly improved die lines and dangling, and Re unevenness and Rth unevenness. It was confirmed that the thickness unevenness was also greatly improved. Surprisingly, it was also confirmed that the roll contamination was greatly improved and an unexpected effect was obtained. Furthermore, the humidity dependence of Re and Rth was small, and it was confirmed that the saturated norbornene resin film sample of the present invention had no adverse effects due to the polymer having fluorine atoms.

  On the other hand, Comparative Sample 1-13 to Comparative Sample 1-18 using other materials as release agents had poor die lines, and poor Re unevenness, Rth unevenness, thickness unevenness, and roll contamination. Further, Comparative Sample 1-12 containing a polymer having a fluorine atom but having too much content was problematic because the film film was whitened and white turbidity was observed. As described above, an excellent saturated norbornene resin film could be produced by adding a polymer having a fluorine atom to the saturated norbornene resin according to the present invention.

Sample 1-3 as a representative of the present invention has Re of 5.4 nm, Rth of 15.1 nm, haze of 0.2%, transparency of 93.5%, and molecular orientation axis of 0.15. Axis deviation is 0.2%, Kisimi value is static friction coefficient is 0.56 and dynamic friction coefficient is 0.49, curl value is 0.1 for dry and 0.15 for wet, The moisture permeability coefficient is 5 g / m ² · day, 3 foreign substances are observed, the dimensional stability is 0.01% or less, and the bright spot foreign substances are 0.02 mm to 0.05 mm less than 10/3 m. It was confirmed that the film was 0.05 to 0.1 mm and less than 4/3 m, and had no bright spot foreign matter of 0.1 mm or more. Other samples of the present invention also exhibited almost the same various characteristics and could be applied as excellent optical films (particularly as polarizing plate protective films).

(Example 2)
The saturated norbornene resin film sample 1-3 of the present invention was laminated with 15 μm of an acrylate-based pressure-sensitive adhesive, and a commercially available polarizing film HLC2-5618 (manufactured by Sanlitz) was attached thereon. The obtained polarizing film with saturated norbornene resin film sample 1-3 had a degree of polarization of 99.99%, and was confirmed to have excellent polarizing film characteristics.

(Example 3)
The saturated norbornene resin film sample 1-3 of the present invention obtained in Example 1 was stretched at a stretching temperature of 158 ° C., a stretching ratio of 160% in the longitudinal direction (MD direction) and 120% in the lateral direction (TD direction). Sample 3-1 (stretched film) was obtained. The stretching speed was 1 m / min. The properties of the obtained stretched film sample 3-1 were evaluated in Table 1. As a result of stretching, Re unevenness, Rth unevenness, and thickness unevenness were further reduced, which was excellent. Re was 60.5 nm and Rth was 213 nm.

Example 4
Next, examples in which a saturated norbornene resin film is applied to a polarizing plate will be described.
The saturated norbornene resin film sample 3-1 of the present invention was bonded to an acrylate-based pressure-sensitive adhesive with a thickness of 15 μm, and a commercially available polarizing film HLC2-5618 (manufactured by Sanlitz) was attached thereon to produce a polarizing plate. At this time, the polarizing axes of the polarizing plates and the longitudinal direction of the saturated norbornene resin film were laminated so as to be 90 degrees. After attaching the obtained polarizing plate made of a saturated norbornene resin film to a 20-inch VA liquid crystal display device described in FIGS. 2 to 9 of JP-A-2000-154261 at 25 ° C. and a relative humidity of 60%, Is brought into 25 ° C and 10% relative humidity, and the color change is visually evaluated on a 10-point scale (the larger the change, the greater the change), and the area where display unevenness occurs is visually evaluated. When the percentage (%) of the occurrence of selenium was determined, the color tone change of the saturated norbornene resin film of the present invention was 1, which was very excellent. Further, according to Example 1 of JP-A-2002-86554, the saturated norbornene resin film of the present invention is similarly applied to a polarizing plate stretched using a tenter so that the stretching axis is at an angle of 45 ° with respect to the absorption axis. Although it was used, good results were obtained as described above.

(Example 5)
(1) Mounting on VA panel The polarizing plate produced in Example 4 of the present invention is a backlight side polarizing plate so that the viewing side polarizing plate is 26 "wide and the absorption axis of the polarizer is long. The polarizer was punched into a rectangle so that the absorption axis of the polarizer had a short side.The front and back polarizing plates and the retardation plate of the VA mode liquid crystal TV (KDL-L26RX2 manufactured by Sony Corporation) were peeled off and A liquid crystal display device was prepared by combining the polarizing plates prepared in Sample 3-1 of the present invention in combination, and after being attached to the polarizing plate, it was held at 50 ° C. and 5 kg / cm ² for 20 minutes for adhesion. The absorption axis of the polarizing plate on the viewing side is in the horizontal direction of the panel, the absorption axis of the polarizing plate on the backlight side is in the vertical direction of the panel, and the adhesive material surface is on the liquid crystal cell side. , Measuring machine (ELDIM, EZ-C ntrat 160D) was used to calculate the viewing angle (contrast ratio in the range of 10 or more) from the luminance measurement of the black display and the white display. Good viewing angle characteristics were obtained, and light leakage and polarizing plate peeling tests were carried out to confirm that there were no problems.

1) Hold in an environment of 60 ° C and 90% relative humidity for 200 hours, take out in an environment of 25 ° C and 60% relative humidity, and display the liquid crystal display device in black 24 hours later, light leakage strength and peeling of the polarizing plate from the liquid crystal panel The presence or absence of was evaluated.
2) Hold at 80 ° C dry environment for 200 hours, take out to 25 ° C and 60% relative humidity environment, display the liquid crystal display device black one hour later, and evaluate the light leakage strength and whether the polarizing plate is peeled off from the liquid crystal panel did. Dry means a relative humidity of 10% or less.

  According to the production method of the present invention, it is possible to provide a saturated norbornene resin film in which die streaks, thickness unevenness, and optical property unevenness are greatly reduced. If the saturated norbornene resin film of the present invention is incorporated into a liquid crystal display device, it is possible to greatly suppress changes in visibility due to display unevenness and humidity, which have been problems in the past. Therefore, the saturated norbornene resin film of the present invention has high industrial applicability.

It is the schematic which shows the structure of an extruder.

Explanation of symbols

22 Extruder 32 Cylinder 40 Supply port A Supply part B Compression part C Weighing part

Claims (14)

  A saturated norbornene resin film comprising a polymer having a fluorine atom in an amount of 0.01 to 5% by mass relative to the solid content of the film and having a residual solvent amount of 0.01% by mass or less.   The saturated norbornene resin film according to claim 1, wherein the polymer having a fluorine atom is a polymer obtained by polymerizing a monomer containing a fluorinated alkyl group-containing ethylenically unsaturated monomer. The saturated norbornene resin film according to claim 2, wherein the fluorinated alkyl group-containing ethylenically unsaturated monomer is represented by the following general formula (FM-1).
Formula _{(FM-1) CH 2 =} C (R 1) -COO- (X) n-Rf
(In the formula, Rf is a perfluoroalkyl group having 1 to 20 carbon atoms or a partially fluorinated alkyl group, Rf may be linear or branched, and an oxygen atom and / or It may have a functional group containing a nitrogen atom in the main chain, R ¹ represents a hydrogen atom, an alkyl group which may be fluorinated, a chlorine atom or a fluorine atom, and X is a divalent linking group. And n represents an integer of 1 to 10.)   The saturated norbornene resin film according to any one of claims 1 to 3, further comprising 0.005 to 2% by mass of fine particles having an average primary particle size of 0.005 to 2 µm. The saturated norbornene resin according to any one of claims 1 to 4, which contains 0.05 to 5 g / m ^{2 of} at least one selected from the group consisting of a plasticizer, an ultraviolet absorber and a stabilizer. the film.   6. The saturated norbornene according to claim 1, wherein the in-plane retardation (Re) is 0 nm to 500 nm and the thickness direction retardation (Rth) is −300 nm to 700 nm. Resin film.   The fluctuations in the slow axis direction of Re and the direction perpendicular to the slow axis are both 5% or less, and the fluctuations in the slow axis direction of Rth and the direction perpendicular to the slow axis are both 5% or less. The saturated norbornene resin film according to any one of claims 1 to 6, wherein   A method for producing a saturated norbornene resin film comprising a step of melt-forming a mixture of a saturated norbornene resin and a polymer having 0.01 to 5% by mass of fluorine atoms based on the solid content of the saturated norbornene resin. .   The method for producing a saturated norbornene resin film according to claim 8, further comprising a step of stretching the melt-formed film at 0.90 to 5 times in at least one of a casting direction and a width direction.   A saturated norbornene resin film produced by the production method according to claim 8.   A polarizing plate comprising at least one layer of the saturated norbornene resin film according to any one of claims 1 to 7 and 10 laminated on a polarizing film.   The optical compensation film which used the saturated norbornene resin film as described in any one of Claims 1-7 and 10 for the base material.   The antireflection film which used the saturated norbornene resin film as described in any one of Claims 1-7 and 10 for the base material.   The liquid crystal display device using the saturated norbornene resin film as described in any one of Claims 1-7 and 10.

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