TW200815192A - Optical film roll and its manufacturing method - Google Patents

Abstract

The invention is to provide an optical film which is homogeneous and uniform optically by minimizing foreign substances incorporated in a protective film in an optical film roll keeping the optical film overlaid/wound with the protective film. In the optical film roll making the optical film made of a cyclic olefin resin overlaid/wound with the protective film, the number of fish eyes with the diameters of at least 30 μm in the protective film is 5/m<SP>2</SP> or below.

Description

[Technical Field] The present invention relates to an optical film roll obtained by laminating an optical film formed of a cyclic olefin resin and a protective film. The protective film of the present invention is laminated and rewinded into an optical film roll, and when it is cut out as a polarizing plate or a phase difference plate, the protective film is used for surface protection, and 'this protection The film is adhered to the surface of the liquid crystal display panel, and can be used for protection of various screen display devices such as liquid crystal display devices and other organic EL display devices and PDPs. [Prior Art] A general surface protective film is provided with an adhesive layer on a base film of polyethylene terephthalate or polyethylene. The surface protective film is bonded to the object to be protected by the adhesive layer, and is prevented from being damaged or contaminated with respect to the object to be protected. For example, an optical film such as a polarizing plate or a phase difference plate may be mentioned as the optically-protected body. The single side of the optical film can be protected by the surface protective film in various manufacturing steps. On the other hand, an adhesive layer is provided on the opposite side of the optical film. Further, a release liner (sepeartor) is provided on the adhesive layer. The optical film with the surface protective film produced in this manner is stored in a state of being wound into a roll, or cut into a size corresponding to the size of the liquid crystal cell, so that the superposition is superposed. , in the form of paper (sheetsh ap ed) and other holders. These steps are usually carried out in a clean room. However, the dust generated by the operator, 200815192 inspector, the stamping debris during stamping, and the tiny foreign matter such as dust during transportation are completely removed. difficult. However, when a small foreign matter is mixed between the layers of the roll or the superposition film, an indentation due to foreign matter occurs. The optical film itself cannot be used when it has an indentation. Further, compared with the optical film, the adhesive layer has a low modulus of elasticity and tends to have an indentation. When the adhesive layer is indented, when the optical film is bonded to the LCD panel through the adhesive layer, air is intruded in the concave portion and the display is defective. In order to solve this problem, Patent Document 1 proposes a surface protective film in which a foreign matter absorbing layer is provided on one surface of a substrate film. However, in addition to the protective film and the substrate film, the foreign matter absorbing layer itself may be installed in other ways. In the case of providing the layer itself, there is one more step, which is complicated not only in the process of fabricating the optical film, but also The cost has also risen and it is not a good strategy in the economy. [Problem to be Solved by the Invention] It is an object of the present invention to provide an optical body which is homogeneous and has no optical unevenness in order to suppress foreign matter in a protective film as much as possible. film. -6- 200815192 [Means for Solving the Problem] The present invention relates to an optical film roll formed by laminating an optical film formed of a cyclic olefin resin and a protective film, wherein the protective film has a diameter of 3 Ομηι or more. The number of the optical film roll is preferably 0. The optical film roll is preferably a (co)polymer of a compound represented by the following general formula (1).

(In the formula (1), R1 to R4 represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or another monovalent organic group, which may be the same or different. Further, any two of R1 to R4 may be used. Mutual bonding, can form a single-ring or multi-ring structure. m shows 〇 or positive integer, p shows 〇 or positive integer). Further, the center line average roughness Ra of the protective film is preferably 0.005 to 0 · 0 5 μ m. Further, the protective film is preferably made of a polyolefin resin, and the present invention is an optical film formed of a cyclic olefin resin, and the number of fish eyes having a diameter of 30 μm or more is 5/m2 or less. The protective film is superposition and rewinded, and the optical film roll is manufactured. -7- 200815192 [Inventive Effect Factory According to the present invention, in the conventional optical film roll, the protective film having the fish eye laminated and wound back is pressed against the surface of the optical film for a long period of time, and although uneven with the surface, optical unevenness In the case where the protective film having less fish eyes of the present invention is used, a homogeneous optical film free from optical unevenness can be obtained (the best mode for carrying out the invention). "Optical film" The optical film of the present invention is ring-shaped. An optical film formed of an olefin resin. &lt;Cyclic olefin-based resin&gt; The cyclic olefin-based resin used in the optical film of the present invention may, for example, be the next (co)polymer. Ester (1) A ring-opening polymer of a monomer not specifically described in the above general formula (1). (2) A ring-opening copolymer of a specific monomer and a copolymerizable monomer represented by the above general formula (1). (3) Hydrogenation of a (co)polymer of the above (1) or (2) (co)polymer. (4) The ring-opening (co)polymer of the above (1) or (2) is cyclized by a Friedel Kraft reaction, and then hydrogenated (co)polymer 〇 (5) The above general formula (1) a saturated copolymer of a specific monomer and a compound containing an unsaturated double bond-8 - 200815192. (6) An addition (co)polymer selected from the specific monomers represented by the above general formula (1), one or more monomers of a vinyl cyclic hydrocarbon monomer and a cyclopentadiene monomer, and hydrogenation thereof (co)polymer. (7) A cross-copolymer of a specific monomer and an acrylate represented by the above general formula (1). &lt;Specific monomer&gt; Specific examples of the specific monomer described above may be exemplified by the following compounds, but the present invention is not limited to the specific examples. It may, for example, be bicyclo[2·2·1]hept-2-ene, tricyclo[4.3.0·12,5]-8-decene, tricyclo[4·4·0·12,5]-3 -undecene, tetracyclo[4.4.0.12,5.17,1()]-3-dodecene, pentacyclo[6·5.1 ·13,6.02,7"9,13]-4-pentadecene, 5 -Methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2·2·1]hept-2-ene, methoxycarbonylbicyclo[2.2.1]heptene, 5-methyl -5-methoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyanobicyclo[2·2·1]hept-2-ene, 8-methoxycarbonyltetracyclo[4.4.0· I2 ,5·! 7'1G]-3-dodecene, 8-ethoxycarbonyltetracyclo[4_4·0· 12,5.17,1()]-3-dodecene, 8-n-propoxycarbonyl Tetracyclo[4.4.0·12,5.17,1()]-3-dodecene, 8-isopropoxycarbonyltetracyclo[4.4.0· 12,5·17,1()]-3-ten Diene, • 9- 200815192 8-n-butoxycarbonyltetracyclo[4.4.0. 12'5.17,1()]-3-dodecene, 8-methyl-8-methoxycarbonyltetracyclo[ 4.4.0. 12'5.17'1q]-3-dodecene, 8-methyl-8-ethoxycarbonyltetracyclo[4·4·0· 12,5·17,1()]-3· Decadiene, 8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0. l2,5.l7,1G]-3-dodecene, 8-methyl-8-isopropoxycarbonyl Fourth Ring [4.4.0. 12 '5.17'1()]-3-dodecene, 8-methyl-8-n-butoxycarbonyltetracyclo[4.4.0. 12'5·17,1()]-3-dodecene, 5-ethylenebicyclo[2.2.1]hept-2-ene, 8-ethylenetetracyclo[4.4.0·12'5.17'1g]-3-dodecene, 5-phenylbicyclo[2·2 ·1]hept-2-ene, 8-phenyltetracyclo[4 · 4 · 0 . 1 2,5 · 17 '1G ]-3 -dodecene, 5-fluorobicyclo[2·2·1]g 2-ene, 5-fluoromethylbicyclo[2.2.1]hept-2-ene, 5-trifluoromethylbicyclo[2.2.1]hept-2-ene, 5-pentafluoroethylbicyclo[2.2. 1]hept-2-ene, 5.5-difluorobicyclo[2·2.1]hept-2-ene, 5.6-difluorobicyclo[2.2.1]hept-2-ene, 5.5-bis(trifluoromethyl)bicyclo [2.2.1] Hept-2-ene, 5.6-bis(trifluoromethyl)bicyclo[2.2.1]hept-2-ene, 5-methyl-5-trifluoromethylbicyclo[2·2·1 G-8-ene, 5.5.6-trifluorobicyclo[2·2·1]hept-2-ene, 5.5.6-tris(fluoromethyl)bicyclo[2.2.1]hept-2-ene, 5.5 .6.6- Tetrafluorobicyclo[2.2.1]hept-2-ene, 5.5.6.6-tetrakis(trifluoromethyl)bicyclo[2.2.1]hept-2-ene, 5,5-difluoro-6, 6-bis(trifluoromethyl)bicyclo[2·2·1]hept-2-ene,-10-200815192 5.6-difluoro-5,6-bis(trifluoromethyl)bicyclo[2 ·1·1]hept-2-ene, 5,5,6-trifluoro-5-trifluoromethylbicyclo[2.2.1]hept-2-ene, 5-fluoro-5-pentafluoroethyl-6 ,6-bis(trifluoromethyl)bicyclo[2.2.1]hept-2-ene 5.6-one gas &lt;-5-seven gas-isopropyl-6-di-mirror methyl double mourning [2·2· 1] Geng-2-reserved ' 5-chloro-5,6,6-trifluorobicyclo[2.2.1]hept-2-ene, 5.6-dichloro-5,6-bis(trifluoromethyl)bicyclo[ 2.2.1] hept-2-ene, 5.5.6-trifluoro-6-trifluoromethoxybicyclo[2.2.1]hept-2-ene, 5.5.6-trifluoro-6-heptafluoropropoxy Bicyclo[2.2.1]hept-2-ene, 8-fluorotetracyclo[4·4·0· 12'5·17'1()]-3-dodecene, 8-fluoromethyltetracycline [4 ·4·0· 12'5.17'1()]-3-dodecene, 8-difluoromethyltetracyclo[4·4·0·12'5.17'1()]-3-dodecene, 8-trifluoromethyltetracyclo[4.4.0·12,5.17,1()]-3-dodecene, 8-pentafluoroethyltetracycline [4.4.0· 12'5.17'1{)]- 3-dodecene 8.8-difluorotetracyclo[4.4.0. 12,5·17'1()]-3-dodecene, 8.9-difluorotetracycline [4.4.0. 12'5·Γ' 1()]-3-dodecene, 8,8-bis(trifluoromethyl)tetracyclo[4.4.0.12, 5.17,1()]-3-dodecene, 8,9 stomach bis(trifluoro Methyl)tetracyclo[4·4·0. 12,5·17,10]-3-dodecene, 8_A Trifluoromethyltetracyclo[4.4.0·12,5.17,1()]-3-dodecene, 8.8.9-trifluorotetracycline [4.4.0. 12,5.17,1()]-3 - dodecene 8.8.9-tris(trifluoromethyl)tetracyclo[4·4·0·l2,5.l7,1G]-3-dodecene, 8.8.9.9-tetrafluorotetracycline [4.4. 0. 12'5.17,1()]-3-dodecene, 8.8.9.9- four (trifluoromethyl)tetracyclo[4·4·0· 12,5·17'1()]-3 -dodecene 11 - 200815192 8.8-difluoro-9,9-bis(trifluoromethyl)tetracyclo[4·4·0· 12,5·17,1()]-3-dodecene, 8.9 - Difluoro-8,9-bis(trifluoromethyl)tetracyclo[4·4·0· 12,5'17,1g]-3-dodecene, 8.8.9-trifluoro-9-trifluoro Methyltetracycline [4.4.0· 12, 5.17, 1 () 3-dodecene, 858.9-trifluoro-9-trifluoromethoxytetracyclo[4.4.0.12, 5.17,1()]-3 - dodecene 8.8.9-trifluoro-9-pentafluoropropoxytetracyclo[4.4.0.12, 5.17,1()]-3-dodecene 8-fluoro-8-pentafluoroethyl-9, 9-bis(trifluoromethyl)tetracyclo[4.4.0· 12'5·Γ'1()]-3-dodecene, 8.9-difluoro-8-heptafluoroisopropyl-9-trifluoro Methyltetracyclo[4.4.0.12, 5.17,1()]-3-dodecene, 8-chloro-8,9,9-trifluorotetracyclo[4.4.0. 12,5.17,1g]-3- Decadiene, 8.9-dichloro-8,9-double (three Methyl)tetracyclo[4.4.0. 12'5.17,1()-3-dodecene, 8-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[4·4·0·12 '5·Γ'1()]-3-dodecene 8-methyl-8-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[4.4.0.12,5.17,1()]- 3-dodecene and the like. These may be used alone or in combination of two or more. Preferably, in the above specific formula (1), R1 and R3 are a hydrogen atom or a hydrocarbon number of from 1 to 10, more preferably from 1 to 4, particularly preferably from 1 to 2, and R2 and R4 are shown. In the hydrogen atom or the monovalent organic group, R2 and R4 are up to -12 - 200815192. One less polar group having a polar group other than a hydrogen atom and a hydrocarbon group, m is an integer of 0 to 3, and ρ is an integer of 0 to 3, Preferably, m + p = 〇 〜 4, more preferably 0 〜 2, and particularly preferably m = l, p = 0. The specific monomer having m = l and p = 0 is preferable in that the obtained cyclic olefin resin has a high glass transition temperature and excellent mechanical strength. The polar group of the specific monomer may, for example, be a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amine group, a decylamino group, a cyano group or the like, and the polar groups may be bonded through a bond such as a methylene group. The base is bonded. Further, the polar group may, for example, be a hydrocarbon group having a polar divalent organic group such as a carbonyl group, an ether group, a decane ether group, a thioether group or an imine group, which is bonded to a bond group. Among these, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group or an allyloxycarbonyl group is preferred, and an alkoxycarbonyl group or an allyloxycarbonyl group is preferred. Further, at least one of R2 and R4 is a monomer having a polar group represented by the formula -(CH2)nCOOR, and the obtained cyclic olefin-based resin has a high glass transition temperature and low hygroscopicity, and is excellent in various materials. The point of adhesion is better. In the formula relating to the above specific polar group, R is a hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 4 carbon atoms, particularly preferably 1 to 2 carbon atoms, preferably an alkyl group. Further, η is usually 〇~5, and the smaller the η is, the higher the glass transition temperature of the obtained cyclic olefin resin is, and the specific monomer having η of 0 is preferably synthesized. . Further, in the above general formula (1), R1 or R3 is preferably an alkyl group, an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2, particularly preferably a methyl group, especially, the alkane. When the base system is bonded to the same carbon atom as the carbon atom to which the specific polar group represented by the above formula -(CH2)nCOOR is bonded, the hygroscopicity of the cyclic olefin resin obtained from -13 to 200815192 can be obtained. The point of reduction is better. &lt;Copolymerizable monomer&gt; Specific examples of the copolymerizable monomer include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and dicyclopentadiene. The carbon number of the cycloolefin is preferably 4 to 20, more preferably 5 to 12. These may be used alone or in combination of two or more. The proper use range of the specific monomer/copolymerizable monomer is from 100/0 to 50/50, more preferably from 100/0 to 60/40. &lt; Ring-Opening Polymerization Catalyst&gt; In the present invention, in order to obtain (1) a ring-opening polymer of a specific monomer, and (2) a ring-opening polymerization reaction of a ring-opening copolymer of a specific monomer and a copolymerizable monomer, It can be carried out in the presence of a metathesis catalyst. The metathesis catalyst is (a) at least one selected from the group consisting of W, Mo and Re, and (b) is a Group IA element of the periodic table of Diming (for example, Li, Na, K, etc.), a Group IIA element ( For example, Mg, Ca, etc.), Group IIB elements (eg, Zn, Cd, Hg, etc.), lanthanum elements (eg, B, A1, etc.), Group IVA elements (eg, Si, Sn, Pb, etc.), or Group IVB elements (eg, Among the compounds of Ti, Zr, and the like, a catalyst is selected from a combination of at least one of the element-carbon bond or the element-hydrogen bond. Further, in this case, in order to increase the activity of the catalyst, it is also possible to add the additive (c) described later. (a) The composition of the compound W, the representative of the compound of Mo or Re, and the representative of the compound - 14, 2008, 192, for example, WCU, MoCU, ReOCl3, etc., Japanese Patent Laid-Open No. I-132626, page 8 of the lower left column, line 6 to The compound described in the 17th line on the right is blocked on page 8. Specific examples of the component (b) include n-C4H9Li, (C2H5)3A1 '(C2H5)2A1C1, (C^HsAlClu, (c2H5)A1C12, methylalmoxane, LiH, etc., JP-A-H32626, page 8 Alcohols, aldehydes, ketones, amines, etc., can be suitably used in the representative examples of the component (C) of the compound described in the third column of the upper right column and the third row of the right column of the eighth column. The compound shown in the first column of the lower right column of the eighth page of the Japanese Patent Laid-Open Publication No. b 13 26 26 to the seventh column of the upper left column of page 9. The amount of the metathesis catalyst used is the above (a) component and specific The molar ratio of the monomer is "(a) component · specific monomer", usually in the range of 1: 5 〇〇 ~ 1: 50,000, preferably 1: 1,000 〜1: 1 〇, 〇〇〇之之The ratio of (a) component to component (b) is in the range of 1:1 to 1:50, preferably 1:2 to 1:30, in terms of metal atomic ratio (a):(b). The ratio of the component to the component (c) is in the range of the molar ratio (c): (a) of 0.0 05: 1 to 15: 1, preferably 〇·〇 5: 1 to 7: 1. &lt;Polymerization Solvent &gt; Solvent used in ring-opening polymerization (construction) The solvent of the sub-regulator solution, the solvent of the specific monomer and/or the metathesis catalyst, has -15-200815192 such as pentane, hexane, heptane, octane, decane 'decane and the like. a cycloalkane of cyclohexane, cycloheptane, cyclooctane, decahydronaphthalene, norguanidine, etc., aromatic hydrocarbon such as benzene, toluene, xylene, ethylbenzene, cumene, chlorobutane, Bromohexane, dichloromethane, dichloroethane, hexylene dibromide, chlorobenzene, chloroform, tetrachloroethylene, etc., halogenated alkane, halogenated aryl, etc., ethyl acetate, n-butyl acetate, a saturated carboxylic acid ester such as isobutyl acetate, methyl propionate or dimethoxyethane; an ether such as dibutyl ether, tetrahydrofuran or dimethoxyethane; these may be used alone or in combination. In the case of the above, the aromatic hydrocarbon is preferred. The solvent: the specific monomer (weight ratio), usually 1:1 to 10:1, preferably 1:1~ 5:1. &lt;Molecular weight modifier&gt; The molecular weight of the obtained ring-opening (co)polymer is adjusted, depending on the polymerization temperature, the type of catalyst, In the present invention, the molecular weight modifier can be adjusted by coexisting in the reaction system. Here, examples of the appropriate molecular weight modifier include ethylene, propylene, and 1-butene. Pentene, 1-hexene, 1-heptene, octene, i-tellurium-i-pinene and the like, and α-olefins, and benzene, in the case of 1, butene, 1-hexene The molecular weight regulators may be used alone or in combination of two or more kinds of ruthenium molecular weight modifiers, and the molar amount of the specific monomer to be subjected to ring-opening polymerization is 0.005 to 〇6 m. Preferably, it is 0〇2~-16, 200815192 0.5 m. (2) In order to obtain a ring-opening copolymer, a specific monomer and a copolymerizable monomer may be subjected to ring-opening copolymerization in a ring-opening polymerization step, and further, a conjugated diene such as polybutadiene or polyisoprene. Compound, styrene-butadiene copolymer 'B--non-common-type fine copolymer', main chain of norbornene, etc., two or more unsaturated hydrocarbon systems containing carbon-carbon double bonds It is also possible to carry out ring-opening polymerization of a specific monomer in the presence of a polymer or the like. The ring-opening (co)polymer obtained in the above manner can be used as it is, and the (3) hydrogenated (co)polymer obtained by further hydrogenating is useful as a raw material of a resin having high impact resistance. &lt;Hydrogenation Catalyst&gt; The hydrogenation reaction is carried out by a usual method, that is, a hydrogenation catalyst is added to a solution of a ring-opening polymer, which is usually at a pressure of 30,000 to 30 Torr, preferably 3 to 20,000 Torr. The hydrogen gas is carried out at 0 to 200 ° C, preferably at 20 to 180 ° C. As the hydrogenation catalyst, those used in the hydrogenation reaction of a usual olefinic compound can be used. As the hydrogenation catalyst, a heterogeneous catalyst and a homogeneous catalyst can be exemplified. The heterogeneous catalyst may, for example, be a solid catalyst in which a noble metal catalyst such as palladium, platinum, nickel, rhodium or ruthenium is supported on a carrier of carbon, cerium oxide, aluminum oxide or titanium oxide. Further, in terms of the homogeneous catalyst, naphthenic acid nickel/triethylaluminum, ethyl ethyl ethynyl nickel/triethylaluminum, cobalt octoate/n-butyllithium, Titanium dichloride ( -17- 200815192 titan〇cene ) /-diethylaluminum chloride, cesium acetate, chlorotris(triphenylphosphine) 锗'dichlorotris(triphenylphosphine) ruthenium, chlorohydrogen Carbonyl tris(triphenylphosphine) 钌'dichlorocarbonyl tris(triphenylphosphine) ruthenium or the like. The form of the catalyst may be either a powder or a granule. These hydrogenation catalysts' ring-opening (co)polymers·hydrogenation catalysts (weight ratio) are used in a ratio of 1:1 X 10·6 to 1:2. As a result, the hydrogenated (co)polymer obtained by hydrogenation has a high heat stability of %, and its properties are not deteriorated even when it is formed during molding or when it is used as a product. Here, the hydrogenation rate is usually 50% or more, preferably 70% or more, and more preferably 90% or more. Further, the hydrogenation ratio of the hydrogenated (co)polymer is 50% or more, preferably 90% or more, more preferably 98% or more, and most preferably 99% or more, as measured by NMR at 500 MHz. The higher the hydrogenation rate, the more excellent the stability against heat or light, and the stable properties can be obtained over a long period of time when the optical film of the present invention is used as a wavelength plate. Φ In addition, the hydrogenated (co)polymer used as the cyclic olefin resin of the present invention preferably contains 5% by weight or less of the gel content in the hydrogenated (co)polymer, and further preferably 1% by weight or less. Especially good. Further, in the case of the cyclic olefin-based resin of the present invention, the ring-opening (co)polymer of the above (1) or (2) may be cyclized by a Friedel Kraft reaction, or may be used. Hydrogenated (co)polymer. &lt;cyclization by Fudd-Kraft reaction&gt; The method of cyclizing the ring-opening (co)polymer of (1) or (2) by the special reaction of Frederick -18-200815192 A well-known method using an acidic compound described in Japanese Laid-Open Patent Publication No. SHO-50-543-99-99 is specifically limited. As the acidic compound, specifically, a Lewis acid or a Bronsted acid such as A1C13'BF3, FeCl3, A1203, HCl, CH2C1C00H, zeolite, activated clay or the like can be used. The ring-opened (co)polymer which is cyclized is hydrogenated in the same manner as the ring-opened (co)polymer of (1) or (2). Further, as the cyclic olefin resin of the present invention, (5) a saturated copolymer of the above specific monomer and an unsaturated double bond-containing compound may be used. &lt;Unsaturated double bond compound&gt; The unsaturated double bond compound may, for example, be ethylene, propylene, butylene or the like, preferably a carbon number of 2 to 12, more preferably an olefin having 2 to 8 carbon atoms. a compound. The proper use range of the specific monomer/unsaturated double bond compound is 90/10 to 40/60, more preferably 85/15 to 50/50 by weight. In the present invention, in order to obtain (5) a saturated copolymer of a specific monomer and an unsaturated double bond-containing compound, a usual addition polymerization method can be used. &lt;Addition polymerization catalyst&gt; As the catalyst for synthesizing the above (5) saturated copolymer, at least one selected from the group consisting of a titanium compound, a ruthenium compound and a vanadium compound, and an organoaluminum compound as a co-catalyst can be used. In the case of the 'titanium compound, titanium tetrachloride, titanium trichloride, etc. -19-200815192 can be exemplified, and in terms of the chromium compound, bis(cyclopentadienyl)zirconium chloride and dichlorobis(cyclopentadienyl) can be exemplified. Ethene) chromium. Further, in terms of the vanadium compound, the general formula VO(OR)aXb, or V(OR)cXd can be used [however, R is a hydrocarbon group, X is a halogen atom, 〇^a$3, 0SbS3, 2S (a + b) S3, 0Sc $4,0$d$4,(c + d) ^ 4 ]. A vanadium compound as shown, or such an electron donating additive. The above electron donor may, for example, be an oxygen-containing electron donor of an alcohol, a phenol, a ketone, an aldehyde, a carboxylic acid, an ester of an organic or inorganic acid, an ether, an acid amide, an acid anhydride, an alkoxy halane or the like. A nitrogen-containing electron donor such as ammonia, an amine, a nitrile or an isocyanate. Further, as the organoaluminum compound as a promoter, at least one selected from the group consisting of at least one aluminum-carbon bond or aluminum-hydrogen bond may be used. In the above, for example, in the case of using a vanadium compound, the ratio of the vanadium compound to the organoaluminum compound to the aluminum atom of the vanadium atom (A1/V) is 2 or more, preferably 2 to 50, and particularly preferably 3 to 3. The scope of 20. The solvent used for the polymerization reaction in the addition polymerization can be used in the same manner as the solvent used in the ring-opening polymerization reaction. Further, in order to adjust the molecular weight of the obtained (5) saturated copolymer, hydrogen can be usually used. Further, as the cyclic olefin resin of the present invention, (6) addition molding of one or more monomers selected from the above specific monomers and ethylene-based cyclic hydrocarbon monomers or cyclopentadiene monomers can be used. Copolymer and hydrogenated copolymer thereof-20-200815192 &lt;Ethylene-based cyclic hydrocarbon-based monomer&gt; Examples of the ethylene-based cyclic hydrocarbon-based monomer include, for example, '4-ene, 2-methyl-4-isopropene Ethylene cyclopentene-based vinylcyclopentane, 4-isopropenylcyclopentane, etc., vinylated 5-membered cyclic hydrocarbon monomer, 4-vinylcyclohexene, 4_ Isohexene, 1-methyl-4-isopropenylcyclohexene, 2-methyl-4-ethyl, 2-methyl-4-isopropenylcyclohexene, etc., ethylenecyclohexene monoolefin Ethylene, ethylene monomer such as 2-methyl-4-isopropenylcyclohexane, styrene, α-methylstyrene, 2-methylstyrene', storage, 4-methylbenzene, 1 - Ethylene naphthalene, 2-ethyl bhodium naphthalate, 4-ene, p-methoxystyrene, etc., styrene monomer, d-ene), 1-propene, diterpene, d-limonene, 1- Limonene, two singular monomers, 4-ethyl sulphonate, 4-isopropoxy guanidine Hept-based monomer, 4-vinyl cycloheptane, 4-isopropenyl cycloheptane, cycloheptene based monomer. Preferred is styrene, α-methylstyrene. These may be used alone or in combination of two or more. &lt;Cyclopentadiene-based monomer&gt; For the monodiene monomer to be used in the (6) addition copolymer of the present invention, for example, cyclopentadiene '1-methylcyclopentylmethylcyclopentane Diene, 2-ethylcyclopentadiene ' 5-methylcyclopentyldimethylcyclopentadiene, and the like. Preferred is cyclopentadiene. These may be used alone or in combination of two or more. Ethylene cyclopentene monomer, propylene cyclohexene cyclohexene such as 4-system monomer, 4-ethylcyclohexane 3-methylphenylphenyl benzene (terpene pentene, etc. a single type, cyclopentadiene, 2-ene, 5,5 - alone, -21 - 200815192 selected from the above specific monomers, ethylene-based cyclic hydrocarbon monomers and cyclopentadiene monomers The addition (co)polymer of the above monomers may be obtained by the same addition polymerization method as the above (5) specific monomer and a saturated copolymer containing an unsaturated double bond compound. The hydrogenated (co)polymer of the polymer can be obtained by the same hydrogenation method as the hydrogenated (co)polymer of the above (3) ring-opened (co)polymer. Further, in terms of the cyclic olefin resin of the present invention, (7) An interactive copolymer of the above specific monomer and acrylate can be used. &lt;Acrylate&gt; The acrylate used in the production of the above-mentioned specific monomer and acrylate interpolymer is For example, methacrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate a heterocyclic group having 2 to 20 carbon atoms such as a linear, branched or cyclic alkyl acrylate having a carbon number of 1 to 20, a glycidyl acrylate or a 2-tetrahydrofurfuryl acrylate. An acrylate having a polycyclic structure having a carbon number of 7 to 30, such as an aromatic cyclyl acrylate having 6 to 20 carbon atoms such as acrylate or benzyl acrylate, isodecyl acrylate or dipentyl acrylate. In the invention, in order to obtain (7) a cross-copolymer of the specific monomer and the acrylate, when the total of the specific monomer and the acrylate is 100 mol in the presence of Lewis acid, usually, the specific monomer The ratio of 30 to 70 moles, acrylate is 70 to 30 moles, preferably 40 to 60 moles of the above specific monomers, and the ratio of acrylates to 6 to 40 moles - 22 - 200815192 ' The above specific monomer is 45 to 55 moles, and the acrylate is radically polymerized at a ratio of 55 to 45 moles. The amount of Lewis acid used to obtain (7) the above-mentioned specific monomer and acrylate copolymer , relative. In the acrylate i 〇〇 Moer became 〇 · 001 ~ 1 Mo Further, an organic peroxide or an azobis-based radical polymerization initiator which is known to cause radical generation may be used, and the polymerization temperature is usually -20 ° C to 80 ° C, preferably 5 Further, the solvent for the polymerization reaction can be the same as the solvent used for the ring-opening polymerization reaction. Further, the term "interactive copolymer" as used in the present invention means a structure derived from the above specific monomer. The units are not contiguous, that is, the adjacent structural units from the above specific monomers must be a copolymer having a structure derived from the structural unit of the acrylate, and the structural units derived from the acrylate are adjacent to each other. The structure of existence cannot be denied. The proper molecular weight of the cyclic olefin resin used in the present invention is preferably 0.2 to 5 dl/g, more preferably 0.3 to 1.5 (in terms of intrinsic viscosity [7?] inh (measured at 30 ° C in chloroform). Preferably, the number average molecular weight (?η) of the converted polystyrene measured by gel permeation chromatography (GPC) is 8,000 to 100,000, more preferably 10,000 to 80,000, and particularly preferably 12,000. ～50,000, the weight average molecular weight (Mw) is 20,000 to 300,000, more preferably 30,000 to 250,000, and particularly preferably in the range of 40,000 to 200,000. Intrinsic viscosity [7?] Uh, number average molecular weight and weight average When the molecular weight is in the above range, the heat resistance and water resistance of the cyclic olefin resin can be improved, and the mechanical properties and the moldability of the optical film of the present invention are excellent. The glass transition temperature (Tg) of the cyclic olefin resin is usually 110 ° C or higher, preferably 110 to 350 ° C, more preferably 120 to 250 ° C, and particularly preferably 120 to 200 ° C. Tg is less than 1 l〇 °C, due to high temperature conditions It is not appropriate to deform by secondary processing such as coating film or printing. On the other hand, when Tg exceeds 305 ° C, molding processing becomes difficult, and the possibility of resin deterioration due to heat during forming processing In the case of the cyclic olefin-based resin, the specific hydrocarbon-based resin described in Japanese Laid-Open Patent Publication No. Hei 9-22 No. Hei. Or a known thermoplastic resin, a thermoplastic elastomer, a rubbery polymer, an organic fine particle, an inorganic fine particle, etc. Further, the cyclic olefin resin of the present invention is improved in heat deterioration resistance without impairing the effects of the present invention. An additive such as a known antioxidant or an ultraviolet absorber may be added to the light resistance, for example, a group selected from the group consisting of a phenol compound, a thiol compound, a sulfide compound, a disulfide compound, and a phosphorus compound. At least one compound can increase the heat deterioration resistance by adding 〇·〇1 to 1 part by weight to 1 part by weight of the cyclic olefin resin of the present invention. The compound: a phenolic compound may, for example, be a triethylene glycol-bis[3-(3-tris-24-200815192 butyl-5-methyl-4-hydroxyphenyl)propionate], 1, 6-hexanediol-bis[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6- (4 - mercapto-3,5-di-tert-butylanilino)-3,5-diindole, pentaerythritol-four [3-(3,5-di-tertiary butyl-4) -hydroxyphenyl)propionate],2,2-thio-divinylbis[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate], octadecyl- 3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate],N,N-hexylenebis(3,5-di-tri-butyl-4-hydroxy-hydrocinna Indoleamine, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tri-butyl-4-hydroxybenzyl)benzene, three-(3,5-di -Tributyl-4-hydroxybenzyl)-triisocyanate, 3,9-bis[2-[3-(3-tris-butyl-4-hydroxy-5-methylphenyl)propanyl Oxygen]-1,1-dimethylethyl]-2,4,8510-tetraoxahelix [5·5]~( '院, et al. Preferred is octadecyl-3-(3,5-di-tertiarybutyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tri ( 3,5-di-tris-butyl-4-hydroxybenzyl)benzene, neopentyl alcohol-tetra[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionic acid Ester], particularly preferably octadecyl-3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate). Thiol-based compound: Examples of the thiol-based compound include a tertiary thiol alcohol, an alkylthiol such as hexyl thiol, 2-hydrothiobenzimidazole, and 2-hydrothio-6-methyl. Benzimidazole, 1-methyl-2-(methylhydrothio)benzimidazole, 2-hydrothio-1-methylbenzimidazole, 2-hydrothio-4-methylbenzimidazole, 2-Homothio-5-methylbenzimidazole, 2-hydrothio-5,6-dimethylbenzimidazole, 2-(methylhydrothio)benzimidazole, 1-methyl-2 -(Methylthiosulfonyl)benzimidazole-25-200815192 2-Hydroxythio-1,3-dimethylbenzimidazole, thioacetic acid, and the like. Sulfide compound: In terms of a sulfide compound, 2,2-thio-diethyl bis[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate] , 2,2-thiobis(4-methyl-6-tertiary butylphenol), 2,4-bis(n-octylthiomethyl)

)-6-methylphenol, dilauryl 3,3'-thiodipropionate, di-glycine 3,3, thiodipropionate, distearyl 3,3,-sulfur Dipropionate, pentaerythritol-based four (3-laurylthiopropionate), double thirteen-yard 3,3'-thiodipropionate, and the like. Disulfide-based compound: a disulfide-based compound may, for example, be bis(4-chlorophenyl)diide, bis(chlorophenyl)disulfide, bis(=chlorophenyl) sulfide, bis (2) ,4,6-trichlorophenyl)disulfide, bis(2-nitrophenylnaphthyldithiobis(2-chloronaphthyl) disulfide, ethyl 2,2,-dithiodibenzoate , bis(4_acetamidine) disulfide, bis(4-aminomethylphenyl) disulfide, ii,-dinaphthyl disulfide, 2,2,-dinaphthyl disulfide , naphthyl) disulfide, 2,2,-bis (1-chloro

2,2'-bis(1-cyanophthyl) disulfide, disulfide, dilaurylthio 2,2丨-bis (dipropionate-based compound: -26-200815192 phosphorus compound, Tris(4-methoxy-3,5-diphenyl). phosphite 'tris(nonylphenyl) phosphite, tris(2, aryl-tertiary butylphenyl) Phosphate ester, bis(2,6-di-tert-butyl-4-methylphenyl)isopentyl alcohol diphosphite, bis(2,4-di-tri-butylphenyl)nepentaerythritol Alcohol diphosphite, etc. Further, a diphenyl ketone compound such as 2,4-dihydroxydiphenyl ketone or 2-hydroxy-4-methoxydiphenyl ketone, N-(benzyloxycarbonyl) a benzotriazole-based compound such as oxybenzotriazine or a oxalic acid-based benzoic acid such as 2-ethylglyoxime or ethyl-2f-ethoxyxantanilide, relative to the present When 100 parts by weight of the cyclic olefin resin of the invention is added in an amount of 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, the light resistance can be improved. Further, the cyclic olefin resin according to the present invention is borrowed. By melt extrusion in the form of a film or the like, by melt extrusion The thermal history, the selection of the antioxidant to prevent the thermal deterioration of the resin is an extremely important technical element. That is, in the case where the film obtained by melt extrusion is subjected to drawing processing, it cannot be lowered. The linear phase transition temperature (Tg) of the cyclic olefin-based resin glass which is melt-extruded is + 20 ° C to Tg + 130 ° C, preferably Tg, in order to reduce the degree of reduction. + a hindered phenol compound having a melting point in a temperature range of 30 ° C to Tg + 130 ° C is preferably used as an antioxidant. The melting point is less than +20 ° C than the Tg of the melt extruded cyclic olefin resin, even if When a hindered phenol-based compound is used, the amount of phase difference is greatly lowered when the amount of addition is increased. On the other hand, the melting point is more than +1 3 〇° than the Tg of the melt-extruded cyclic olefin resin. In the case of C, the antioxidant is not dissolved in the addition of -27-200815192, but it is a cause of film defects such as fisheye or foreign matter. Further, the melting point is Tg + 20 °C in the cyclic olefin resin.

When Tg+13°C is used as an antioxidant, when the compound other than the hindered phenol-based compound is used as an antioxidant, the cyclic olefin-based resin of the present invention can be melt-extruded. The forming condition can be used as appropriate. Specific examples of the above antioxidant may, for example, be 1,3,5-trimethyl-2,4,6-tris(3,5-di-tri-butyl-4-hydroxybenzyl)benzene, N. , N,-hexylene bis(3,5·di-tris-butyl-4-hydroxy-hydrocinnamylamine), three-(3,5-di-tri-butyl-4-hydroxybenzyl) - isocyanate, tris(2,4-di-tertiary butylphenyl) phosphite, etc., but the present invention is not limited to these, and the like, and the like, there is a cyclic olefin-based resin which is melt-extruded. Tg has an uncomfortable situation. Further, these may be used in combination or may be used alone without departing from the scope of the effects of the present invention. The amount of the antioxidant added is usually 0.01 to 5 parts by weight, preferably 0.05 to 4 parts by weight, more preferably 0.1 to 1.5 parts by weight, per 100 parts by weight of the cyclic olefin resin. When the amount of the antioxidant added is less than 1 part by weight of the ruthenium, the resin is liable to be gelled during the extrusion processing, and as a result, the resulting film is recognized as a defect. On the other hand, when the amount of the additive exceeds 5 parts by weight, the occurrence of eye mucus may occur during processing, and the scale may become a die line, a fish eye on the film, burnt, or the like. The reason is not good. Such an antioxidant can be added at the time of producing a cyclic olefin resin, and -28-200815192 can be simultaneously blended with particles of a cyclic olefin resin at the time of melt extrusion. Further, in the case where the cyclic olefin resin of the present invention is formed by melt extrusion, a flame retardant, an ultraviolet absorber, a dye, a pigment or the like may be used in addition to the above-mentioned antioxidant, insofar as the effects of the present invention are not impaired. additive. Of course, in this case, in the case of an additive having a melting point, the melting point thereof is preferably in the range of the melting point of the essential antioxidant of the present invention. &lt;Film Forming&gt; In the method of molding a cyclic olefin-based resin film, there are a solvent casting method (flow casting method) or a melt extrusion method, and the film thickness uniformity and surface smoothness can be achieved. A good point is the solvent casting method, and the melt extrusion method is preferred on the production cost side. [Solvent-casting method] The method of obtaining a cyclic olefin-based resin film by a solvent casting method is not particularly limited, and a known method can be applied. For example, a method in which the above cyclic olefin-based resin is dissolved or dispersed in a solvent to a moderate concentration, and is injected onto a suitable substrate, or coated, dried, and then peeled off from the substrate. Hereinafter, the conditions of the method for obtaining a cyclic olefin-based resin film by a solvent casting method are shown, but the present invention is not limited to these conditions. When the cyclic olefin-based resin is dissolved or dispersed in a solvent, the concentration of the resin is usually from 0.1 to 90% by weight, preferably from 1 to 50% by weight, more preferably from 10 to 35% by weight. %. When the concentration of the resin is lower than the above range -29 - 200815192, it is difficult to ensure the thickness of the film, and it is difficult to obtain the surface smoothness of the film due to foaming accompanying evaporation of the solvent. On the other hand, when the concentration exceeds the above range, the thickness or surface of the cyclic olefin-based resin film which is obtained by excessively high viscosity of the solution tends to be less uniform. Further, the viscosity of the solution at room temperature is usually 1 to 1, 〇〇〇, 〇〇〇mPa*s, preferably 1 〇 to 1 〇〇, 〇〇〇mPa, s, more preferably 100 to 50,000. mPa.s, especially good for 1, 〇〇〇~40,000 mPa.s. Examples of the solvent include aromatic solvents such as benzene, toluene, and xylene; and cellosolve solvents such as methyl cellosolve, ethyl cellosolve, and 1-methoxy-2-propanol; a ketone solvent such as an alcohol, acetone, cyclohexanone, methyl ethyl ketone or 4-methyl-2-pentanone; an ester solvent of methyl lactate or ethyl lactate; cyclohexane, ethylcyclohexane a cycloolefin solvent such as alkane or 1,2-dimethylcyclohexane; a halogen-containing solvent such as 2,2,3,3-tetrafluoro-1-propanol, dichloromethane or chloroform; tetrahydrofuran, dioxane An ether solvent such as 1-ether alcohol or 1-butanol or the like. Further, in addition to the above, the use of SP値 (solubility parameter) is 10 to 30 (MPa1/2), preferably 10 to 25 (MPa1/2), more preferably 15 to 25 (MPa1/2), which is particularly preferable. A solvent of a range of 15 to 20 (MPa1/2) _ 'a cyclic olefin resin film having good surface uniformity and optical properties can be obtained. These solvents may be used alone or in combination of two or more. In the case of a mixed system, it is preferred that the range of SP値 in the case of being a mixed system is within the above range. In this case, in the case of the mixed system SP, it can be predicted from the weight ratio, for example, when the two types are mixed, the respective weight fractions are W1 -30-200815192 and W2, and the SP値 is SP1 and SP2. SP値 can be obtained by the following formula SP 値=W1 · SP1+W2 · SP2 ^. In the method of applying the above solution to a substrate, in addition to the method using, for example, a mold or an applicator, a spray method, a brush coating method, a roll coating method, a spin coating method, or a dipping may be employed. (dipping) law, etc. Further, it is also possible to control the thickness, the surface smoothness, and the like under repeated coating. The substrate may, for example, be a polyester film such as a metal drum, a steel belt, a polyethylene terephthalate (PET) or a polyethylene naphthalate (PEN), or a polytetrafluoroethylene (product). Name; Teflon (registered trademark)) W Temple. The drying step of the solvent casting method is not particularly limited, and it can be carried out by a method generally used, for example, a method of passing a plurality of rolls through a drying furnace. However, in the drying step, when bubbles occur in the evaporation of the solvent, the characteristics of the film are remarkably lowered. To avoid this, the drying step can be divided into two or more steps to control the temperature or air volume of each step. It is better. In particular, the drying step of the substrate to the peeling is divided into two or more steps, and the temperature is 〇~50 ° C, preferably 10 to 40 ° C in the first drying step, in the second step. When the temperature in the drying step after the step is 50 to 200 ° C, preferably 70 to 180 ° C, the Rth ( 5 50 ) of the obtained film can be adjusted to an appropriate range ( 30~300nm), so it is very appropriate. Further, in order to make the phase difference R0 (550) in the film surface 0 to -31 - 200815192 3 0 0 nm, the stress TF (MPa) at the time of film peeling is preferably in the range of 0.01 MPa STF S5 MPa. When TF does not reach O.OIMPa, the shell cannot be peeled off well. On the other hand, when the film is peeled off from the roll by more than 5 MPa, R 〇 ( 5 50 ) &gt; 300 nm is not preferable. Here, the maximum refractive index in the in-plane of the film is nx at a light wavelength of 550 nm, the refractive index in the direction perpendicular to nx in the film plane is ny, and the refractive index in the thickness direction of the film is nz, so that the film thickness is d. In [nm], the phase difference R0 ( 550) [ nm ] = ( nx - ny ) xd in the film plane is the phase difference Rth ( 550 ) [ nm ] = { ( nx + ny ) / 2 - η z } xd means. Further, when the phase difference R0 ( 5 50 ) in the plane of the film exceeds 300 nm, light leakage is liable to occur, and there is a contrast reduction. Further, when the phase difference Rth (550) in the thickness direction of the film is within the above range, the optical film is used as a viewing angle compensation purpose, and the contrast of the obtained liquid crystal panel is large, and the color shift is changed. Small, making the viewing angle characteristics very good. [Melt extrusion method] The method for obtaining a cyclic olefin resin film by a melt extrusion method is not particularly limited, and a known method can be applied. For example, a method in which a cyclic olefin-based resin in a molten state is extruded from a mold attached to an extruder to press the resin onto the surface of the mirror roll, and then cooled and peeled off to form a sheet is obtained. -32- 200815192 In order to melt the cyclic olefin-based resin, it is preferred to melt the resin by an extruder, and the molten resin is quantitatively supplied by a gear pump to be filtered by a metal filter or the like. After the impurities are removed, it is preferred to extrude the film on one side of the mold. The method of cooling and extruding the film extruded from the mold includes a nip roll method, an electrostatic addition method, an air knife method, a rolling method, a single-sided belt method, a double-sided belt method, and a three-roller method. In order to manufacture a sheet having less optical distortion, a single-sided tape type may be used, and a sheet manufacturing apparatus called a sleeve type, an electrostatic addition method, or the like is preferable. For example, a mirror roll and a metal strip are disposed under the discharge port of the mold, and a film forming apparatus in which the peeling roll is disposed in parallel with the mirror roll is disposed. The above-mentioned metal belt is held in a state in which tension can be applied by two holding rolls provided in contact with the inner surface thereof. The resin discharged from the discharge port is pressed between the mirror roll and the metal belt, transferred to the mirror roll, and cooled, and then peeled off by a peeling roll to form a film. Further, at the positions of both ends of the discharged film, the electrode is placed under the discharge port of the mold with respect to the mirror roll, and the film is attached to the mirror roll side without optical deformation to make the film surface. It is also an appropriate method to become a good method. As the extruder, any of a single shaft, a two shaft, a planetary type, a co-kneader or the like can be used, and a single shaft extruder is preferably used. Further, in terms of the spiral shape of the extruder, a vent type, a front end with a squeegee type, a full flight type, etc., preferably a full flight type may be used. For gear pumps for resin metering, either internal lubrication or external lubrication can be used, with external lubrication being preferred. -33- 200815192 The filter used for the filtration of the foreign matter may, for example, be a leaf desk type, a candle filter type, a leaf type, a screen mesh or the like. Among them, in order to reduce the distribution of residence time of the resin, the leaf desk type is optimal, and the nominal opening of the mesh opening of the filter is 20 μm or less, preferably ΙΟμπι. Hereinafter, it is more preferably 5 μπι or less. It is preferably 3 μιη or less. When the nominal opening is larger than 20 μm, in addition to the foreign matter visible in the eye, it is difficult to remove the gel or the like, so that it is not preferable in terms of producing a filter for an optical film. In terms of the mold, it is necessary to make the resin flow inside the mold uniform, and in order to maintain the uniformity of the film thickness, it is necessary to distribute the internal pressure of the mold near the die exit in the width direction. In order to satisfy such a condition, a manifold mold, a fish tail mold, a coat hanger mold or the like can be used, and among these, a coat mold is preferred. In addition, the flow rate of the mold is adjusted to use a bending lip type. In addition, it is particularly preferable to use a mold that is automatically controlled by a heat bolt to perform thick adjustment. If the choke bar is installed for flow adjustment, or the iip block for thickness adjustment is installed, the height difference may occur in the mounting portion, or the air may enter the gap in the mounting portion. It is also a cause of scorching, which is also a cause of becoming a mold line. The discharge port of the mold is preferably a coated film such as a superhard coating film such as tungsten carbide. Further, the material of the mold may, for example, be steel such as S C tantalum or stainless steel such as SUS, but is not limited thereto. Also, an electroplated person who applies chromium, nickel, titanium or the like to the surface can be used by PVD ( -34- 200815192)

The physical Vapor Deposition method is a method in which a film such as TiN, TiAIN, TiC, CrN, or DLC (diamond-like carbon) is formed, and other ceramics are flame-sprayed, and the surface is nitrided. Since such a mold has a high surface hardness and a small friction with the resin, it is possible to prevent the occurrence of burnt dust and the like in the obtained transparent resin sheet, and it is preferable to prevent the occurrence of the mold line. The mirror roll is preferably one having a heating means and a cooling means inside, and φ has a surface roughness of 0.5 μm or less, particularly preferably 0.3 μηη or less. In terms of the mirror roll, it is preferable to use electroplating for the metal roll, and it is preferable to perform chrome plating or electroless nickel plating. The method of heating the mirror roll is preferably a jacket type oil temperature adjustment method or a dielectric heating method. The heating method of the roller is not particularly limited. The temperature of the roller is in the film forming range, and the temperature difference is preferably no difference. The temperature difference in the width direction of the allowable roller is preferably within 2 ° C, more preferably within 1 ° C. . • Single-sided belt-type device, or sleeve-type retraction device, in the case of metal belts, it is better to use a seamless beltless belt. As the material constituting the metal strip, stainless steel, nickel, or the like can be used. Further, it is preferable that the surface of the holding roller for holding the metal tape is coated with a rubber body or the like which can have a polyoxymethylene rubber or other heat resistance. The thickness of the metal strip is preferably 0.1 to 0.4 mm, and when it is less than 0.1 mm, the flexure is large, and the belt is not directly damaged. On the other hand, when the thickness is larger than 〇.4 mm, it is not preferable because it does not deform with the film during processing. -35- 200815192 By the above apparatus, a film of, for example, a second mode can be manufactured. In general, before the introduction of the cyclic olefin-based resin in the extruder, the resin contained in the resin, the gas (oxygen or the like), the residual solvent, and the like are removed in advance, and the resin can be dried at a suitable temperature equal to or lower than the resin Tg. The dryer for drying is preferably vacuum dried using an inert gas circulation dryer. Further, since the moisture absorption in the hopper (h 〇pper ) or the absorption of oxygen can be suppressed, it is also possible to seal the hopper with an inert gas such as nitrogen or argon or to use a vacuum hopper that can be maintained in a reduced pressure state. . In the extruder cylinder, the resin is oxidized during melt extrusion to prevent gelation or the like from occurring, and it is preferably sealed by an inert gas such as nitrogen or argon. The cyclic olefin-based resin which is melted by the extruder is extruded into a sheet shape toward the lower side in the vertical direction. The temperature distribution of the die exit is preferably controlled within ±1 °C because the difference in melt viscosity of the resin is reduced. Thereafter, the extruded resin is cooled by a mirror roll and a metal belt. Then, the resin transferred on the surface of the mirror roll is peeled off from the surface of the mirror roll by a peeling roll, and a sheet-like film can be produced. In the present invention, the processing temperature of the resin, that is, the set temperature of the extruder and the mold, is such that the resin having a uniform molten state can be discharged from the mold, and the resin can be suppressed from the viewpoint of suppressing deterioration of the resin. Tg +loot: Above, Tg + 200 ° C or less is preferred. Further, when the mirror roll and the metal are used to press the resin, that is, the pressure at the time of transfer of the resin by the mirror roll, the surface pressure is preferably from 0. 01 to 〇.8 MPa, particularly preferably from 0.1 to 〇. 6MPa. More preferably, it is 0.15 to 0.45 MPa. When the pressure is -36-200815192 as described above, the cause of Rth (550) of the obtained film can be adjusted to an appropriate range, so it is very good. At this time, in order to make the angle Θ of the optical axis ' in the thickness direction of the film and the normal line with respect to the film surface 0 to 3 °, it is preferable to make the peripheral speed of the mirror roll and the metal strip close. In terms of the proper range, when the peripheral speed of the mirror roll is 1.00, the peripheral speed of the metal strip is 0.95 to 1.05, and particularly preferably 0·99 to 1.01. If it is such a range of the peripheral speed, the optical axis in the thickness direction of the film can be made to have an angle 0 of 0 to 3 with respect to the normal line of the film surface. Further, when the Θ exceeds 3°, the color shift or contrast differs depending on the orientation of the liquid crystal panel, and the result of the asymmetry with respect to the transmission axis of the polarizing plate is not preferable. Further, in order to set the film in-plane retardation R0 (550) to 0 to 300 nm, the peeling temperature Tt (° C.) and the peeling stress TF (MPa) in the film peeling condition are each at Tg-30°. CSTtSTg + 5 ° C, 0.01 MPa ^ TF ^ 5 MPa range is preferred. When it exceeds this range, when the film is peeled off from the roll, it becomes R0 (5 50) &gt; 300 nm is not preferable. &lt;Film stretching processing&gt; The optical film of the present invention is an optical film obtained by a flow casting method or a melt extrusion method as described above, and can be further stretched. In the case of the stretching processing method in this case, specifically, a well-known one of the axial stretching method or the biaxial stretching method can be exemplified. That is, there is a horizontal-axis stretching method by the stretcher method, a roll-to-roll compression stretching method, a vertical axis stretching method using two sets of rolls having different circumferences, or a combination of a horizontal one axis and a vertical one axis. Shaft stretching method -37-200815192, stretching method by expansion method, and the like. In the case of the one-axis stretching method, the stretching speed is usually from 1 to 5, 〇〇〇% / min, preferably from 50 to 1, 〇〇〇%/min, more preferably from 100 to 1,000%/min. Very good for 100~500%/min. In the case of the biaxial stretching method, there are cases in which stretching is carried out in two directions at the same time or stretching treatment in a direction different from the initial stretching direction after stretching in one axis. In this case, the angle of intersection between the two stretching axes for controlling the elliptical shape of the refractive index of the film after stretching is not particularly limited as long as it can be determined by the desired characteristics, and is usually in the range of 120 to 60 degrees. Further, the stretching speed may be the same in each stretching direction, or different, and is usually 1 to 5, 〇00%/min, preferably 50 to 1,0 00%/min, more preferably 1 〇〇~ 1,000%/min, particularly preferably 100 to 5.00%/min. The stretching processing temperature is not particularly limited, and is based on the glass transition temperature Tg of the resin of the present invention, and is usually Tg: t3 0 °c. Preferably, it is Tg ± 15 ° C, more preferably in the range of Tg - 5 ° C ~ Tg + 15 ° C. Within this range, occurrence of unevenness in phase difference can be suppressed, and control of the refractive index ellipsoid can be made easy. The stretching ratio is not particularly limited because it can be determined by the desired characteristics, and is usually 1.0 1 to 10 times, preferably 1·03 to 5 times, more preferably 1.03 to 3 times. When the draw ratio is 10 times or more, the control of the phase difference becomes difficult. The stretched film can be cooled as it is, and maintained at a temperature of Tg-20 ° C to Tg for at least 10 seconds, preferably 30 seconds to 60 minutes, more preferably 1 minute to 60 minutes, for thermal setting. It is better. Thereby, a phase difference film which is stable from -38 to 200815192 with a small change in the phase difference of the transmitted light can be obtained. The dimensional shrinkage rate by heating of the optical film of the present invention in the case where the stretching process is not carried out is carried out by heating in a loot for 500 hours, usually 5% or less, preferably 3% or less, more preferably 1 Below %, it is particularly preferably 0.5% or less. Moreover, the dimensional shrinkage rate by heating of the optical film of the present invention is usually 10% or less, preferably 5% or less, more preferably 3% or less, in the case of heating at 100 ° C for 500 hours. Good is less than 1%. In order to make the dimensional shrinkage within the above range, and the selection of the specific monomer or copolymerizable monomer of the resin raw material of the present invention, it is possible to control by a casting method or a stretching method. The film stretched as described above can impart a phase difference of the transmitted light by stretching the molecules, and the phase difference can be controlled by the stretching ratio, the stretching temperature, the thickness of the film, and the like. For example, in the case where the thickness of the film before stretching is the same, the film having a larger stretching ratio tends to have an absolute increase in the phase difference of the transmitted light, so that the transmission of light can be obtained by changing the stretching ratio. A retardation film with a desired phase difference. On the other hand, when the draw ratio is the same, the thicker the thickness of the film before stretching, the larger the absolute difference in the phase difference of the transmitted light tends to be, so that the thickness of the film before stretching can be changed to obtain the transparency. The light imparts a phase difference film having a desired phase difference. Further, in the above-described stretching processing temperature range, the lower the stretching temperature, the higher the absolute difference in the phase difference of the transmitted light tends to be, so that the phase of the phase difference which is expected to be transmitted to the transmitted light can be obtained by changing the stretching temperature. Poor film. The thickness of the optical film (retardation film) stretched in the above manner is usually -100 to 200815192 degrees, preferably 100 μm or less, preferably 100 to 20 μm, more preferably 80 to 20 μm. When the thickness is made thinner, it is possible to greatly reduce the size and film thickness required for the use of the phase difference film. Here, in order to control the thickness of the retardation film, it is possible to control the thickness of the optical film before stretching or to control the stretching ratio. For example, the thickness of the retardation film can be further reduced by making the optical film before stretching thinner and making the stretching ratio larger. Further, the amount of the residual solvent in the film used in the optical film of the present invention is usually 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less, and particularly preferably 5% by weight or less. Here, when the amount of the residual solvent exceeds the above range, the size tends to largely change due to the change in time during actual use, and the Tg may be lowered by the residual solvent, and the heat resistance may be lowered. Further, the thickness distribution of the above film is usually within ±10% with respect to the average enthalpy, preferably within 5%, more preferably within 1%, and particularly preferably within 0.5%. Further, the variation per 1 cm of thickness is usually 1% or less, preferably 0. 1% or less, more preferably 0.01% or less, and particularly preferably 0. 0 0 5 % or less. By controlling the thickness distribution of the optical film within the above range, when the stretching process is performed as the case may be, unevenness in phase difference or misalignment of the optical axis can be prevented. Here, the thickness distribution was measured by a film thickness measuring device "Profiler 140E" manufactured by MO CON Co., Ltd. at intervals of 1 mm. <<Protective Film>> The protective film of the present invention is made of a cyclic olefin resin, and protects the surface of the optical film of -40 - 200815192, and the optical film and the protective film are laminated and wound to form the present invention. Optical film roll. Here, the protective film of the present invention may have an adhesive layer on one side of the protective film, or may have an adhesive layer on one side of the protective film and a conductive layer on the other side. The material of the protective film used in the present invention is preferably excellent in transparency, mechanical strength, thermal stability, moisture shielding property, isotropic property, and the like, and may, for example, be polyethylene terephthalate or polyethylene. A polyester-based polymer such as a diester, a cellulose-based polymer such as diethyl cellulose or triethyl fluorenyl cellulose, an acrylic polymer such as polymethyl methacrylate, or polystyrene or acrylonitrile. Styrene-based polymer such as styrene copolymer (AS resin), polycarbonate-based polymer, polyethylene, polypropylene, olefin-based resin having a ring-based or no-tendenene structure, ethylene-propylene copolymer Etc. EP (D) Μ, chlorinated ethylene-based polymer, urethane-based polymer such as nylon or aromatic polyamide, quinone-based polymer, lanthanide polymer, polyether maple polymer, Polyetheretherketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinyl chloride polymer, ethylene butyral polymer, arylate polymer, polyoxymethylene Polymer, epoxy polymer, or the above polymerization The blends and the like. It is preferably an olefin-based resin such as polyethylene or polypropylene from the viewpoint of preventing damage of the protective film of the optical film. In the protective film, various additives such as a light stabilizer, an ultraviolet absorber, an antioxidant, and a sputum agent may be blended as needed. Further, a well-known surface modification treatment such as a corona discharge treatment can be performed. -41 - 200815192 The film thickness of the protective film is preferably 5 to 50 μm, more preferably 5 to 3 μm. When it is thinner than 5 μηι, there is a tendency to manufacture it. On the other hand, when it is thicker than 50 μm, the price tends to be high. The protective film used in the present invention is required to have a diameter (φ) of 30 μχ or more contained in the film of 5 pieces/m 2 or less. It is preferably j/m2 or less. Here, the fisheye means that the material which becomes a protective film is heat-melted and kneaded, and the undissolved and deteriorated material of the material is smashed in the film by the extrusion drawing method or the casting method. The meaning of the taker. Further, the size of the diameter of the fish eye varies depending on the material, and is about 1 Ομηι 1 mm, and the height from the surface of the film is about 1 to 50 μm. Here, the method for measuring the size of the fish eye can be measured, for example, by an optical microscope, a contact type surface roughness meter, or a scanning electron microscope. In addition, the diameter of the fisheye (Φ) refers to the largest diameter. In the protective film of the present invention, when the fisheye having a diameter of 30 μm or more exceeds 5/m 2 , the optical film and the protective film are laminated and rolled back into an optical film roll, and the protective film having the fish eye is abutted against the surface of the optical film for a long period of time. , micro-concavities on the surface of the optical film, resulting in optical unevenness. Further, in terms of the surface roughness of the protective film, the center line average roughness Ra is preferably 0·0 0 5~0 · 〇 5 μπι, and further preferably 〇.〇1~〇.〇30111. The surface roughness can be measured using a contact type surface roughness meter. In this way, the protective film of the present invention having a good fisheye grade can be suitably used. For example, when the film is produced, the raw material resin is thermally melted, and a polymer filter having a fine opening of 1 Ομηι or less is used to filter foreign matter, gel, and the like. It can be manufactured by changing the film manufacturing method. -42- 200815192 In addition to the commercially available contents of the polyolefin-based protective film, in addition to the PP-type PT manufactured by Shin-Etsu Film Co., Ltd., the Uefin BO-2400 or YR12 type manufactured by Toray Co., Ltd., UeteCh#73 32 manufactured by Toray Film Processing Co., Ltd. In addition to the Alphand E200 series manufactured by Oji Paper Co., Ltd., 622 1SC-30 manufactured by Sekisui Chemical Co., Ltd., PAC-3 manufactured by San-a Chemical Co., Ltd., and the like can be exemplified, but is not limited thereto. Further, in terms of the adhesive constituting the adhesive layer which can be formed on one surface of the protective film, generally, the adhesive for re-peeling (acrylic, rubber, synthetic rubber, etc.) to be used can be used without limitation. Among them, an acrylic adhesive which can easily control the adhesion is preferable because it is excellent in adhesiveness, workability, durability, and the like. Further, it is preferred that the adhesive layer be crosslinked by a crosslinking agent. Further, in the above-mentioned adhesive, an adhesive, a plasticizer, a sputum, an antioxidant, an ultraviolet absorber, a decane coupling agent or the like can be suitably used as needed. The method for forming the adhesive layer is not particularly limited, and examples thereof include a method of applying an adhesive to a polyester film treated with a polyfluorene oxide, drying the film, and transferring the film to a protective film (transfer method). The adhesive composition is directly coated with a method of drying (direct printing method) or a method of co-extrusion. The thickness of the adhesive layer is not particularly limited, and is preferably about 3 to ΙΟΟμπι, and more preferably about 5 to 40 μm. Further, it is preferable that the opposite side of the face of the adhesive layer of the above protective film is formed to form a conductive layer. The conductive layer is a method for forming a transparent base film by blending a surfactant, a conductive carbon, a metal powder, and the like with a commonly used polymer such as polyester, and a method of forming a transparent base film. The surfactant or the conductive resin is applied, dried, and a conductive material such as a metal or a conductive metal oxide is applied onto the protective film, and a method such as vapor deposition or plating is formed. The thickness of the conductive layer is not particularly limited, and is preferably about 0.01 to Ιμπι, particularly preferably about 0.03 to 0.8 μm. When the thickness of the conductive layer is thinner than Ο.ΟΙμπι, the antistatic effect is lacking, and the effect of removing static electricity is thicker than 1 μm, which is not preferable because the light transmittance is lowered. <<Optical Film Roller>> The optical film roll of the present invention is obtained by laminating an optical film formed of the above-mentioned cyclic olefin resin and a protective film. Here, when the optical film and the protective film are laminated and rolled back, the mirror roll that controls the rotation speed with a certain tension and the optical film and the protective film that are moved up and down with air are attached, and the method of bonding is performed. Can be used properly. In order to prevent the deviation of the winding, an edge position control system (EPC) or the like is used as a method for winding while preventing the offset between both ends of the film. <<Polarizing Plate>> The polarizing plate of the present invention is an optical film of the present invention which is a viewing angle compensation film on at least one side of a polarizing element such as a PVA film, and uses -44-200815192 as an aqueous solution mainly composed of PVA resin. The water-based adhesive, the polar group-containing adhesive, the photocurable adhesive, etc. are attached, and may be heated or exposed as needed to be pressed, and the polarizing element and the viewing angle compensation optical film are adhered. It can be manufactured by joining (lamination). <<Liquid Crystal Panel>> The liquid crystal panel of the present invention has at least one side of a liquid crystal display element formed by liquid crystal holding between two glass substrates, and the polarizing plate of the present invention is bonded to adhere the liquid crystal display element to the polarizing plate (layer It can be manufactured. At this time, a polarizing plate was used on both surfaces of the glass substrate. [Embodiment] [Embodiment] Hereinafter, specific embodiments of the present invention will be described, but the present invention is not limited to the embodiments. In addition, the following "parts" and "%" mean "parts by weight" and "% by weight" unless otherwise specified. Further, in the following examples, the glass transition temperature, the saturated water absorption rate, the point defects of the protective film, the total light transmittance, the haze, the in-plane phase difference of the transmitted light, the transmittance and the degree of polarization of the polarizing plate are It was measured according to the method described below. [Glass transfer temperature (Tg)] Using a differential scanning calorimeter (DSC) manufactured by Seiko Instruments, the glass transition temperature was measured under a nitrogen atmosphere at a temperature increase rate of 20 ° C /min. -45- 200815192 [Saturated water absorption] According to ASTM D5 70, the sample was immersed in water at 23 ° C for 1 week, and the change in weight of the sample before and after immersion was measured, from which the saturated water absorption rate was obtained. [Fisheye and dot-like defect measurement] The protective film or the optical film 1 〇m2 was spread on a black paper, and it was confirmed that the reflected light was shaken under a 10Ow fluorescent lamp. This portion is calculated by making the sway of the reflected light a point defect of the fisheye and optical film of the protective film. Thereafter, the film was observed with a microscope of 50 times to count the number of fish eyes or dot defects of 30 μm or more. The observation of the point defects of the roll-shaped optical film was also performed in the same manner. [Total Light Transmittance, Haze] The haze meter "ΗΜ-150 type" manufactured by Murakami Color Technology Co., Ltd. was used to measure the total light transmittance and haze. [In-plane phase difference (R0)] The "K0BRA-21ADH" manufactured by Oji Scientific Instruments Co., Ltd. was used to measure the in-plane phase difference (R0) when the film light was incident perpendicularly at a wavelength of 50 nm. [Transmittance and Polarization of Polarizing Plate] The "RETS" manufactured by Otsuka Electronics Co., Ltd. was used to measure the transmittance and polarization of the polarizing plate -46-200815192. The measurement wavelength was 55 〇 nm ° [film thickness distribution] The film thickness distribution measuring device (MOCON) was used to measure the film in the longitudinal direction. &lt;Preparation Example 1 &gt; 25 parts of distilled water was placed in a reaction vessel, and 90 parts of butyl acrylate was added to the reaction container, and 8 parts of 2-hydroxyethyl methacrylate, 2 parts of divinyl benzene, and oil were added. After 0.1 part of potassium acid, the stirring blade made of polytetrafluoroethylene (Teflon: registered trademark) was stirred and dispersed. Thereafter, the inside of the reaction vessel was replaced with nitrogen, and the temperature was raised to 50 ° C, and 0.2 part of potassium persulfate was added to start polymerization. Two hours after the start of the polymerization, further, after adding 1 part of potassium persulfate to the polymerization reaction, the temperature was raised to 80 ° C, and the polymerization was continued for 1 hour to obtain a polymer dispersion. Then, the polymer dispersion was concentrated to a solid concentration of 70% using an evaporator to obtain an aqueous adhesive (adhesive having a polar group) as an aqueous dispersion of the acrylate polymer. In this way, the obtained water-based adhesive (hereinafter referred to as "aqueous adhesive A" acrylate-based polymer is subjected to gel permeation chromatography (GPC, solvent: tetrahydrofuran), and the conversion polystyrene is measured. When the number average molecular weight (??) and the weight average molecular weight (Mw), the number average molecular weight (??) is 69,000, and the weight average molecular weight (Mw) is -47-200815192 135,000 °. Further, in the case of the water-based adhesive A, in the measurement 3 0 In the case of the intrinsic viscosity (7/inh) of the chloroform, it is 1.2 dl/g. [Example 1] A cyclic olefin-based resin is a norbornene-based resin (manufactured by JSR Corporation: trade name "ARTON D45 3 1 Glass transfer temperature: 1 30 °C) ° The material was dried at 100 ° C under a drying temperature and dehumidified under nitrogen to lead to an extruder (GM-65, manufactured by GM Engineering Co., Ltd.) at 260 ° C. Melt, use a gear pump to dispense liquid, use a 5 μηη leaf stage filter to remove foreign matter, and extrude from a heated die by an aluminum casting heater set at 250 ° C. At this time, the opening of the T die 0.5mm, the distance between the T-die outlet and the pressure-bonding point of the cooling roll film The pressure roller is adhered to a cooling roll of .250 mm φ at a pressure of 65 mm. The temperature of the cooling roll is 120 ° C, and a cooling roll 2 of 250 ηηηφ is placed on the downstream side thereof, and a peeling roll of 250 mm φ is further provided on the downstream side. The film of the thickness of ΙΟΟμηη was peeled off from the peeling roll at a film surface temperature of 1 〇8 ° C at a temperature of 1 15 t, 1 l 〇 ° C to obtain a film of a decene-based resin film. The film of the decene-based resin was 4 kgf. The tension is taken back and bonded to the protective film to obtain an optical film roll (hereinafter referred to as "optical film roll (a-1)") having a length of 2000 m. The film is made of a mirror roll having a surface roughness of 0.1 S. A masking roller and a pair of urethane rubber are passed between a 10 mm-coated rubber roller through a transparent film and a protective film. The protective film that has been used at this time is a Toray film processed to a thickness of -48- 200815192 30μηι protective film (tretech#73 3 2 ), at this time, the number of fish eyes of the protective film is 0.5/m2. Also, the thickness of the center line surface of the protective film is 〇.〇〇〇6μπι. The point of the optical film after peeling off the protective film The number of the defects was 0.3/m2. The total optical transmittance of the optical film roll (a-Ι) was 93%, and the yoke was 〇. 2%. [Comparative Example 1] The same as in the first embodiment In the method, after the resin was melted to obtain a hafnylene-based resin film, the same masking roller and rubber roller as in Example 1 were used to obtain a length of 2,0 〇〇m when the film was bonded to the protective film. Optical film roll (b-1). A commercially available protective film was used as a polyethylene having a thickness of 30 μm, and the number of fish eyes was 6.5/m2. At this time, the center line surface roughness of the protective film is 0.00 8 μπι. # When it is confirmed that the number of dot defects of the optical film after peeling off the protective film is ', it is 5.5 / m2. Further, the optical film roll (b-Ι) had a total light transmittance of 93% and a haze of 0.3%. [Comparative Example 2] In the same manner as in Example 1, the resin was melted to obtain a film of a reduced-alkenyl-based resin, and then a protective film was bonded in the same manner as in Example 1, and a length of 2 was obtained. m optical film roll (C-1). At this time, the protective film for -49-200815192 is a commercially available polyethylene-based protective film having a thickness of 30 μm, and the number of point defects is 5/m2, but the surface of the center line is damaged due to surface damage. The thickness is 〇. 〇 2 5 μ m. When the number of dot defects of the optical film after peeling off the protective film was confirmed, it was 4.5 / m 2 . Further, the optical film roll (c-1) had a total light transmittance of 93% and a haze of 0.3%. The above results are shown in Table 1. [Table 1] Example 1 Comparative Example 1 Comparative Example 2 Fisheye of protective film (pieces/m2) 0.5 6.5 5 Center line average roughness of protective film (μηι) 0.006 0.008 0.025 Number of dot defects of optical film /m2) 0.3 5.5 4.5 [Example 2] Using the optical film roll (a-1) obtained in Example 1, the film was stretched 1.2 times at a temperature of 130 ° C using a roll nip type vertical-axis stretching machine. Thereafter, the stretched optical film roll (a-2) having a thickness of 70 μm was obtained by stretching at 140 ° C using a stretcher type transverse stretching machine to 1.4 times. The phase difference of the optical film roll (a-2) was such that the phase difference (R0) in the film plane was 60 nm. Further, the optical film roll (a-2) had a total light transmittance of 93% and a haze of 0.1%. Further, when the number of dot defects of the optical film roll (a-2) was confirmed, it was 0 · 1 / m2. -50-200815192 [Comparative Example 3] A stretched optical film roll (b-2) was obtained in the same manner as in Example 2 except that the optical film roll (b-1) was used. The phase difference of the film was such that the phase difference (R0) in the film plane was 63 nm. Further, the total light transmittance was 93%, and the haze was 0.2%. Further, when the number of dot defects of the optical film roll (b-2) was confirmed, it was 3.5 / m2. [Example 3] A polyvinyl alcohol film having a thickness of 50 μm was immersed in a bath of 5 g of iodine, 250 g of potassium iodide, 10 g of boric acid, and 1,0 0 g of water to form a 40 ° C bath. At the same time, a polarizing film was obtained by stretching one-axis stretching to 4 times in about 5 minutes. The optical film roll (a-1) produced in Example 1 and the optical film roll (a-1) produced in Example 2 were each polarized on the surface of the polarizing film using the water-based adhesive obtained in the first modification. The film is continuously bonded to each of the single faces to obtain a polarizing plate (a). When the transmittance and the degree of polarization of the polarizing plate (a) were measured, they were 43% and 99.99%, respectively. In addition, the polarizing plate (a) is in the state of two crossed Nicols, and when it is illuminated by one side with a brightness of 1 〇, 〇〇〇cd, it cannot be completely confirmed from the other side due to the point defect. [Comparative Example 4] In addition to using optical film rolls (b-2) and (cl), others -51 -

200815192 In the same manner as in the stomach example 3, a polarizing plate (b) was obtained. When the transmittance and the degree of polarization of the polarized light were measured, they were 4 2 % and 9 9.8 7 %, respectively. Further, % (b) causes the optical film roll (b-2) to be inward to form a crossed Nicols state, and one of the brightnesses is 〇, and 〇〇〇cd is _ _ ' when viewed from the other side. It can be confirmed that it is caused by a point defect of 3.0 / m2. [Industrial Applicability] The optical film and the protective film of the present invention are laminated and rewinded into the film roll. Even if the film is stored for a long period of time, the fish film is less likely to have fine irregularities on the surface of the film. It will produce optical non-rotation. The optical film obtained by the optical film roll of the present invention can be used for mobile phones, digital information terminals, pocket bells, system LCDs, LCD monitors, LCD TVs, boards, 0A. Various components such as a display for a machine, a display for an AV device, an electroluminescence display element, a touch panel, or the like. Also, it is also useful to record CDs, CD-Rs, MDs, DVDs, DVDs, etc. 1(b) The bias is - "The backlight of the film is optically thin and therefore in the light. Therefore, for example, the navigation system, the dimming surface, the crystal display is not used in the device -52-

Claims (1)

200815192 X. Patent Application No. 1 - Optical film roll characterized in that an optical film formed of a cyclic olefin resin and a protective film are laminated and laminated into an optical film roll, in which the protective film is The number of fish eyes having a diameter of 30 μm or more is 5 pieces/m 2 or less. 2. The optical film roll of claim 1, wherein the cyclic olefinic resin is a (.co)polymer of a compound represented by the following general formula (1). [1] R1 (In the formula (1), R1 to R4 show that a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or another monovalent organic group may be the same or different, and any two of R1 to R4 may be used. They may be bonded to each other to form a single-ring or multi-ring structure, 111 is 0 or a positive integer, and p is 〇 or a positive integer). 3. The optical film roll of claim 1 wherein the center line average roughness Ra of the protective film is 0.005 to 0.05 μηι. 4. The optical film roll of claim 1, wherein the protective film is made of a polyolefin resin. A method for producing an optical film roll, characterized in that an optical film formed of a cyclic olefin-based resin film is laminated with a protective film having a diameter of 30 μm or more and a fisheye of 5/m2 or less (superposition) ) Rewinder. -53 - 200815192 无···································································································· Please reveal the chemical formula that best shows the characteristics of the invention: none -4-