TW200521169A - Optical film and polarizing plate - Google Patents

Abstract

The objective of the invention is to provide an optical film which does not decrease visibility so much when used for a high-quality liquid crystal display device without degrading advantages such as various kinds of optical characteristics, heat resistance, adhesion property or sticking property with other materials and polarizing plate using the optical film, and so on of a conventional optical film essentially comprising a cyclic olefin resin or a thermoplastic norbornene resin. The optical film comprises cyclic olefin resin and has less than 10 spots/m<SP>2</SP> of bright spots. The film is suitable for a liquid crystal display.

Description

200521169 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to the use of cycloolefin resins as the main heat source. _Fubu device does not substantially produce point-like defects, and the use of the optical film Polarizer. [Prior art] Cycloolefin resins have the characteristics of rigidity of the main chain structure, glass' main chain structure has a fluffy base, and has the characteristics of amorphousness, small unevenness in light transmission, and low birefringence, which are heat-resistant optical characteristics. It has attracted attention for its excellent transparent thermoplastic resin. For example, resins include, for example, Japanese Patent Laid-Open Patent Publication No. 1 3 2 625 and No. 132626, JP-A No. 63-218726, JP-A No. 6-1-1 2 0 8 1-JP, No. 6 Zhao &lt; Zhao et al. In recent years, the application of the cycloolefin-based resins to optical lenses such as lenses, optical fibers, and optical semiconductor packaging has been discussed. Attempts have been made to apply the film to an optical film, and the problems of the optical film are known as follows. Films such as polycarbonate and polyester esters, which have been used for optical films, have large photoelastic coefficients, small stress changes, and cycloolefin resin films, such as heat resistance and poor water absorption deformability, as various optical films. Japanese Patent Publication No. Hei 4-2 4 5 2 〇2, Japanese Unexamined Patent No. 4-3 6] 20 cm, optical films for liquid crystals have a high rate of glass transition temperature, high refractive index, transparency, and the ring Olefin series, kaiping; I Kaikai 2-1 3 3 4 1 3 5 1 1 5 9 1 2 kaikai, for example, as shown in optical discs, optical packaging materials, etc., there is a phase difference between improved habit or diethylacetic acid The problem is discussed. For example, Special Publication, Japanese Patent Application Laid-Open No. 5- (2) (2) 200521169 2] and Japanese Patent Application Laid-Open No. 5-64 8 65 describe retardation plates made of cycloolefin resin films. Also, Japanese Patent Application Laid-Open No. 5-2 1 2 8 2 8 and Japanese Patent Application Laid-Open No. 6-5 1 1 1 7 and Japanese Patent Application Laid-Open No. 7-7 7 6 0 8 describe the use of cycloolefin resin films in polarizing plates. Protective film. Japanese Patent Application Laid-Open No. 5-6] 02-6 describes a substrate for a liquid crystal display device made of a cycloolefin resin film. These publications describe that the cycloolefin-based resin film has a water absorption of 0.05% or less, and the main advantage is the low water absorption. However, when such a low water-absorbing cycloolefin-based resin film is used as, for example, a retardation plate or a substrate for a liquid crystal display device, it may be hard-coated, an antireflection film, a transparent conductive layer, or adhered to a polarizing plate, The adhesion of glass creates problems. When used as a protective film for polarizing plates, in addition to the above problems, there is a problem that it is difficult to dry the water of the water-based adhesive generally used for bonding with a polarizing film. On the other hand, there are many known cycloolefin resins, and not all cycloolefin resins may have a water absorption of 0.05% or less. In order to have a water absorption of 0.05% or less, the cycloolefin resin must have a polyolefin structure composed of only carbon atoms and hydrogen atoms or a structure containing a part of halogen. Therefore, in order to solve the problem caused by the low water absorption, optical films containing cycloolefin-based resins having polar groups introduced into the molecule are described in JP 7-2 8 7 1 22, JP 7_2S71 23, and the like. . These optical films are excellent in optical characteristics such as high transparency, low retardation of transmitted light, uniform and stable retardation when stretched, and good heat resistance, adhesion to other materials, and adhesion. Advantages have been used for liquid crystal display elements. However, in recent years, large-scale, thin optical films used in television terminals (3) (3) 200521169 films have become increasingly demanding for liquid crystal display elements with finer features, higher brightness contrast, and superior viewing angle recognition. Therefore, the appearance of an optical film which does not affect the visibility of an image is expected. [Summary of the Invention] [Problems to be Solved by the Invention] An object of the present invention is to provide various optical characteristics and heat resistance of a conventional optical film having a cycloolefin-based resin or a thermoplastic norbornene-based resin as a main component without detracting from it. Or it has the advantages of adhesion and adhesion with other materials, such as an "optical film for significantly reducing the visibility of advanced liquid crystal display elements," and a polarizing plate using the optical film. [Means to Solve the Problem] The present inventors have carefully studied the results in order to solve the above-mentioned problems. It has been found that the highlights of the optical film used have a great influence on the above-mentioned image visibility. Thin film, the number of bright points is less than 10 when converted to 1 m 2 of thin film; preferably 5 or less, more preferably 0, the liquid crystal display element used for advanced images can also ensure good images, and finally completed the present invention . The so-called bright spot in the present invention means a bright spot (partial light leakage) seen when the film is sandwiched between a polarizing plate in a cross-Nico state and a white light source of 1000 cd / m2 is viewed from the vertical direction of the polarizing plate surface with the naked eye. , Slightly bright parts are also counted as bright spots. The present inventors have also found that an optical film obtained by extending the above-mentioned optical film can be used as a film having a function of imparting a retardation to transmitted light.-6-(4) (4) 200521169 (hereinafter referred to as "phase retardation film" "), And the polarizing plate using the optical film and / or retardation film of the present invention has practicality, and the present invention has been completed. [Effects of the Invention] The optical film, retardation film, and polarizing plate of the present invention are composed of a cycloolefin-based resin as a main component, and there are few bright spots due to point defects. They have excellent visibility when used in a liquid crystal display and are heat resistant. It is also excellent in adhesion and adhesion with other materials, which can cope with the advancement of LCD panels, and can be used as a film with light diffusion function, transparent conductivity, and anti-reflection function. The present invention is described in detail below. &lt; Cycloolefin resin &gt; The cycloolefin resin used in the present invention includes the following polymers. The so-called polymer in the present invention also contains a copolymer. (1) Ring-opening polymers of the specific monomers of the following general formula (I). (2) A ring-opening polymer of the specific monomer and copolymerizable monomer of the following general formula (I). (3) The hydrogenated polymer of the ring-opening polymer of (1) or (2) above (4) The ring-opening polymer of (1) or (2) above is cyclized by the one-gram reaction, and then hydrogenated. polymer. (5) A saturated polymer of the specific monomer of the following general formula (I) and an unsaturated double bond-containing compound. (6) Additive polymer of more than one monomer selected from the following specific monomers of general formula (I), ethylenic ring (5) 200521169 hydrocarbon-based monomer and cyclopentadiene-based monomer, and Aerated polymer. (7) An alternative copolymer of the specific monomer of the following general formula (I) and an acrylate.

[Wherein R1 to R4 are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or other monovalent organic groups, which may be the same or different. R] and R2 or R3 and R4 may be integrated to form a divalent hydrocarbon group, or R] or R2 and R3 or R4 may be combined with each other to form a monocyclic or polycyclic structure. m is 0 or a positive integer, and p is 0 or 1. &lt; Specific monomer &gt; Specific examples of the specific monomer include the following compounds, but the present invention is not limited to these specific examples. There are φ bicyclic [2.2.1] hept-2-ene, tricyclic [4.3.0.12,5] -3-decene, tricyclic [4.4 · 0.12,5] -3-undecene, and tetracyclic [4.4. 0.12,5.l7,] G] -3 -dodecene, 5-methylbicyclo [2.2.1] heptan-2-ene, -5-ethanebicyclo [2.2 ·]] hept-2-ene,, 5- Methoxybicyclo [2.2.1] hept-2-ene, 5-methoxymethoxybicyclo [2.2. 丨] hept-2-ene, -8- (6) (6) 200521169 5-cyanobicyclo [2.2. 1] hept-2-ene, 8-methoxycarbonyl tetracyclo [4.4.0.12, 5.l7,] G] -3-dodecene, 8-ethoxycarbonyl tetracyclo [4 · 4.0.12,5 · 17,] ()]-3-dodecene, 8-n-propoxycarbonyl tetracyclo [4.4.0. I2,5.] 7,] G] -3-dodecene, 8-isopropoxycarbonyl tetra Ring [4.4.0 · 12'5 · 17 '] ()] dodecene, 8-n-butoxycarbonyl tetracyclo [4.4.0.12,5.17,1 ()]-3-dodecene, 8 -Methyl-8_ methoxycarbonyl tetracyclo [4.4.0.12,5 · 17, Ι ()]-3-dodecene, 8-methyl-8-ethoxycarbonyl tetracyclo [4.4.0.12'5.Γ'1 ()]-3-dodecene, 8-methyl-8-n-propoxycarbonyl tetracyclol ^ jOl2'5.] 7'10] ''-dodecene, 8-methyl-8-isopropoxycarbonyl Tetracyclo [4.4.0.12'5.17 '] ()]-3-dodecene, 8-methyl-8-n-butoxycarbonyl tetracyclo [4.4.0.12'5.17'ig] -3- + = _, 5_ Ethylene bicyclo [2.2.1] hepta-octaene, 8-ethylene tetracyclo [4.4.0.12'5.17, 1 ()]-3-dodecene, 5-benzenebicyclo [2.2.1] hept-2-ene, 8-benzenetetracyclo [4 · 4 · 0.12 · 5.17: 1 () ] -3 -dodecene, 5-fluorobicyclo [2.2.1] hept-2-ene, 5-fluoromethylbicyclo [2.2.1] hept-2-ene, 5-trifluoromethylbicyclo [2 · 2.1] Hept-2 · ene, 5_pentafluoroethylenebicyclo [2 · 2 · 1] heptene, 5,5_difluorobicyclo [2.2.1] hepta-octaene, 5.6-difluorobicyclo [2.2.1] heptene -2-ene, 5; 5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5.6-bis (trifluoromethyl) bicyclo [2.2 ·]] hept-2-ene '5-methyl -5-trifluorobicyclo [2.2.]] Hept-2-ene, -9- (7) (7) 200521169 5,5; 6-trifluorobicyclo [2.2.1] hept-2-ene, 5.5. 6- Ginseng (fluoromethyl) bicyclo [2.2.]] Hept-2-ene, 5.5.6.6- Tetrafluorobicyclo [2.2.1] hept-2-ene, 5,5,656-Thi (trifluoromethyl) bicyclo [2.2 .]] Hept-2-ene, 5.5-difluoro-6; 6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 556-difluoro-5,6-bis (trifluoromethyl) ) Bicyclo [2.2.1] 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-ene5.6-difluoro-5-heptafluoroisopropyl-6-trifluoromethylbicyclo [2.2.1] hept-2 -Ene, 5-chloro-5,6,6-trifluorobis Cyclo [2.2.1] hept-2-ene, 5.6-dichloro-556-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5; 5,6-trifluoro-6-trifluoro Methoxybicyclo [2.2.1] hept-2-ene, 5: 5,6-trifluoro-6-heptafluoropropoxybicyclo [2.2.1] hept-2-ene, 8_fluorotetracycline [4.4.0.12 ' 5.17'1 ()]-3-dodecene, 8-fluoromethyltetracycline [4.4.0.12'5.l7'1G] -3 · dodecene, 8-difluoromethyltetracycline [4.4.0.12'5 .l7 '] G] -3-dodecene, 8-trifluoromethylenetetracycline [4 · 4 · 0 · 12'5 · Γ ″ 〇] -3-dodecene, 8-pentafluoroethylenetetracycline [ 4.4.0.1 2: 5.17,] G] -3-dodecene, 8,8-difluorotetracycline [4.4.0.12, 5.l7, 1G] -3-dodecene, 859-difluorotetracycline [ 4 · 4.0 · 12: 5.Γ,] ()]-3 · dodecene, 858-bis (trifluoromethyl) tetracyclo [4.4.0.] 2,5.l7 = IG] -3-twelve Ene, 8; 9-bis (trifluoromethyl) tetracyclo [4.4.0 · I2 ·· 5.:! 7'1 G] -3-dodecene, 8-methyl-8-trifluoromethyltetracycline [ 4.4.0.] 255.r ″ Q] -3-dodecene,-10-(8) 200521169 858,9 -trifluorotetracyclo [4.4.0.12, 5.17,] ()]-3-dodecene , 8,8,9-shen (trifluoromethyl) tetracycline [4.4.0.12:5.Γ,Ι ()]-3-dodecene, 858,9; 9-tetrafluorotetracycline [4.4.0.12, 5.17,] ()]-3-dodecene, 8 5 8,9; 9- ) Tetracyclo [4.4.0.11,5.17,1 ()]-3-Dodecene 8.8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.11,5.l7,1G] -3 -Dodecene 8.9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.11,5.17,] g] -3- + diene 858.9-trifluoro-9-trifluoromethyltetracycline [ 4.4.0.12, 2.17,] ()]-3-dodecene, 858.9-trifluoro-9-trifluoromethyltetracyclo [4.4.0.11, 5.17, 1 ()]-3-dodecene, 858.9-tri Fluoro-9-pentafluoropropoxytetracyclo [4.4.0.11,5.17,] ()]-3-dodecene 8-fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [ 4.4.0 · 1 1: 5. 1 7,] G]-3 -dodecene, 8.9-difluoro-8-pentafluoroisopropyl-9-trifluoromethyltetracycline [4.4.0.I2,5. I1,3] -3-dodecene '8-chloro · 8,8,9-trifluorotetracyclo [4.4.0.12,5.17,] g] -3-dodecene, 8; 9-dichloro-8 , 9-Bis (trifluoromethyl) tetracyclo [4.4.0.11'5.17,1 ()]-3-Dec-11-1 (2,2; 2-trifluoroethoxycarbonyl) tetracyclo [4 · 4.0. 11,5.Γ,] ()]-3-decene 2 8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.Ο.] 2,5 ″ 7,3 : 3 Dodecene, etc. (9) (9) 200521169 These can be used alone or in combination of two or more. Among the specific monomers, preferred are the above-mentioned general formula (]): R1 and R3 are hydrogen atoms or carbon atoms of 1 to 10, more preferably 1 to 4, most preferably 1 to 2 hydrocarbon groups, and R2 and R4 are A hydrogen atom or a monovalent organic group, at least one of R2 and R4 shows a polar polar group other than a hydrogen atom and a hydrocarbon group, m is an integer of 0 or 1 to 3, and P is 0 or 1, preferably m = l, p = 0. The specific monomers with m = 1 and p = 0 are good because of the high glass transition temperature and excellent mechanical strength of the obtained cycloolefin resin. The polar groups of the above specific monomers include carboxyl, hydroxyl, alkoxycarbonyl, aryloxycarbonyl, amine, amido, and cyano groups, and these polar groups may also be bonded via a linking group such as a methylene group. In addition, a polar divalent organic group such as a carbonyl group, an ether group, a silane ether group, a thioether group, and an imine group, and a hydrocarbon group to which a linking group is bonded are also polar groups. Among these, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group is preferable, and an alkoxycarbonyl group or an aryloxycarbonyl group is particularly preferable.

In addition, at least one of R2 and R4 is a cyclic olefin resin derived from a monomer of a polar group of (CH2) nCOOR, which has a high glass transition temperature, low hygroscopicity, and excellent adhesion to various materials. Good sex. The specific polarity mentioned above is based on the formula in which R1 and R3 are 1 to 2 carbon atoms, preferably 1 to 4 hydrocarbon groups, and more preferably methyl or ethyl. In addition, η is usually an integer of 0 or 1 to 5. The smaller the η 値 is, the higher the glass transition temperature of the cycloolefin-based resin is. Therefore, the specific monomer of the η-series 0 is easy to synthesize. In the above general formula (I), an alkyl group or r3 is preferred, an alkyl group having 1 to 4 carbon atoms is preferred, an alkyl group having 1 to 2 is more preferred, and a methyl group is particularly preferred. In particular, the alkyl group is Combined with the above formula -12-(10) (10) 200521169

—— (CH2) The same carbon atom of the carbon atom to which the specific polar group of nCOOR is bonded, the hygroscopicity of the resulting dilute hydrocarbon resin can be reduced. &lt; Copolymerizable monomer &gt; Specific examples of the copolymerizable monomer include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and dicyclopentadiene. The number of carbon atoms of the cycloolefin is preferably 4 to 20, and more preferably 5 to 12. These can be used individually by 1 type or in combination of 2 or more types. The specific use range of the specific monomer / copolymerizable monomer is a weight ratio of i 0 〇 / 0 to 50/50, and more preferably 100/60 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 polymer of a specific monomer and a copolymerizable monomer, It is carried out in the presence of a metathesis catalyst. The metathesis catalyst contains (a) at least one species of compound selected from W, Mo and Re, and (b) is selected from Group IA elements of the Deming Periodic Table (for example, li, Na, K, etc.), Group 11A Element (e.g. M g, C a, etc.), π B element (e.g.

Zn, Cd, Hg, etc.), Group ΙΠΑ elements (such as B 'A1, etc.), Group IVA elements (such as Si, S η, P b, etc.) or Group IVB elements (such as Ding, Zr, etc.) Is a catalyst selected from a combination of at least one compound selected from the group consisting of at least one compound having at least one carbon bond or element one hydrogen bond of the element. At this time, in order to improve the catalyst activity, the additive (c) described later can also be added. (a) Representative examples of W'M0 or Re compounds with appropriate components are -13- (11) (11) 200521169 WC16, MoC16, ReOCl3, etc. JP 1 3 2 62 6 and the lower left column on page 8. The compounds listed in line 17 in the upper right column of lines 6 to 8. (b) Specific examples of the components include n-C4H9Li, (C2H5) 3 A1, (C2H5) 2AICI, (C2H5)]. 5A1C]]. 5, (C2H5) A1C12, methylurea, and LiH, etc. 1 3 2 62 The compounds described in Bulletin 6 and page 8 in the upper right column on line 8 and page 8 in the lower right column on line 3. The representative examples of the additive (c) component are alcohols, aldehydes, ketones, amines, etc., and those applicable are disclosed in Japanese Unexamined Patent Publication No. 1- 1 3 2 6 2 6 and the lower right column on page 8 from line 16 to the first. The compound shown in line 17 of the upper left column on page 9. The amount of the metathesis catalyst used is the molar ratio of the above (a) component to the specific monomer. "(A) Component: specific monomer" is usually in the range of 1: 500 ~ 1: 50, 000: 10,000. ~ 1: 1〇, 〇〇〇 is better. The ratio of (a) component to (b) component is based on metal atomic ratio (a): (b) is 1: 1 to 1:50, and 1: 2 to 1:30 is preferred. The ratio of (a) component to (c) component is based on the molar ratio (c): (a) 0.005: 1 to 15: 1, and 0.05: 1 to 7: 1 are preferred. &lt; Solvent for polymerization reaction &gt; The solvents used for the ring-opening polymerization reaction (solvents for the molecular weight regulator solution, specific monomers, and / or solvents for the metathesis catalyst) are pentane, hexane, heptane, octane, Alkanes such as nonane and decane, cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decahydronaphthalene, norbornane, aromatic hydrocarbons such as toluene, xylene, ethylbenzene, and hexane, -14- (12) 200521169 Compounds such as chlorobutane, bromohexane, dichloromethane, dichloroethane, hexamethylene dibromo, chlorobenzene, chloroform, tetrachloroethylene, and other halogenated alkanes, toothed aryl groups, ethyl acetate, Saturated carboxylic acid esters such as n-butyl acetate, isobutyl acetate, methyl propionate, dimethoxyethane, ethers such as dibutyl ether'tetrahydrofuran, dimethoxyethane, etc. These can be used alone or in combination . Among these, aromatic hydrocarbons are preferred. The amount of the solvent used is "solvent: specific monomer (weight ratio)", and it is usually 1: 1 to 10: 1, more preferably 1: 1 to 5: 1. <Molecular weight regulator> The molecular weight of the obtained ring-opened polymer can be adjusted by the polymerization temperature, the catalyst species, and the type of cereals. In the present invention, the molecular weight regulator is coexisted in the reaction system for adjustment. Here, suitable molecular weight regulators include α-olefins such as ethylene, propylene, Ding Shaobu,]-pentan, hexadecane, 1-octane, 1, green, non-green, and 1.decane. Styrene, especially butylene and hexene are particularly preferred. These molecular weight regulators can be used individually or in mixture of 2 or more types. The amount of the molecular weight regulator is 0.00 5 to 0.6 mol, and more preferably 0.02 to 0.5 mol relative to 1 specific mole of the specific monomer used for the ring-opening polymerization reaction. In order to obtain (2) a ring-opening polymer of a specific monomer and a copolymerizable monomer, the ring-opening polymerization step may be performed by ring-opening polymerization of the specific monomer and the copolymerizable monomer, and may also be more suitable for polybutadiene and polyisocyanate. Equally conjugated diene compounds, styrene-butadiene copolymers, ethylene-non-conjugated diene copolymers, polynorbornene and other unsaturated hydrocarbon polymers containing 2 or more carbon-carbon double bonds in the main chain In the presence of ring-opening polymerization of -15- (13) 200521169 monomer. The ring-opening polymer obtained above can be used directly, and the olefinic unsaturated bond in the molecule can be obtained by hydrogenation (3). The hydrogenated polymer is useful because it has better heat resistance and light resistance. &lt; Hydrocatalyst &gt; The hydrogenation reaction is carried out in a usual manner, that is, a hydrogenation catalyst is added to the ring-opened polymer solution, and a hydrogen pressure of normal pressure to 300 atmospheres, preferably 3 to 200 atmospheres, is added to the hydrogenation catalyst. 0 to 200 ° C, preferably 20 to 180 ° C. The hydrogenation catalyst may be used for a hydrogenation reaction of an olefinic compound. The hydrogenation catalyst includes a heterogeneous catalyst and a uniform catalyst. Heterogeneous catalysts include solid catalysts supported on carbon, silicon oxide, aluminum oxide, titanium oxide, and other carriers with precious metal catalysts such as palladium, platinum, nickel, rhodium, and ruthenium. The homogeneous catalysts are nickel naphthenate / triethylaluminum, acetoacetone nickel / triethylaluminum, cobalt octoate / n-butyllithium, titanium aromatic dichloride / diethylaluminum chloride, rhodium acetate, Phenylphosphine) rhodium, ruthenium (triphenylphosphine) ruthenium, chlorohydrocarbon (triphenylphosphine) ruthenium, dichlorocarbonyl (triphenylphosphine) ruthenium, etc. The form of the catalyst can be powder or granular. These hydrogenation catalysts are used as a ring-opening polymer: hydrogenation catalyst (weight ratio) 1: 1 X 1 0_7 ~ 1: 1 X 1 (Γ 2). In this way, the hydrogenated polymer obtained by hydrogenation That is, it has excellent thermal stability, and during the forming process, it becomes the heating during use of the product, and its characteristics are not deteriorated. The hydrogenation rate is 500 MHz, and the 値 measured by H-NMR is more than 50%, preferably 90% or more. More than 98% is better, more than 99% is better. The higher the hydrogenation rate, the better the stability of heat and light for -16-(14) (14) 200521169. It can be obtained when used as the retardation film of the present invention. Long-term stability characteristics. When an aromatic group is present in the molecule, it is sometimes beneficial to optical properties and heat resistance. The aromatic group does not have to be hydrogenated. Depending on the desired characteristics, there are conditions under which the aromatic group is not substantially hydrogenated. (4) After the ring-opening polymer of (1) or (2) above is cyclized by ephedrine reaction, the method for obtaining a hydrogenated polymer is as follows. &Lt; Ephetic cyclization &gt; The method for cyclizing the ring-opening polymer of the above (1) or (2) by the reaction is not particularly limited, and may be described in JP-A-Sho 5 0-; [5 4 3 9 9 The conventional method of using acid compounds. Specific examples of acid compounds include A1C13, BF3, FeCl3, AI2O3, HC1, CH3C1C00H, zeolite, activated clay, and other Lewis acid, Bronsted acid. Ring-opened polymers, The olefinic unsaturated bond in the molecule can be hydrogenated like the ring-opening polymer of (1) or (2) above. (5) Method for obtaining the saturated polymer of the above-mentioned specific monomer and an unsaturated double bond-containing compound There are the following methods: &lt; Compounds containing unsaturated double bonds &gt; Compounds containing unsaturated double bonds include, for example, ethylene, propylene, butene, etc., preferably 2 to 12, and more preferably carbon atoms Olefin compounds of 2 to 8. The preferred range of use of compounds containing unsaturated double bonds in specific monomers is -17- (15) (15) 200521169 weight ratio 90/10 to 40/60, more preferably 85 / 15 ~ 50/50. In the present invention, a saturated polymer of (5) a specific monomer and an unsaturated double bond-containing compound may be subjected to a general addition polymerization method. &Lt; Addition polymerization catalyst &gt; Catalyst for synthesizing the above (5) saturated polymer, which is selected from the group consisting of titanium compounds and pin compounds And at least one of vanadium compounds, and catalyst organoaluminum compounds. Titanium compounds include titanium tetrachloride, titanium trichloride, and the like, and chromium compounds include bis (cyclopentadiene) chromium chloride and bis (cyclopentadiene). Dichloride, etc. "The general formula for compounds is V (OR) aXb or v (OR) cXd [where R is a hydrocarbon group, X is a halogen atom, ο $ a $ 3, 0 ^ bg 3, 2 = ( a + b) ^ 3,0 ^ c ^ 4,0 ^ d $ 4,3 c + d) S 4 o] vanadium compounds, or electron supply adducts of these. The above-mentioned electron donors include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic or inorganic acids of vinegar, acids, amidines, anhydrides, j: oxygen-containing electron donors such as ammonium oxide, ammonia, amines, and nitriles , Nitrogen-containing electron donors, such as isocyanates. The catalyst organoaluminum compound is at least one selected from those having at least one carbon-carbon bond or aluminum-hydrogen bond. Among the above, for example, when the ratio of the vanadium compound to the organic compound when a vanadium compound is used, the atomic ratio (A 1 / V) of the vanadium atom is preferably 2 or more ′ 2 to 50, and particularly preferably 3 to 20. (16) 200521169 ′ can be the same as those used in the polymerization of solvent used for ring-opening polymerization, usually used for addition polymerization. The obtained (5) saturated polymer was made of hydrogen. (6) Addition of the above specific monomer and one or more monomers selected from the group consisting of a fine cyclic hydrocarbon-based monomer and a cyclopentadiene-based monomer, and a method for preparing a hydrogenated polymer thereof and a hydrogenated polymer thereof There are the following methods. &lt; Ethylene-based cyclic hydrocarbon-based monomer &gt;

Ethylene-based cyclohydrocarbon-based monomers include, for example, ethylene-cyclopentene-based monomers such as 4-ethylenecyclopentene, and 5-membered cycloalkylenes such as dilute cyclopentadiene-based monomers. , 4_ethylene cyclohexene, isoprene cyclohexene, buprene-isoprene cyclohexene, octamethylethane flammable cyclohexene, 2-methyl_isocyanate hexamethane, and other ethylene 2-hexamethylene monomers , 4-ethyl thiocyclohexyl, 2-methyl methisopropane hexanox ethane, etc.

Cyclohexane fired monomers, styrene, α-methylstyrene, 2-methylstyrene '% toluene ethyl green, methyl styrene, vinylene naphthalene, 2-ethyl naphthalene, cardiac styrene, p-methoxyphenethyl green, etc. Styrene-based monomers, terpenes, terpenes, diendenes, d-panesene, ppanene, dipinene and other terpene-based monomers, such as ethylene vinyl cycloheptene, 4-isopropene cycloheptene Ethylene cycloheptene-based monomers such as olefins, and ethylene cycloheptane-based monomers such as I ethylene cycloheptane and I isopropene cycloheptane. Preferred are styrene and α-methylstyrene. These can be used alone or in combination of two or more. The above-mentioned specific monomer and an addition-molded polymer of one or more monomers selected from the group consisting of a vinyl-based cyclic hydrocarbon-based monomer and a cyclopentadienyl-based monomer may be subjected to the above-mentioned special monomers and unsaturated compounds as described in (5) above. It is obtained by addition of -19-(17) (17) 200521169 to a saturated polymer of a compound with a double bond. The hydrogenated polymer of the above-mentioned shaped polymer can be obtained by the hydrogenation method of the hydrogenated polymer of the ring-opened polymer (3). The method for producing (7) the above-mentioned alternating polymer of the specific monomer and acrylate is as follows. &lt; Acrylic acid ester &gt; Acrylic acid esters used in the production of (7) the above-mentioned alternating monomers of specific monomers and acrylic acid esters include, for example, methyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, etc. ~ 20 carbon atoms, such as straight chain, branched or cyclic alkyl acrylates, propylene acrylate, 2-tetrahydrofuran acrylate, etc., 2 to 20 carbon atoms such as heterocyclic group-containing acrylates, benzyl acrylates, etc. Polyacrylates having a polycyclic structure having 7 to 30 carbon atoms, such as aromatic ring group-containing acrylates, isophorone acrylates, and dicyclopentyl acrylates having a number of 6 to 20. In order to obtain (7) an alternating copolymer of the above specific monomers and acrylates, in the presence of Lewis acid, when the above specific monomers and acrylates add up to 〇〇mol, usually the above specific single system is 30 ~ 70 mol, acrylate 70 ~ 30 mol, preferably the above specific monomer 40'60 mol, acrylate 60 ~ 40 mol, more preferably the above specific monomer 45 ~ 66 mol, acrylate 55 ~ 45 moles for free radical polymerization. The amount of Lewis acid used to obtain (7) the alternating copolymer of the above specific monomer and acrylic acid is relative to the acrylic acid ester] 〇〇mol 〇 · 001〜〗 mol. In addition, conventional free radical polymerization initiators such as organic peroxides or azobis radical polymerization initiators can be used. The polymerization temperature is usually -2 0 t ~ 8 0 t, 5 t ~ 6 0 -20- (18) ( 18) 200521169 ° C is better. The polymerization solvent can be used as it is used in a ring-opening polymerization reaction. In the present invention, "alternating copolymer" means that the structural units derived from the specific monomers described above are not adjacent, that is, the structural units derived from the specific monomers described above, whose neighbors must be the structure of the structural units derived from acrylic esters, It also contains a structure in which the structural units from acrylate are adjacent to each other. The polymer of the above (1) to (7) or a hydrogenated polymer thereof used as a cycloolefin-based resin of the present invention, and the (hydrogenated) polymer preferably has a gel content of 5% by weight or less. 〖Weight% is especially preferable. When the gel content exceeds 5% by weight, the surface properties of the film for optical use are problematic, and bright spots are liable to occur. The preferred molecular weight of the cycloolefin resin used in the present invention is the inherent viscosity [7?] Inh 0 · 2 ~ 5dl / g, more preferably 0.3 ~ 3dl / g, and even more preferably m.5dl / g, gel The polystyrene-equivalent average molecular weight (Mη) determined by permeation chromatography (GPC) is 8,000 to 100; 000, 105000 to 80,000, more preferably 1 250 0 0 to 5 0,000, especially weight average molecular weight (Mw) It is suitable that 2 0,000 to 3 0 0,0 0 0, 3 50 0 0 0 to 25 0,000 is more preferable, and 40; 000 to 200,000 is more preferable. When the intrinsic viscosity [々] inh, the number average molecular weight, and the weight average molecular weight are within the above ranges, the heat resistance, water resistance, drug resistance, and mechanical properties of the cycloolefin-based resin are different from those when used as the retardation film of the present invention. The balance of stability is good. The glass transition temperature (T g) of the cycloolefin-based resin used in the present invention is usually above 120 ° C, [20 to 3 50 ° C, 130 to 25 °. (: Better, 140 ~ 200 ° C is more preferred. When Tg is less than 120 ° C, due to the heat from the laser light source and its adjacent members -21-(19) (19) 200521169, the resulting cycloolefin system is The optical characteristics of the resin film become large and unsatisfactory. On the other hand, if the Tg exceeds 350 ° C, the resin is likely to be deteriorated when heated to the vicinity of Tg during processing such as stretching, etc. The fine smoke used in the present invention The saturated water absorption at 23 ° C is preferably 0. 05 to 2% by weight, more preferably 0.1 to 1% by weight. If the saturated water absorption is within this range, the phase difference is uniform, and the resulting cycloolefin The resin film has excellent adhesion to the glass substrate, and does not peel during use. It is also compatible with antioxidants and can be added in large quantities. If the saturated water absorption rate is less than 0.05% by weight, it is transparent to the glass substrate. The body has poor adhesion and is easy to peel off, and if it exceeds 2% by weight, the cyclic olefin resin film changes easily due to water absorption. The saturated water absorption is determined by immersion in 2 3 ° C water for 1 week in accordance with ASTMD 570. It is obtained by weight. The cyclic olefin resin suitable for the present invention has a photoelastic coefficient Cp) is 0 to 100 (X 1 (TI2Pa ″), and the stress optical coefficient (CR) is 1; 50 0 to 450 0 0 (xl 0 ·] 2Pa.]) 〇 photoelastic coefficient (Cp) and stress optical coefficient (Cr) has been described in various documents (P 0) yme 1 · J 〇urna 1, V ο 1. 27, N 〇 9 pp 9 4 3-9 5 0 (1 955), Journal of the Japanese Society of RHEOLOGY, 乂〇1 .; 19, 1 ^ 〇.2, ?? 93- 9 7 (199 1) 'Photoelasticity test method, Nikkan Kogyo Shimbun, 7th Showa 50th edition)' The former table polymer in glass The degree of phase difference due to stress in the state, and the latter indicates the degree of phase difference due to stress in the flow state. A large photoelastic coefficient (Cp) indicates that the polymer is frozen due to external factors or itself when used in a glass state. Phase stress caused by strain and other strains are sensitive to phase difference. For example, in the present invention, when the lamination is carried out -22- (20) 200521169 the residual change, temperature change, humidity change, and other material shrinkage during bonding are small. Stress' so that valleys tend to produce unnecessary phase differences. For this reason, the photoelastic coefficient (C p) should be as small as possible. When the stress optical coefficient () is large, the desired retardation can be obtained with a small extension ratio when the phase difference appearance is imparted to the epoxidized hydrocarbon resin film, and it is easy to obtain a film that can impart a large retardation to obtain the same phase. Compared with the one where the stress optical coefficient (Cp) is small, the film can be thinned, which is a great advantage. Based on the above viewpoint, the photoelastic coefficient (Cp) ranges from 0 to 100 (x 1 (τ I2Pa ·]). Preferably, 0.80 (xl (T12Pa ~)) is more preferable, 〇 ~ 50 (χΐ〇 ·] 2ρ & ·]) is particularly preferable, 〇 ~ 30 (X 1 0'1 2P a'1) is more preferable, 0 ~ 20 (xlCT12pa ·]) Best. When the photoelastic coefficient (C p) exceeds 1 00 (X 1 〇 · 12 pa · 1), the laminated retardation plate used in the present invention generates stress during bonding, and is generated according to environmental changes during use. The phase difference changes, and the allowable error range from the optimum angle of the optical axis is shifted, and the amount of light transmission will decrease when used. The water vapor transmission rate of the cycloolefin resin used in the present invention is a 25 μm thick film under the conditions of 40 ° C and 90% RH, usually 1 ~ 400g / m2 • 2 4 hr, 3 5 0 g / m2 · 2 4 h ι · better, ι 〇 ~ 3 0 0 g / m2 · 2 4 h i_ better ° When the water vapor transmission rate is within this range, it is used to dry the water-based adhesive for bonding with polarizing plates No problem occurs, and the change in characteristics caused by the humidity of the polarizer's operating environment can be reduced and avoided, so it is better. _SP 値 (solubility parameter) for the cycloolefin resin used in the present invention is preferably 10 to 30 (MPa 1/2), 2 to 25 (MPa 1/2) is more preferable, and 15 to 20 (M P a ) Especially good. When SP 値 is in the above range, the cyclogreen hydrocarbon resin can be well dissolved in a general-purpose solvent, and a stable film can be manufactured. The obtained film has uniform properties. -23- (21) (21) 200521169 Adhesiveness and adhesion to the substrate Can be good, and can properly control water absorption. The cycloolefin resin used in the present invention is selected from the group consisting of (1) and (2) ring-opening polymers, (3) '(4) hydrogenated polymers, ( 5) Saturated polymers, (6) addition polymers, or hydrogenated polymers thereof, or (7) alternating copolymers. To the extent that the effects of the present invention are not impaired, antioxidants, ultraviolet absorbers, etc. may be added thereto. And more stable. • Antioxidants 2,6-di (tertiary butyl) -4_cresol, 2,2, -dioxo-3,3, di (tertiary butyl) -5,5-dimethyldiphenylmethane, [Methylene_3_ (3,5 • bis (tertiary butane) -4-hydroxyphenyl) propionate] methane, 1,], 3_ginseng (2 · methyl-4 · hydroxy-5-5- (tertiary (Butene) benzene) butane, 1,3,5_trimethyl_2,4,6_ginseng (3,5-bis (tertiary butyl) _4-hydroxybenzyl) benzene, stearyl · 々 · (3 , 5-bis (tertiary butyl) -4 -hydroxyphenyl) propionate, 2,2, · dioxy · 3,3, _di (tertiary butyl) -5,5, diethylbenzenemethane, 3 , 9_bis [I,] _ dimethyl · 2- (fluorene-tertiary butyl-4H5-tolyl) propanyloxy] ethyl], 2,4,8,10 -silo [5,5] ten Monoalkane, ginseng (2,4-di (tertiary butyl) phenyl) phosphite, cycloneopentane tetrayl bis (2,4-di (tertiary butyl) phenyl) phosphite, cycloneopent Alkyl tetrayl bis (2,6-bis (tertiary butyl) -4-tolyl) phosphite, 2,2-methylene bis (4,6-di (tertiary butyl) phenyl) octyl phosphite Esters 0 • Ultraviolet absorber: -24-(22) 200521169 2,4-Dihydroxybenzophenone, 2-hydroxy-cardiomethoxydi The addition amount of these antioxidants, such as ketone, is usually 0.01 to 3 parts by weight based on 100 parts by weight of the ring. Within the scope of the invention, conventional, thermoplastic elastomers, rubber polymers, organic fine particles, and the like can also be incorporated. To the extent that the effects of the present invention are not impaired, additives conventionally used for resin processing such as lubricants can be added for the purpose of improvement. &lt; Manufacturing method &gt; The method for forming the film of the present invention is not particularly limited. Hydrocarbon-based resins are conventionally melt-molded or solution-casting methods (solvents are used to make films or sheets. Among them, film-thickness is easy to obtain). Solvent casting methods are usually used for films with excellent smoothness. Solvent casting methods include, for example, a method in which a cycloolefin resin dissolving agent is formed into a liquid with an appropriate concentration, and the carrier is peeled off after being cast or dried on a suitable carrier. Cycloolefin When the resin is dissolved or dispersed in the solvent, the resin concentration is 0 to 90% by weight, uo% by weight is preferred, and 1 is more preferred. If the resin concentration does not reach the above, it is difficult to ensure that the solvent of the film evaporates and foaming is rare. On the one hand, such as film surface smoothness, the viscosity of the solution is too high if the above concentration is exceeded, and the resulting surface may be difficult to obtain uniformity. The viscosity of the solution at room temperature is usually 〖～ 丨 ： 0 〇〇 · 0 〇0 For transparency, thermoplastic resin, and processability of inorganic fine particles, it can also be cast with a cycloolefin agent.) Uniformity and surface or dispersion in the solution, usually dried to make it 0 ~ 3 5 Weight 〇 / 〇 thickness, and the following problems. In addition, the thickness of the film v mPa · S) (23) (23) 200521169, 10 ~ 10,000 (m Pa · S) is preferred, 100 ~ 50; 000 (m Pa. S ) Is more preferable, and 1000 to 40,000 (mPa · S) is particularly preferable. Solvents used are aromatic solvents such as benzene, toluene, xylene, etc., Sailusu-based solvents such as Methelex, Ethelox, Bumethox-2-propanol, diacetone alcohol, acetone, cyclohexanone, butane Ketone solvents such as ketones, 4-methyl-2-pentanone, cyclohexanone, ethylcyclohexanone, and 1,2-dimethylcyclohexanone; ester solvents such as methyl lactate and ethyl lactate; 2, 2, Halogen-containing solvents such as 3,3-tetrafluoro-1 -propanol, dichloromethane and chloroform; ether solvents such as tetrahydrofuran and dioxane; alcohol solvents such as 1-pentanol and 1-butanol. In addition to the above, SP 値 (solubility parameter) is usually 10 to 30 (MPa172), preferably 10 to 25 (MPa1 / 2), more preferably 15 to 25 (MPa172), and even more preferably 15 to 2 0 (MPa A solvent in the range of 1/2) can obtain a thin film with good surface uniformity and optical characteristics. These solvents can be used alone or in combination of two or more. When two or more solvents are used, the SP of the mixture is preferably within the above range. At this time, the SP 値 of the mixture can be obtained from its weight ratio. For example, for a mixture of two kinds, the weight fraction of each solvent is W], W2, SP 値 when the SP 値 is SP 1, SP 2 can be obtained by the following formula: : SP 値 = W1 · SP1 + W2 · SP2. When the cycloolefin-based resin is dissolved in a solvent, it may be at room temperature or may be heated. In order to shorten the dissolution time, heating is preferred. Stir well to obtain a homogeneous solution. When coloring is necessary, colorants such as dyes and pigments can be appropriately added to the solution. Leveling agents can also be added to improve the surface smoothness of the film. General leveling agents -26-(24) 200521169 can be used, such as fluorine-containing non-ionic surfactants, special acrylic fluorene-based leveling agents, polysand oxygen-based leveling agents can be used. The cycloolefin-based resin solution obtained by the above method is preferably formed into a film by coating or the like, and is preferably subjected to a defoaming treatment. With this treatment, thin bubbles can be suppressed. Generally, the method for manufacturing the film of the present invention by a solvent casting method is as follows: the solution is applied to a metal light, a steel strip, a polyethylene terephthalate (PET), and a polyethylene terephthalate (PEN) using a die or a coating machine. It is a method in which a polyester film is made of a substrate made of tetrafluoroethylene, and then the solvent is dried and the film is removed from the substrate. It can also be manufactured by applying a resin solution to a substrate by spraying, brushing, or spin-coating, followed by drying the solvent, and peeling the film from the substrate. It can also be applied repeatedly to control the smoothness of thick surfaces. When polyester is used as the substrate, a surface-treated film can be used. The surface treatment methods include general hydrophilization treatment methods, such as a method of coating and laminating resins such as acrylic resins, sulfonate group-containing resins, or corona discharge treatments to improve the hydrophilicity of the film surface. The drying (solvent removal) step of the above solvent casting method is not special, and it can be implemented according to a commonly used method, for example, through a method of drying a furnace through a plurality of rolls. The bubbles are generated by the evaporation of the solvent during the drying step, and the film characteristics are significantly reduced. To avoid this, the drying step is divided into two steps. It is better to control the temperature or air volume in each step. The amount of the residual solvent in the film is usually 10% by weight or less and 5% by weight or less, more preferably 0.5% by weight or less, and more preferably 0.5% by weight or less. Resin resin square film will be coated with phthalic acid, poly, will be immersed, removed, the surface of the fluorene, in a restricted square and thinner than the solvent -27- (25) (25) 200521169 the amount is more than 10 % By weight, when the film is actually used, the dimensional change over time is not good. In addition, the Tg is lowered due to the residual solvent, and the heat resistance is also lowered, which is not good. The extension step described later is performed well. The amount of the residual solvent may be appropriately adjusted within the above range. To be specific, in order to make the phase difference appear stably and uniformly during the stretching orientation, the amount of the residual solvent is usually 10 to 0% by weight, more preferably 5 to 0.1% by weight, and even more preferably 1 to 0. 1% by weight. A small amount of residual solvent may make it easier to extend the process or control the retardation. The thickness of the film of the present invention is usually 1 to 500 μm, preferably 1 to 3 00 μm, more preferably 1 to 200 μm, and most preferably 1 to 100 μm (1000 to 100000 ηm). When the thickness is less than 1 μΐΏ, it is difficult to handle. On the other hand, when it is 500 μΓη or more, the film is called "curled" when it is rolled into a roll shape, and sometimes it is difficult to obtain it after processing. The thickness distribution of the film of the present invention is generally within ± 値 20%, preferably within ± 10%, more preferably within ± 5%, and particularly preferably within ± 3%. In addition, the thickness variation per Icm is usually preferably 10% or less, preferably 5% or less, more preferably 1% or less, and more preferably 0.5% or less. Such a thickness control can prevent uneven phase difference in the extended orientation. &lt; Phase retardation film &gt; The optical film obtained by the above method is subjected to an extension process to obtain a retardation film. This retardation film is capable of imparting a retardation to transmitted light because the polymer chain of the material cycloolefin-based resin has been oriented in a certain direction. Here, "oriented in a certain direction", the molecular chain is regularly oriented in the uniaxial direction, biaxial direction or thickness direction of the film when the whole membrane is observed. Orientation -28- (26) 200521169 The degree of regularity varies with processing methods, processing conditions, etc., and depends on the desired characteristics. Specific examples of the stretching processing method for manufacturing the retardation film of the present invention include a conventional uniaxial stretching method and a biaxial stretching method. It can also be used, the uniaxial stretching method of the tenter method, the f ratio compression stretching method, the longitudinal uniaxial stretching method using two sets of rollers with different circumferences, or the biaxial stretching method combining a transverse uniaxial and a longitudinal uniaxial method. Extension method of plastic law. For uniaxial elongation, the elongation rate is usually between 5% and 0.00% / min, preferably between 50% and 1,000% / min, more preferably between 100% and 1500% / min, and between 100% and 5%. 〇〇% / minute is particularly good. The biaxial stretching method includes those that perform stretching in two directions at the same time, and that after uniaxial stretching, the stretching is performed in a direction different from the original stretching direction. At this time, in order to control the shape of the refractive index ellipsoid of the stretched film, the intersection angle of the 2 extension axes is determined by the desired characteristics without special restrictions, and is usually in the range of 120 to 60 degrees. The extension rate can be the same or different in each extension direction, usually 1 ~ 5,000% / minute, preferably 50 ~ 150,000% / minute, more preferably 100 ~ 150000% / minute, 100 ~ 5 00% / minute is particularly good. The extension processing temperature is not particularly limited. Based on the glass transition temperature T g of the ring-burning hydrocarbon tree used in the present invention, it is generally τ g ± 30 ° C, preferably T g 15 ° C, Tg -5 ° C ~ Tg + 15t: better. Within the above range, it is preferable to suppress the occurrence of the phase difference and to easily control the refractive index ellipsoid. The elongation factor is not particularly limited because it is determined according to the desired characteristics, and is generally 1.0 to 10 times ′ 1 · 0: &gt; 5 times is more preferred ′]., And 3 to 3 times is more preferable. If the stretching ratio exceeds 10 times, the phase difference may be difficult to control. &gt; 29- (27) (27) 200521169 The stretched film can be directly cooled, preferably at least 10 seconds under the ambient gas at a temperature of Tg-20 ° C ~ Tg, 30 seconds to 60 minutes Good,] minutes ~ 60 minutes is better, for heat fixation. This makes it possible to obtain a stable retardation film with little change in the phase difference of transmitted light over time. When the film is not stretched, the dimensional shrinkage of the optical film of the present invention due to heating is usually less than 5%, and preferably less than 3% when heated at 80 ° C for 500 hours. (K5% or less is better, (K5% The following is particularly preferred. The dimensional shrinkage of the retardation film of the present invention upon heating is usually 10% or less, preferably 5% or less, and more preferably 3% or less when heated at 80 ° C for 500 hours. The following are particularly preferred. The specific monomers used as raw materials for the cycloolefin-based resin of the present invention, the appropriate selection of other copolymerizable monomers, the casting method, the conditions, the extension method, the conditions thereof, or the appropriate selection of the above-mentioned heat-fixing conditions can make The dimensional shrinkage is within the above range. The film stretched as above has molecular orientation due to stretching, and imparts a phase difference to the transmitted light. This phase difference can be controlled with the stretching magnification, stretching temperature, or film thickness. For example, the same film thickness before stretching The larger the extension magnification, the larger the absolute difference in the transmitted light ’s retardation, so you can change the extension magnification to obtain a retardation film that gives the desired retardation from the transmitted light. On the other hand, the same extension magnification, the film before extension Thicker, then The larger the absolute difference in the phase difference of the emitted light, the larger the film thickness before stretching can be to obtain a retardation film that gives the desired phase difference to the transmitted light. In addition, in the above-mentioned stretching processing temperature range, the lower the stretching temperature, the lower the transmitted light. The larger the absolute retardation of the retardation, the more the retardation film can be obtained by changing the extension temperature to give the desired retardation of the transmitted light. -30-(28) (28) 200521169 The thickness of the retardation film extended as above is 0.1 ~ 100 μm is preferred, 0.5 to 80 μΐΉ is more preferred, 1 to 70 μm is more preferred, and ι to 60 μm is best. Products with a phase difference film in a thin thickness can greatly respond to the requirements for miniaturization and thinning The thickness of the retardation film can be controlled by the appropriate selection of the film thickness before stretching and the appropriate selection of the stretching ratio. For example, making the film thin before stretching and increasing the stretching ratio can make the retardation film thin. Phase of the retardation film The rate difference, that is, the phase difference imparted to the transmitted light, is determined by the required effect of the retardation film, and also varies with the wavelength of the transmitted light. It cannot be said at one time, usually 1 ~ ΙΟΟΟΟηιυ, 5 ~ 5 000nm. Good, 1 0 ~ 100nm is more preferable. Controlling the phase difference 値 is less than inm, it is difficult to control. Phase difference films with a phase difference 値 more than 1000 nm are not only difficult to manufacture, but sometimes it is difficult to ensure the uniformity of the phase difference later described. Transmission phase The phase difference of the light of the difference film is preferably high uniformity. The variation of the wavelength of 55 Onm is usually less than ± 20%, preferably less than 10%, and more preferably ± 5%. The variation of the phase difference exceeds ± 20 ° When it is used in liquid crystal display elements, etc., the color is uneven and the display performance is deteriorated. The optical film of the present invention can be used alone, or two or more sheets can be laminated, and the polarizing film can be bonded as a protective film and used as a polarizing plate. The present invention The structure of the polarizing plate in which the optical film is used as a protective film has the following examples, and the present invention is not limited to these examples, and can be appropriately changed according to desired characteristics. 1) Triethyl cellulose (abbreviated as T A C) + polarizing film + optical film of the present invention 2) optical film of the present invention + polarizing film + optical film of the present invention -31-(29) 200521169

3) TAC + polarizing film + optical film B of the present invention In these polarizing plate structures, the optical I-type retardation film of the present invention is not necessary for the polarizing plate to have a low phase film thickness, high functionality, and Compensation function in VA mode. The "optical film A of the present invention" and "this I" refer to the difference (including one that is not substantially zero) or the difference in the direction of the optical axis. When and the direction of the optical axis are different. When the optical films of the present invention are laminated with each other, or when they are laminated on other films, sheets or substrates, they can be used as adhesives, these adhesives, and adhesives. Natural rubber, synthetic rubber, vinyl acetate / chloroene ether with excellent transparency. Hardening adhesives such as acrylic resins, modified cyclic olefin-based trees having functional groups such as hydroxyl groups, cyano groups, and the above resins and other hardening agents such as compounds, polyurethane adhesives, synthetic resin-based adhesives, and epoxy-based adhesives In order to improve the lamination workability of the optical film of the present invention, it is possible to use an adhesive layer or an adhesive or an adhesive such as the above when used for adhesion; &lt; a film with an antireflection layer &gt; The optical film of the invention can be bonded to at least one of the film A + the film of the optical table of the present invention, and the optical film B can reduce the liquid crystal and have a good light. However, the phase difference is also included. The optical film of the present invention is preferably thinner. The specific examples include adhesives such as ethylene copolymers and polyethylene resins, and dry lamination for the addition of ester systems containing isocyanate groups. With Wait. It is laminated in a film, sheet or base. Layering agent, adhesive. Single-sided laminated reflection prevention -32-(30) (30) 200521169 layers. The method for forming the anti-reflection layer may be, for example, an inorganic system such as silicon, titanium, giant, pin, and other metal oxides, such as vinylidene fluoride, hexafluoropropylene, and tetrafluoroethylene (co) polymers. Fluorine-containing (meth) acrylate (co) polymers and other organic anti-reflection layers such as fluorinated compounds are formed by sputtering, evaporation, coating, dipping, etc. to a thickness of about 0.0 1 to 10 μη]. . The thickness of the anti-reflection layer is usually from 0.01 to 50 μm, preferably from 0.1 to 30 μm, and more preferably from 0.5 to 20 μm. If it is less than 0.01 μm, the antireflection effect cannot be exhibited. If it is more than 50 μm, the thickness of the coating film is uneven, and the appearance is deteriorated. The optical film of the present invention having an antireflection layer may be laminated with a conventional hard coat layer and an antifouling layer. Because of the plural functions described above, the optical film of the present invention is suitable for use as, for example, an anti-reflection layer and a polarizing film protective film having a retardation plate function. When used for a liquid crystal display element, the number of parts can be reduced compared to the past. The optical film of the present invention has a smaller number of bright points in terms of about 1 m2 of the film, which is usually less than 10, preferably 7 or less, more preferably 5 or less, particularly 3 or less, or 0 or the most. good. The reason for such a bright spot is that the detailed generation mechanism is unknown, but it should be caused by the unevenness of the phase difference in a small range. That is to say, there are impurities, gels, bubbles, etc. in the film. Although the size is invisible to the naked eye, the parts of the impurities, gels, bubbles, etc. that are present during extension processing are concentrated due to stress. The phase difference of this part is The phase difference from the surrounding part is different, and light leakage occurs due to the difference in the phase difference. In order to manufacture the above-mentioned optical film with a bright spot number of 0 or very few, each of the steps -33- (31) (31) 200521169 requires the following measures. 1) Film forming stage: melt forming method is used for molten resin, and solution casting method (solvent casting method) is used for resin solution, filtering and removing impurities. At this time, compared to filtering with a fine-mesh filter in one stage, the method of filtering with a fine-mesh filter in order from a thicker filter in order has better productivity and quality. The mesh size of the final filter through which the molten resin or resin solution passes is preferably less than 10 μm, more preferably less than 5 μm, particularly preferably less than 3 μm, and most preferably less than 1 μm. At this time, the shape of the filter is not particularly limited, and from the general versatility and productivity, a tube type or a blade type is preferred. The filtration area at this time is appropriately adjusted according to the pressure drop before and after the filter. The better is to adjust the pressure drop to 10 MPa or less, more preferably 5 MPa or less, and 3 MPa or less. If the pressure drop exceeds i0MPa, the substance causing the bright spots is easy to pass through and is not good. During the film-making stage, the molten resin or resin solution should be prevented as much as possible and the generated bubbles should be removed. Specifically, in order to suppress the foaming of air, moisture, and low-molecular substances caused by heating in the resin, hot air dryers and vacuum dryers are used to remove air, moisture, and low-molecular substances in advance. The flow of the molten resin passes through at least a reduced pressure p to degas. Finally, it is also effective to reduce the pressure at the discharge portion of the molten resin such as a T die. The better is to make the pressure immediately before the discharge be 5 MPa or less, more preferably 1 MPa or less, and even more preferably 0.5 MPa or less. This can suppress foaming. On the other hand, for resin solutions, defoaming before casting is extremely important. The defoaming method is not particularly limited, and conventional methods such as a method of heating the solution to stand and a method of reducing the pressure can be adopted. 2) Curing and drying stage: Melt-molding method, after the film-forming step -34- (32) (32) 200521169 Move to the curing step of the resin. It is better to carry out in an environment that minimizes impurities that cause bright spots. For example, it is appropriate to perform this step in a clean ambient gas with a cleanliness level below 1000, a level below 1000, and a particularly preferred level below 1000. In this way, the adhesion of impurities on the surface of the optical film or a part of the optical film that causes the bright spots can be minimized. It is preferable that no impurities are present in or near the portion directly in contact with the film. For the solution casting method, the drying step of the solution is followed by the film-forming step. In this case, it is also appropriate to dry in the above-mentioned high-cleanness environment, and a multi-stage drying method that gradually increases the drying temperature is used. The multi-stage drying method can be used to suppress the generation of bubbles accompanying the drying of the solvent. 3) Extension stage: In the extension stage, it is generally heated to a temperature near the glass transition temperature of the resin. At this time, it is extremely important to suppress the foaming and the adhesion of impurities. Specifically, low molecular weight components (low boiling point components) such as residual solvents should be reduced as much as possible in a clean environment as described above. When stretching, it is effective to remove adhesion impurities on the surface of the film with an adhesive roller, etc., and remove the static side for stretching. It is also advisable to subject the film to uniform tension. 4) Cutting and bonding stage: The optical film of the present invention is bonded / cut (or cut / bonded) when manufacturing a polarizing plate or the like. In this case, it is particularly effective to implement the above-mentioned clean environment, and it is particularly effective to reduce or remove the generated debris. Specifically, it is better to use a sharp tool near room temperature, and cutting with a tool from the resin's glass transition temperature (/ 3) to / 3 + 100 t is effective. It is also effective in removing chips and impurities caused by the environment from the film surface. Specifically, the method is to use an adhesive roller to directly contact the surface of the film -35-(33) (33) 200521169 method, or blow with clean air. The optical film ′ of the present invention is converted to about lm2 of the film, and the number of impurities causing bright spots is preferably 10 or less, more preferably 5 or less, particularly 3 or less, and 0 or 1 is most preferable. The term “impurity system” used herein refers to a person who substantially blocks the transmission of light when the light is transmitted through the film. The presence of such impurities in the thin film results in poor pixel characteristics and poor characteristics. The size of the impurities that can be measured depends on the desired performance. It is usually not more than 10 μπι (the diameter of a circle is the diameter, and the length of the other shape is the length of the long direction). The more strict is 1 μπ! the above. Of course, depending on the required performance, smaller impurities may be measured. &lt; Use &gt; The optical film of the present invention can be used in, for example, a mobile phone, a digital information terminal, a pager, a navigation system, a liquid crystal display for a car, a liquid crystal monitor's dimmer panel, a display for an OA device, and a display for an AV device And other polarizing plates for liquid crystal display elements and electroluminescence elements. Can also be used for touchpads, protective films for optical discs, etc. Can also be used as CD, CD-R, M D 'M 0, D v D and other optical disc recording. Reproducing device, the wavelength plate of the LCD projector. [Implementation Modes] [Examples] The present invention will be described in more detail by way of examples below, and the present invention is not limited to the following examples as long as it does not exceed the gist thereof. And the following "parts" and "%" are divided by -36- (34) 200521169 Non-exclusive statement means "parts by weight" and "weight percent". The methods for measuring various kinds of radon in the present invention are as follows. [Glass transition temperature (Tg)] Using a differential scanning calorimeter (DSC) manufactured by SEIKO INSTRUMENTS, in a nitrogen ambient gas, heating rate: 20. (: Condition measurement per minute [saturated water absorption] According to AS TM D 5 7 0, immerse the sample in water at 2 ° C for 1 week, and measure the weight change before and after immersion. [Total transmittance] Use SUGA Haze meter manufactured by Testing Machine Co., Ltd .: η G Μ-2 DP type measurement. [Phase difference of transmitted light] φ Using KOBRA-21 ADH, manufactured by Oji Measurement Equipment Co., Ltd., to measure the in-plane thickness of the film at 590 nm and Phase difference in the thickness direction. [Bright spot measurement] The sample is sandwiched between polarizers in the cross-Nico state and placed on a white light source at -100 Ocd / m2 to measure the light leakage that can be discerned by the naked eye. The number of measurement samples is]. Based on the average value, the number of bright points converted per 1 m2 is calculated to be -37-(35) (35) 200521169 [Confirmation of visibility] The 22-type LCD TV (LT22A13W) manufactured by Samsung Electronics has a cleanliness of 1 〇〇 Decomposed under the environment, remove the assembled retardation film and polarizing plate, and install samples to confirm the visibility. &Lt; Synthesis example &gt; 8-methyl-8-carboxymethyltetracycline [4.4.0.12 = 5.17,] ()] 3-5 parts of dodecene (monomer input -1), 20 parts of 1-hexene (molecular weight regulator), and 750,000 parts of toluene were fed into nitrogen to obtain In a reaction vessel, heat the solution to 6 (TC.) Secondly, add the polymerization catalyst triethylaluminum (1.5 mol / 1) in toluene to the solution in the reaction vessel. Liquid 0.62 parts, tertiary butanol and methanol Modified solution of tungsten hexachloride (tertiary butanol. Methanol: Tungsten = 0.3 5 Molar: 0.3 Molar: 1 Molar) in toluene solution (concentration 0. 05 Molar / 1) 3 · 7 parts, the It is heated and stirred at 80 ° C for 3 hours to obtain a ring-opening copolymer solution through the ring-opening copolymerization reaction. The polymerization conversion of this polymerization reaction_stomach 9 7%, the inherent viscosity of the obtained ring-opening copolymer measured in chloroform at 30 ° C (P inh) was 0.75 dl / g. 4 00 parts of the ring-opened copolymer solution thus obtained were fed into an autoclave, and RuHCl (CO) [P (C6H5) 3] 3 was added to the gastric ring copolymer solution. For 48 parts, under the conditions of a hydrogen pressure of 100 kg / cm2 and a reaction temperature of 1 65 ° C, the stirrer was heated for half an hour for a hydrogenation reaction. After cooling the obtained reaction solution (hydrogenated polymer solution), @ ^ Decompression. This reaction solution was injected into a large amount of methanol to separate and recover the solidified polysaccharide and dried to obtain a hydrogenated polymer (specific cycloolefin resin). -38-(36) (36) 200 521169 The thus-obtained hydrogenated polymer (hereinafter referred to as "resin (a-1)".) The hydrogenation rate determined by 4 0 Μ Η z] Η-NMR was 99.9%. Resin (a-1) The glass transition temperature (τ g) measured by DS c method was 17 0 C. Resin (a-1) The number average molecular weight (Mη) measured by g PC method (solvent: tetrahydrofuran) was 39,000, the weight average molecular weight (Mw) was 1 3,7 00, and the molecular weight distribution (Mw / Mn) Is 3.5. This resin (a-1) is at 2 3. (: The saturated water absorption was determined to be 0.45%, and SP 値 was measured to be 19 (MPa1 / 2). [Example 1] The above resin (a-1) was dissolved in toluene to a concentration of 30% (room temperature). The viscosity of the solution was 3 050 0 0] Opa · S), and the antioxidant neopentyl tetrakis [3-(3,5 -di (tertiary butyl)-4 -hydroxyphenyl) propyl] was added to 100 parts by weight of the polymer. Acid ester] 〇.] Parts by weight, a 2.5 μη sintered metal fiber sintered filter 'made by PALL Japan' followed by a 1 μm same filter and a 0.2 μm same filter were used, and the pressure dropped to 1 MPa After filtering the solution flow rate within a, use INVEX LABCOATER, manufactured by Inoue Metal Industries, which is set in a class OO clean room, to coat propanoic acid with a hydrophilized (easy adhesive) surface treatment thickness] 〇〇μηι p E Ding film (LUMI.LER U94, manufactured by TORAY Co., Ltd.) can be dried to a thickness of 100 μm, dried at 50 ° C for a second time, and then dried at 9CTC. The PET film is peeled to obtain an optical film ( a-2). The remaining solvent amount of the obtained films is 0.5%. The total light transmittance of these films is more than 93%. The optical film is based on the number of bright points and phase conversion of the film about m2. The position difference is shown in Table 1. -39- (37) (37) 200521169 [Example 2] Before the optical film (a-2) was stretched in a clean environment of 100, use an adhesive roller to remove the film attached to the film surface. Impurities are heated to 180 ° Tg + 10 ° C in a tenter, and stretched at a rate of 300% / min in the film plane to a length of 1.5 times, and then in the film plane. Extend 1 to 20 times in the horizontal direction, and then maintain the state under the ambient gas of Tg-20 ° C and 90 ° C for 1 minute. Cool and take it out to room temperature to obtain a retardation film (a-3). Except for the optical film The extension ratio of (a-2) is changed to 1.20 times in the vertical direction and 1.25 times in the horizontal direction. The retardation film (a-4) is obtained as above. These retardation films (a-3), (a-4) are The in-plane retardation 薄膜 of the film with a wavelength of 5 50nm, and the retardation in the thickness direction are shown in Table 1. The retardation films (a-3) and (a-4) are also listed in terms of the number of bright points converted by the film about lm2. The results are shown in Table 1. [Comparative Example 1] The filter was made of Japan PALL with a pore size of 5 μm 2 metal fiber sintered filter, except that it was cast in a solvent-free room as a solvent. (B-2). The total light transmittance of the film is 93% or more. The number of bright points and phase difference of the optical film in terms of film thickness m2 are shown in Table 1. [Comparative Example 2 1 Using an optical film (b -2), except that an adhesive roller is not used, and extended processing is performed in a room not controlled by dust, the retardation films (b-3) and (b-4) are obtained as in Example 2. -40- (38) 200521169 These retardation films (b-3) and (b-4) are films with a wavelength of 55nm. The in-plane retardation 値, the thickness direction retardation 値, and the film thickness are shown in Table 1. The number of bright spots of the retardation films (b-3) and (b-4) in terms of film thickness of about lm2 is shown in Table 1. Table 1 Film thickness In-plane phase thickness direction Number of bright spots in the direction of thickness type (μηι) Difference (nm) Disparity (m) (units / m2) Example 1 a-2 1 00 1 35 0 Example 2 a-3 68 40 80 0 a-4 60 40 120 0 Comparative example 1 b-2 100 1 35 16 Comparative example 2 b-3 67 40 80 28 b-4 60 40 120 3 1 [Modulation example 1]

Feed 250 parts of distilled water into the reactor, and add 90 parts of butyl propionate, 8 parts of 2-hydroxyethyl methacrylate, 2 parts of divinylbenzene and 0.1 parts of potassium oleate to the reaction vessel. The stirring blade made of TEFLON (registered trademark) is stirred for dispersion. After the inside of the reaction vessel was replaced with nitrogen, the temperature of the system was raised to 50 t: and 0.2 parts of potassium persulfate was added to start polymerization. After 2 hours, potassium persulfate was further added, and the temperature was raised to 8 ° C, and the polymerization reaction was continued. The polymer fraction was obtained for 1 hour; the polymer dispersion was concentrated by an evaporator until the solid content concentration reached 7 0 / 〇, water-based adhesive made of acrylic polymer (adhesive with polar group). -41-(39) (39) 200521169 Acrylic acid-based polymer that constitutes the water-based adhesive obtained in this way When the polystyrene equivalent number average molecular weight (Mη) and weight average molecular weight (Mw) were measured by the Gpc method (solvent: tetrahydrofuran), Mη was 6 9000, and Mw was 1 350. The aqueous adhesive of the present invention is The inherent viscosity (W inh) measured in chloroform at 30 ° C was 1.2 d 1 / g. [Example 3] Polyvinyl alcohol (hereinafter abbreviated as "p VA,") at an iodine concentration of 0.03 by weight %, Potassium chloride concentration 0.5% by weight of 3 (rc aqueous solution dyeing bath at 3 times the stretching ratio after the pre-stretching, more than 5% by weight of boric acid concentration and 8% of potassium iodide in water solution '5 5 ° C The cross-linking method was twice as long as the post-extension and dried to obtain polarized photons. In the water-based adhesive obtained in Example 1, the optical film (a-2) was bonded on both sides of the polarizer, and the retardation film (a-3) was bonded on one side with a PVA-based adhesive to obtain a polarizing plate (a-5). The transmittance and polarization degree of the polarizing plate () were tested to be 4 4.0% and 99. 9%. This step was performed in an environment with a cleanliness of 1,000, and the attached impurities were removed with an adhesive roller before bonding. [Example 4] Using another polarized photon obtained in Example 3, an optical film (^ 2) was bonded on one side with the aqueous adhesive of the present invention, and a retardation film (a-4) was bonded on the other side. On the surface of the optical film (a_2), S i NX was vapor-deposited with a film thickness of 80 η ι under a vacuum of 10 · 4Τ〇Γ1, and more sequentially T b F e C 〇 with a film thickness of 20 nm, SiNx At a thickness of 30nm, the outer layer is pre-evaporated with A] w50nm to give reflection-42-(40) (40) 200521169. The anti-reflection layer is provided on the above-mentioned anti-reflection layer to provide a reaction with a reflux cooler and a stirrer. Methyltrimethoxy is mixed in the container for 5 to 5 parts, and 25 parts of colloidal silica dispersed in methanol (solid content concentration 30%) is produced by chemical industry (stock), methanol soluble ) 10 minutes and 6 parts of tap water. After heating and reacting at 70 ° C for 2 hours, 3 to 8 parts of isopropyl alcohol was added. The coating composition was' coated with a jet gun to a dry coating film of 5 μm at 1 40 The polarizing plate (a-6) was formed by heating at 60 ° C for 60 minutes to form a hardened coating film. The transmittance and polarization of the polarizing plate (a-6) were tested and were 47.0% and 99.9%. This step is performed in an environment of cleanliness], and the attached impurities are removed with an adhesive roller before bonding. [Example 5] The above-mentioned polarizing plates (a-5) and (a-6) were each checked for visibility with a liquid crystal television. It can be confirmed that there is no bright picture caused by flickering and discoloration. [Comparative Example 3] A polarizing plate (b-4) was obtained in the same manner as in Example 3 except that the optical film (b-2) and the retardation film (b-3) were used. The transmittance and polarization of the polarizing plate (b-5) were tested to be 4 4.0% and 99.9%. [Comparative Example 4] A polarizing plate (b-6) was obtained in the same manner as in Example 4 except that the optical film (b-2) and the retardation film (b-4) were used. The transmittance and polarization of the polarizing plate (b-6) were tested to be 47.0% and 99.9%. The above-mentioned polarizing plates (b-5) and (b-6) were confirmed by liquid crystal televisions. -43- (41) 200521169. Visible bright spots caused by flickering, discoloration, and significantly reduced image quality.

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Claims (1)

200521169 (1) X. Scope of patent application 1. An optical film, which is characterized by being made of cycloolefin resin, and has a number of bright spots of 10 or less per square meter. 2. The optical film according to item 1 of the patent application scope, wherein the number of bright spots is 0 / m2. 3. A retardation film, which is characterized by extending and processing the optical film as described in the first or second patent application scope. 4. A polarizing plate, which is a polarizing plate formed by laminating a protective film on two sides of a polarizing film, characterized in that at least one of the protective films is for optical use as in any one of claims 1 to 3 of the scope of patent application film. 5 · —A kind of polarizing plate is a polarizing plate made of a protective film on the two sides of a polarizing film, which is characterized by at least one of the protective films, and is more like any one of the scope of patent applications 1 to 3. The optical film is laminated. -45- 200521169 Qiming said that the single abbreviation symbol has no U: The table is a table for the original table and the table refers to the table: the table and the table, &gt; ^ \ ly \) / When there is a chemical formula, please disclose the chemical formula that best shows the characteristics of the invention: None