JP2006321902A - Transparent resin composition and film for optical use comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transparent resin composition excellent in transparency, heat resistance and heat stability in processing at high temperature. <P>SOLUTION: The transparent resin composition comprises 100 pts.wt. of a specific cyclic olefin polymer compounded with 0.001-2 pts.wt. of a fatty acid amide based lubricant and/or a metal soap based lubricant. The resin is excellent in heat stability in processing at high temperature, and manifests a negative birefringence. The film for optical use composed of the resin is excellent in transparency and heat resistance, etc. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention provides a transparent resin composition that is excellent in transparency, heat resistance, and thermal stability during high-temperature processing, and can be suitably used for an optical film or the like.

  In recent years, flat panel displays typified by liquid crystal displays, organic ELs, PDPs, etc. have features that are thin and lightweight to meet market needs, and are rapidly spreading or expanding their use range. In these flat panel displays, a number of polymer films are used, such as a polarizer protective film, a retardation film, a viewing angle compensation film, a transparent electrode film, a light diffusing film, a light reflecting film, an electromagnetic wave shielding film, It is used for display surface protection films. These polymer films generally require very high transparency, excellent surface smoothness and thickness accuracy so as not to deteriorate the visibility of the display. Examples of optical films used in flat panel displays include polyethylene terephthalate film, polycarbonate film, polyether sulfone film, cyclic polyolefin film, linear polyolefin film, polymethyl methacrylate film, triacetyl cellulose film, and thermosetting resin. A film etc. can be mentioned as a representative example.

  The resin that can be used for these optical films is a material that is required to have excellent properties such as heat resistance depending on the use environment. By using various additives, the properties of the material can be obtained. Has been proposed (see, for example, Patent Document 1).

JP 2001-143945 A

  In general, the addition of an antioxidant effectively works to improve the heat resistance of a resin that can be used in an optical film. As the antioxidant, a type that binds to an oxygen radical typified by a phenol-based antioxidant and a phosphorus-based antioxidant and a type that binds to a carbon radical typified by a lactone-based stabilizer are known. Although the thermal stability is improved by the addition of the antioxidant, the effect of suppressing the oxidative deterioration due to the heat generated during the processing is not perfect.

  Therefore, an object of the present invention is to provide a transparent resin composition excellent in transparency, heat resistance and the like, and excellent in thermal stability during processing capable of forming a molten film, and an optical film comprising the same.

  As a result of diligent investigations on the above-mentioned problems, the present inventors have found that a transparent resin composition obtained by blending a specific lubricant with a specific cyclic olefin polymer at a specific ratio exhibits negative birefringence, transparency, The present inventors have found that it is excellent in heat resistance and the like and excellent in thermal stability during high-temperature molding, and has completed the present invention.

  That is, the present invention provides the following general formula (1)

（ここで、Ｘ及びＹは独立にメチレン基、酸素原子、硫黄原子又はテルル原子を表わし、ｎは０または正の整数を表わす。）
で表わされる繰り返し単位からなる環状オレフィン重合体１００重量部に対し、脂肪酸アミド系滑剤及び／又は金属石鹸系滑剤０．００１〜２重量部を配合することを特徴とする透明性樹脂組成物及びそれよりなる光学フィルムに関するものである。

(Here, X and Y independently represent a methylene group, an oxygen atom, a sulfur atom or a tellurium atom, and n represents 0 or a positive integer.)
A transparent resin composition comprising 0.001 to 2 parts by weight of a fatty acid amide-based lubricant and / or a metal soap-based lubricant with respect to 100 parts by weight of a cyclic olefin polymer comprising a repeating unit represented by It is related with the optical film which consists of.

  The present invention is described in detail below.

  The cyclic olefin polymer used in the present invention is a polymer represented by the general formula (1), and X and Y in the general formula (1) independently represent a methylene group, an oxygen atom, a sulfur atom or a tellurium atom, n represents 0 or a positive integer.

  As a method for producing the cyclic olefin polymer represented by the general formula (1), any method can be used as long as the cyclic olefin polymer represented by the general formula (1) is obtained. Since the cyclic olefin polymer represented by 1) is obtained, an unhydrogenated polymer is obtained by polymerizing a polymerizable monomer produced by a Diels-Alder reaction of vinyl ethers and alicyclic dienes, and then hydrogenated. It is preferable to use the method to do.

  Examples of the vinyl ether used to obtain the polymerizable monomer include tricyclodecane vinyl ether, and examples of the alicyclic diene include cyclopentadiene and dicyclopentadiene.

  The charged molar ratio of the alicyclic diene to the vinyl ether in the Diels-Alder reaction between the vinyl ether and the alicyclic diene is preferably from 0.6 to 15, particularly preferably from 1.5 to 10. The reaction can be carried out without solvent or in a solvent inert to the reaction. Examples of the solvent include alkanes such as pentane, octane and nonane; cycloalkanes such as cyclohexane, cycloheptane and cyclooctane; benzene And aromatic hydrocarbons such as toluene, xylene, halogenated alkanes, halogenated aromatic hydrocarbons, carboxylic acid esters, cyclic ethers, and dialkyl ethers. Moreover, 50-300 degreeC of reaction temperature is preferable, Especially preferably, it is 100-250 degreeC, More preferably, it is 180-240 degreeC. There is no limitation on the reaction method, and either batch reaction or continuous reaction can be used. Among them, continuous reaction is preferable from the viewpoint of economy.

  There is no restriction | limiting in particular as a method of superposing | polymerizing the polymerizable monomer manufactured by Diels Alder reaction at the time of manufacturing the cyclic olefin polymer used by this invention, Among these, metathesis ring-opening polymerization is preferable. At that time, it is preferable to use a metathesis ring-opening polymerization catalyst because the polymerization can be efficiently performed. As the metathesis ring-opening polymerization catalyst, a known one can be used, for example, ruthenium, palladium, and the like. , Rhodium, iridium, platinum, tungsten, molybdenum, rhenium compound at least one metal compound (I) and periodic table group 1, group 2, group 3, group 4 metal compound (II) are used in combination be able to.

Specific examples of tungsten, molybdenum, and rhenium compounds include halides, oxyhalides, alkoxy halides, carboxylates, acetylacetonate coordination products, acetylacetonate coordination products of oxides, acetonitrile coordination products, Examples include hydride complexes and the like. Among them, halides, oxyhalides, and the like are preferable because high polymerization activity can be imparted. Particularly, WCl ₆ , WOCl ₄ , MoCl ₅ , MoOCl ₃ , ReCl ₃ , WCl ₂ (OC ₆ H ₅ ). ₄ , MoO ₂ (acac) ₂ and W (OCOR) ₅ are preferable, and WCl ₆ and MoCl ₅ are more preferable.

  Specific examples of the metal compounds of Group 1, Group 2, Group 3, and Group 4 of the periodic table include, for example, n-butyllithium, diethyl zinc, triethylaluminum, diethylaluminum chloride, ethylaluminum dichloride, diethylaluminum hydride, and trimethylgallium. , Trimethyltin, n-butyltin and the like are exemplified, and diethylaluminum chloride, tetramethyltin and tetraphenyltin are particularly preferable.

  The ratio of the metal compound (I) to the metal compound (II) is preferably 1/1 to 1/30, particularly preferably 1/2 to 1/20 as the molar ratio of metal atoms. Further, alcohols, aldehydes, ketones, amines and the like may be added as activity improvers.

  In the metathesis ring-opening polymerization, a molecular weight regulator can be used. As the molecular weight regulator, for example, α-olefins such as ethylene, 1-hexene, 1-heptene are preferably used. More than one type can be used in combination. The amount of the molecular weight regulator used can be appropriately selected depending on the polymerization temperature, the type of polymerization catalyst, and the amount of the polymerization catalyst. Among them, 0.001 to 0.5 mol is preferable per 1 mol of the charged monomer, and particularly 0.002 To 0.4 mol is preferred.

  Examples of the solvent used in the metathesis ring-opening polymerization include alkanes such as pentane, octane and nonane; cycloalkanes such as cyclohexane, cycloheptane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; Examples include alkanes; halogenated aromatic hydrocarbons; carboxylic acid esters; cyclic ethers; dialkyl ethers and the like.

In the metathesis ring-opening polymerization, it is possible to copolymerize using other monomers. Examples of the other monomers include 1-hexene, cyclobutene, cyclopentene, cyclooctene, 1,5-cycloocta Diene, 1,5,9-cyclododecatriene, bicyclo [2.2.1] -2-heptene, tricyclo [5.2.1.0 ^2,6 ] -3-decene, tricyclo [5.2.1 .0 ^2,6] -8-decene, tricyclo ^[6.2.1.0 l, 8]-9-undecene, tricyclo ^[6.2.1.0 l, 8]-4-undecene, tetracyclo [4 .4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -11-pentadecene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,14 ] -4-hexadecene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] - pentadeca-4,11-diene and the like are exemplified, among which 1-hexene, cyclobutene, cyclopentene, cyclooctene and the like are preferred, especially 1-hexene are preferred.

  There is no restriction | limiting in particular as hydrogenation of the unhydrogenated polymer at the time of obtaining the cyclic olefin polymer used by this invention, Among them, the cyclic olefin polymer represented by General formula (1) is obtained with sufficient reaction efficiency. Therefore, it is preferable to use a hydrogenation catalyst, and as the hydrogenation catalyst, a conventional hydrogenation catalyst of an olefinic compound can be used. For example, palladium, platinum, nickel, rhodium, ruthenium, etc. are carbon, silica, Supported catalysts supported on alumina and titania; nickel naphthenate, nickel acetylacetonate, cobalt octenoate, titanocene dichloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium, dichlorotris (triphenylphosphine) ruthenium, chlorohydro Carbonyl tris (triphenylphosphine) Ruthenium, dichloro (triphenylphosphine) ruthenium, homogeneous catalyst such as ruthenium hydride triphenylphosphine is exemplified. In order to promote hydrogenation, it is preferable to use a cocatalyst together with the catalyst. Examples of the cocatalyst include alkylaluminums such as triethylaluminum and alkyllithiums such as n-butyllithium. .

  There is no restriction | limiting in particular in the form of the hydrogenation catalyst to be used, even if it is a powder form and a granule, it can be used without a problem. The amount of hydrogenation catalyst used is preferably 0.5 to 2 ppm by weight with respect to the hydrogenation catalyst. The hydrogenation rate is usually 60% or more, preferably 90% or more, more preferably 98% or more.

  The reaction pressure at the time of hydrogenation is preferably normal pressure to 300 atm, particularly preferably 3 to 200 atm. As reaction temperature, 0-200 degreeC is preferable, Most preferably, it is 20-180 degreeC.

The hydrogenation solvent is not particularly limited, and any solvent may be used as long as it is not hydrogenated under the above-mentioned hydrogenation reaction conditions. From the viewpoint of economy and workability, it is preferably common to metathesis ring-opening polymerization. It is preferable to use one.

  The transparent resin composition of the present invention contains a fatty acid amide lubricant and / or a metal soap lubricant with respect to a specific cyclic olefin copolymer, and these lubricants are granulated from the transparent resin composition. In the process and primary molding process, etc., it works to improve the processability by adjusting the fluidity, friction, and slip of the resin, resulting in thermal degradation of the resin, generation of burns and gels, yellowing, and reduced transparency The generation of cracked gas is suppressed. In addition, when formed into a film or the like, the lubricant exhibits an effect of preventing the film from being blocked or damaged.

  The fatty acid amide lubricant and / or metal soap lubricant used in the present invention is 0.001 to 2 parts by weight, preferably 0.005 to 1 part by weight, particularly preferably 100 parts by weight of the specific cyclic olefin copolymer. Is a blend of 0.05 to 0.3 parts by weight. Here, when the blending amount of the fatty acid amide-based lubricant and / or the metal soap-based lubricant is less than 0.001 part by weight, the resulting transparent resin composition has poor processability, and from such a resin composition A molded product such as a film is inferior in color tone, transparency, appearance and the like. On the other hand, when it exceeds 2 parts by weight, the transparency of the obtained transparent resin composition may be lowered.

  Examples of the fatty acid amide-based lubricant used in the present invention include saturated fatty acid amides such as lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide; oleic acid amide, erucic acid amide, ricinoleic acid amide Unsaturated fatty acid amides such as N-stearyl stearic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide, N-oleyl palmitic acid amide, etc. Substituted amide; methylol amide such as methylol stearic acid amide and methylol behenic acid amide; methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, ethylene vinyl Isostearic acid amide, ethylene bishydroxy stearic acid amide, ethylene bis behenic acid amide, hexamethylene bis behenic acid amide, hexamethylene bis behenic acid amide, hexamethylene bis hydroxy stearic acid amide, N, N′-distearyl adipic acid amide, Saturated fatty acid bisamides such as N, N′-distearyl sebacic acid amide; ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide Unsaturated fatty acid bisamides such as m-xylylene bisstearic acid amide, aromatic bisamides such as N, N′-distearylisophthalic acid amide, etc., among which the processability of the obtained transparent resin composition Excellent and extremely transparent Since the those, ethylene bis-stearic acid amide, and particularly preferably a methylene bis-stearic acid amide.

  The metal soap lubricant used in the present invention refers to a metal salt of a higher fatty acid, such as lithium stearate, magnesium stearate, calcium stearate, calcium laurate, calcium ricinoleate, strontium stearate, barium stearate, barium laurate. , Barium ricinoleate, cadmium stearate, cadmium laurate, cadmium ricinoleate, cadmium naphthenate, cadmium 2-ethylhexoate, zinc stearate, zinc laurate, zinc ricinoleate, zinc 2-ethylhexoate, lead stearate, 2 Basic lead stearate, lead naphthenate and the like are mentioned, among them, the processability of the obtained transparent resin composition is excellent, and since it becomes extremely excellent in transparency, calcium stearate, Magnesium stearate, and particularly preferably zinc stearate.

  Moreover, the transparent resin composition of the present invention may contain other lubricants such as hydrocarbon lubricants, fatty acid lubricants, ester lubricants, alcohol lubricants and the like.

  The transparent resin composition of the present invention can be produced by general mixing and kneading a specific cyclic olefin polymer and a fatty acid amide-based lubricant and / or a metal soap-based lubricant. Examples of the kneading apparatus include melt kneading apparatuses such as a single screw extruder, a twin screw extruder, a brabender, a roll, a kneader, and a Banbury mixer. Alternatively, a method may be used in which the respective components are dissolved or dispersed in a solvent and mixed.

  Further, the transparent resin composition of the present invention has a hindered amine light stabilizer, an ultraviolet absorber, a light stabilizer, for the purpose of preventing thermal coloring and light deterioration due to irradiation with light such as visible light, ultraviolet light, and near infrared light. You may contain a near-infrared absorber etc. as needed. Moreover, you may contain a plasticizer as needed in the range which does not impair transparency in order to provide fluidity | liquidity and toughness. Furthermore, it may contain antioxidants, pigments, antiblocking agents, antistatic agents, surfactants, polymer electrolytes, conductive complexes, inorganic fillers, dyes, oils, etc. as necessary, and the transparency is impaired. Other resin may be contained only when it is not.

  The transparent resin composition of the present invention can be formed into a molded body by a conventionally known molding method, for example, injection molding, injection compression molding, gas assist method injection molding, extrusion molding, multilayer extrusion molding, rotational molding, hot pressing. It can be formed into an injection-molded article, tube, sheet, film, pipe, bottle or the like by a method such as molding, blow molding or foam molding. Among them, an optical film is preferable because it is a film having excellent transparency, heat resistance, and appearance. The optical film preferably has a haze of 1% or less and a yellow index (YI) of 2 or less because it can be used for display devices such as LCDs that require high transparency. Is preferably 0.7% or less and the yellow index (YI) is preferably 1 or less.

  Since the transparent resin composition of this invention is excellent in heat resistance, workability, and mechanical strength, it is preferable to use a retardation film. As a method for producing the retardation film, for example, a raw film is formed by a publicly known method such as a casting method (solution casting method), a melt extrusion method, a calendar method, and a compression molding method, and then the raw film is stretched. It can be obtained by molding. Examples of the stretching process include a process performed continuously in a process of forming a raw film; a process of winding the raw film once and then subjecting the film to a stretching apparatus; In addition, film stretching methods are generally classified into flat method stretching that stretches in the film in-plane direction and tubular method stretching that swells and stretches in a tube shape, and among them, flat method stretching with high accuracy in thickness and stretch ratio. Is particularly preferred. The flat method stretching is classified into a uniaxial stretching method and a biaxial stretching method. Examples of the uniaxial stretching method include a free width uniaxial stretching method and a constant width uniaxial stretching method. On the other hand, examples of the biaxial stretching method include a two-stage free width biaxial stretching method, a sequential biaxial stretching method, and a simultaneous biaxial stretching method. Further, the sequential biaxial stretching includes an all tenter method and a roll tenter method. As the stretching method for producing the retardation film from the transparent resin composition of the present invention, any of the above stretching methods may be used, and the most suitable method can be selected.

  Further, when the stretch molding process is performed, it is preferable to stretch the resin composition at a temperature range of −20 ° C. to glass transition temperature + 20 ° C. measured by a differential scanning calorimeter at a rate of temperature increase of 10 ° C./min. .

  The retardation film can be suitably used as an optical compensation member for LCD, for example, a retardation film for LCD such as STN type LCD, TFT-TN type LCD, OCB type LCD, VA type LCD, IPS type LCD; Examples include an optical compensation member such as a half-wave plate; a quarter-wave plate; a reverse wavelength dispersion characteristic film; and a viewing angle compensation film for a polarizing plate. In addition, as other optical films, for example, retardation films and antireflection films used in information devices such as organic EL, PDP, copying machines, printers, facsimiles, touch panels, optical files, etc .; used in flat panel displays such as LCDs. Suitable for polarizing film protective film, reflector film, separator film, light diffusion film, transparent electrode film substrate, display surface protective film, anti-glare film, anti-reflection film, electromagnetic wave shielding film, ultraviolet absorbing film, far infrared absorbing film, etc. Can be used.

The transparent resin composition of the present invention can be suitably used as a film other than an optical film, and examples thereof include the following uses.
Recording field: electrostatic recording substrate, OHP, 2nd original, slide film, microfilm, X-ray film optical / magnetic memory field: Thermo-plastic recording, ferroelectric memory, magnetic tape, ID card, barcode prevention Fields: Meter windows, television cathode-ray tubes, clean room windows, semiconductor packaging materials, dust-proof films for photomasks, electromagnetic shielding fields: measuring instruments, medical equipment, radiation detectors, IC components, CRT
Photoelectric conversion element field: solar cell window, optical amplifier, photosensor heat ray reflection field: window (architecture, automobile, etc.), incandescent bulb, cooking oven window, furnace sight window, selective transmission film surface heating element field: defroster , Aircraft, automobile, freezer, incubator, goggles, medical equipment, liquid crystal display device electronic parts / circuit materials field: capacitors, resistors, thin film composite circuits, leadless LSI chip carrier mounting, dry film resist electrode field: paper battery Electrode light transmission filter field: UV cut filter, UV transmission filter, UV transmission visible light absorption filter, color separation filter, color temperature conversion filter, neutral density filter, contrast filter, wavelength calibration filter, interference filter, infrared transmission filter, infrared Cut filter, heat Absorption filter, heat ray reflection filter Gas selective permeable membrane field: Oxygen / nitrogen separation membrane, carbon dioxide separation membrane, hydrogen separation membrane Electrical insulation field: Insulating adhesive tape, motor slot liner, transformer interphase insulation, lead wire insulation High voltage cable insulation coating polymer sensor field: optical sensor, infrared sensor, sound wave sensor, pressure sensor Surface protection field: CRT, furniture, system kitchen, automotive interior and exterior, paint protective film sliding material field: hopper chute Lining, sliding material for conveyor belts, sliding material for guide rails, paper feeding rollers for copiers, computer-mouse porous film fields: moisture permeable waterproof materials, filter materials for microfiltration membranes, etc. Other fields: thermal transfer, printer ribbon, Electric cable shield, water leakage prevention film, battery separation film

  Further, the transparent resin composition of the present invention can be suitably used for applications other than films, and examples thereof include relays, burn-in sockets, connectors, sensor housings, variable resistors, used in electric and electronic devices, Polyvaricon case, aeration bobbin, sealing material for transistor, IC, LSI, LED, etc., sealing material for IC memory of IC card, sealing material for motor, capacitor, switch, sensor, etc .; camera, VTR, projector, etc. Shooting lenses, viewfinders, filters, prisms, Fresnel lenses, body materials, etc. used in video equipment; cards, discs, pickup lenses, etc. used in optical recording equipment such as CD players, DVD players, MD players, game machines, etc. Optical fiber and optical fiber used in the optical communication field Light guide plate, light guide, Fresnel lens, prism sheet, light diffusion sheet, transparent used for information equipment such as LCD, organic EL, PDP, copying machine, printer, facsimile, touch panel, optical file Electrode sheet substrates, display surface protection sheets, ink tanks, covers, body materials, etc .; meters, lamps, lenses, sockets, fuse cases, instrument covers, etc. used in the vehicle field such as automobiles, trains, etc .; medical Eyeglass lenses, contact lenses, endoscope lenses, syringes, artificial dialysers, chemical containers, dentures, ampoule cutter containers, etc. used in the equipment field; lighting windows, doors, surveillance camera lenses, carports, terraces in the building materials field Lighting parts, etc .; Lighting parts used in daily necessities, toys, sunglasses, stationery, makeup Container, fishing, food containers, and the like for drinking water container.

  The transparent resin composition obtained by the present invention is excellent in transparency, heat resistance and the like, and is excellent in thermal stability during high-temperature processing, and therefore can be suitably used for optical films and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, a present Example does not restrict | limit this invention at all. The raw materials and availability used in the examples are as follows, and the other reagents were commercially available unless otherwise noted.

Dicyclopentadiene: Wako Pure Chemicals Reagent grade 1 Tricyclodecane vinyl ether: TCD-VE made by Maruzen Petrochemical
Hydroquinone: Wako Pure Chemicals Reagent grade The physical properties shown in the synthesis examples and examples were measured by the following methods.

~ Weight average molecular weight ~
It calculated | required as a standard polystyrene conversion value using the gel permeation chromatography (GPC) (The Tosoh Corporation make, brand name HLC-802A).

~ ¹ H-NMR measurement ~
The composition and hydrogenation rate were calculated by measuring ¹ H-NMR in 60 ° C. heavy toluene using a nuclear magnetic resonance measuring apparatus (trade name JNM-GSX270 type, manufactured by JEOL Ltd.).

~Glass-transition temperature~
Using a differential scanning calorimeter (manufactured by Seiko Denshi Kogyo Co., Ltd., trade name DSC2000), the measurement was performed at a heating rate of 10 ° C./min.

~ Total light transmittance ~
The total light transmittance at the center of the film was measured using an ultraviolet-visible spectrometer (V530) manufactured by JASCO Corporation.

~ Haze ~
The measurement was made according to JIS K7136.

~ Yellow Index (YI) ~
The measurement was performed according to JIS K7105.

~ Surface smoothness ~
Using a laser microscope (VK-8550) manufactured by Keyence Corporation, the center line average roughness (Ra) was determined, and when this value was small, the surface smoothness was excellent.

Reference Example 1 (Synthesis of polymerizable monomer)
A 300 ml glass distillation apparatus was charged with 100 ml of dicyclopentadiene, heated to 220 ° C. with a mantle heater, and the fraction having a boiling point of 39.5 ° C. of cyclopentadiene produced by thermal decomposition was cooled in a dry ice methanol bath. It separated by the technique of liquefying in the receiver.

  Next, 16.26 g (0.247 mol) of cyclopentadiene, 76 g (0.37 mol) of tricyclodecane vinyl ether and 0.1 g (1 mmol) of hydroquinone were charged into a 300 ml stainless steel autoclave and purged with nitrogen. Then, it heated at 220 degreeC and made it react for 5 hours in a heating state. Thereafter, the reactor is cooled, tricyclodecane vinyl ether as a raw material is separated from the contents by distillation under reduced pressure, and tricyclodecane vinyl ether added with cyclopentadiene (tricyclodecanyl-tricyclodecenyl ether) (monomer 1 ) As a main component was separated. Yield was 8 grams.

In addition, in addition to the monomer 1 obtained by adding 1 mol of cyclopentadiene represented by the general formula (2) (component I), the obtained monomer 1 further contains cyclopentadiene in the component I represented by the general formula (3). What was added (component II) was included, and the abundance ratio of these components was component I: component II = 90: 10 (weight ratio). The abundance ratio of the product coincided with that calculated from the intensity ratio of hydrogen in the double bond portion, methine, and methylene portion by ¹ H-NMR.

合成例１（環状オレフィン重合体の合成）
窒素置換した３００ｍｌの反応器に、シクロヘキサン１００ｍｌ、参考例１で得られたモノマー１ ８グラム、触媒として六塩化タングステンの濃度０．１モル／ｌのクロロベンゼン溶液２ｍｌ及びジエチルアルミニウムクロライドの濃度０．１モル／ｌのクロロベンゼン溶液０．２ｍｌを仕込み、窒素気流下、６０℃で、攪拌速度１００ｒｐｍにて攪拌下、５時間反応させた。得られた反応溶液をメタノールに注ぎ単離し、メタノールで数回洗浄を行った後、４０℃で一昼夜減圧乾燥を行い、７．９ｇの未水素化重合体を得た。ＧＰＣ測定により、得られた未水素化重合体の重量平均分子量は１２００００であった。

Synthesis Example 1 (Synthesis of cyclic olefin polymer)
Into a 300 ml reactor purged with nitrogen, 100 ml of cyclohexane, 8 grams of the monomer obtained in Reference Example 1, 2 ml of a chlorobenzene solution having a concentration of 0.1 mol / l tungsten hexachloride as a catalyst and a concentration of 0.1 ml of diethylaluminum chloride 0.2 ml of a mol / l chlorobenzene solution was charged, and the mixture was reacted at 60 ° C. under a nitrogen stream at a stirring speed of 100 rpm for 5 hours. The resulting reaction solution was poured into methanol and isolated, washed several times with methanol, and then dried under reduced pressure at 40 ° C. overnight to obtain 7.9 g of an unhydrogenated polymer. The weight average molecular weight of the obtained unhydrogenated polymer was 120,000 by GPC measurement.

  7 grams of the obtained unhydrogenated polymer, 30 grams of toluene and 0.1 mg of ruthenium hydride triphenylphosphine complex were charged into a 100 cc stainless steel autoclave and stirred to obtain a uniform solution. Subsequently, a hydrogenation reaction was performed with stirring for 4 hours at a hydrogen gas pressure of 10 MPa and a temperature of 160 ° C. After the reaction solution was cooled, excess hydrogen was released and depressurized, and then the reaction solution was poured into a large amount of hydrochloric acid-methanol solution, isolated, and dried under reduced pressure at 50 ° C. overnight to obtain 7 g of a cyclic olefin polymer. The cyclic olefin polymer had a weight average molecular weight of 150,000 and a glass transition temperature of 171 ° C. The hydrogenation rate was 99.5%.

Synthesis Example 2 (Synthesis of cyclic olefin polymer)
Into a 500 ml reactor purged with nitrogen, 180 ml of cyclohexane, 20 grams of the monomer 1 obtained in Reference Example 1, 4 ml of a chlorobenzene solution having a concentration of 0.1 mol / l tungsten hexachloride as a catalyst and a concentration of 0.1 ml of diethylaluminum chloride 0.4 ml of a mol / l chlorobenzene solution was charged, and the mixture was reacted at 60 ° C. under a nitrogen stream at a stirring speed of 100 rpm for 5 hours. The obtained unhydrogenated polymer was charged with 0.2 mg of a ruthenium hydride triphenylphosphine complex, and further hydrogen gas was injected, and a hydrogenation reaction was carried out at a pressure of 10 MPa at a temperature of 160 ° C. with stirring for 5 hours. After the reaction solution was cooled, excess hydrogen was released and depressurized, and then the reaction solution was poured into a large amount of hydrochloric acid-methanol solution, isolated, and dried under reduced pressure at 50 ° C. overnight to obtain 14 g of a cyclic olefin polymer. The cyclic olefin polymer had a weight average molecular weight of 120,000 and a glass transition temperature of 171 ° C. The hydrogenation rate was 99.4%.

Synthesis Example 3 (Synthesis of cyclic olefin polymer)
In a 500 ml reactor purged with nitrogen, 180 ml of cyclohexane, 20 grams of monomer 1 obtained in Reference Example 1, 0.015 g of 1-hexene, 4 ml of a chlorobenzene solution of tungsten hexachloride at a concentration of 0.1 mol / l and diethylaluminum chloride 0.4 ml of a chlorobenzene solution having a concentration of 0.1 mol / l was charged and allowed to react for 5 hours under stirring at a stirring speed of 100 rpm at 60 ° C. in a nitrogen stream. The obtained unhydrogenated polymer was charged with 0.2 mg of a ruthenium hydride triphenylphosphine complex, and further hydrogen gas was injected, and a hydrogenation reaction was carried out at a pressure of 10 MPa at a temperature of 160 ° C. with stirring for 5 hours. After the reaction solution was cooled, excess hydrogen was released and depressurized, and then the reaction solution was poured into a large amount of hydrochloric acid-methanol solution, isolated, and dried under reduced pressure at 50 ° C. overnight to obtain 14 g of a cyclic olefin polymer. The cyclic olefin polymer had a weight average molecular weight of 60,000 and a glass transition temperature of 170 ° C. The hydrogenation rate was 99.8%.

Example 1
After 100 parts by weight of the cyclic olefin polymer obtained in Synthesis Example 1 was dry blended with 0.05 parts by weight of ethylenebisstearic acid amide as a fatty acid amide lubricant, a 30 mmφ twin screw extruder (manufactured by Nippon Steel Works, Ltd., Extruded to product name TEX30) to obtain a resin composition. The resulting resin composition had a glass transition temperature of 170 ° C.

  Next, the obtained resin composition was subjected to a twin-screw extruder equipped with a T die, and extruded under the conditions of a T die temperature of 265 ° C. and a cooling roll temperature of 135 ° C. to obtain a film having a thickness of 100 μm. The film was cut into a 200 mm square, and the film thickness, total light transmittance, haze, YI, and Ra were measured. The results are shown in Table 1. The obtained film was excellent in transparency, color tone, and appearance, and was suitable for an optical film.

Example 2
After 100 parts by weight of the cyclic olefin polymer obtained in Synthesis Example 2 was dry blended with 0.05 parts by weight of calcium stearate as a metal soap lubricant, a 30 mmφ twin screw extruder (manufactured by Nippon Steel Works, trade name: TEX30 And extruding to obtain a resin composition.
The resulting resin composition had a glass transition temperature of 170 ° C.

  Next, the obtained resin composition was subjected to a twin-screw extruder provided with a T-die, and extruded under conditions of a T-die temperature of 270 ° C. and a cooling roll temperature of 135 ° C. to obtain a film having a thickness of 100 μm. The film was cut into a 200 mm square, and the film thickness, total light transmittance, haze, YI, and Ra were measured. The results are shown in Table 1. The obtained film was excellent in transparency, color tone, and appearance, and was suitable for an optical film.

Example 3
100 parts by weight of the cyclic olefin polymer obtained in Synthesis Example 3 was dry blended with 0.05 parts by weight of methylene bis stearamide as a fatty acid amide lubricant and 0.05 parts by weight of magnesium stearate as a metal soap lubricant. Then, it used for extrusion to 30 mmphi twin screw extruder (Nippon Steel Works make, brand name TEX30), and obtained the resin composition. The resulting resin composition had a glass transition temperature of 170 ° C.

  Next, the obtained resin composition was subjected to a twin-screw extruder provided with a T die, and extruded under conditions of a T die temperature of 275 ° C. and a cooling roll temperature of 135 ° C. to obtain a film having a thickness of 100 μm. The film was cut into a 200 mm square, and the film thickness, total light transmittance, haze, YI, and Ra were measured. The results are shown in Table 1. The obtained film was excellent in transparency, color tone, and appearance, and was suitable for an optical film.

Example 4
100 parts by weight of the cyclic olefin polymer obtained in Synthesis Example 3 was dry blended with 0.05 parts by weight of methylene bis stearamide as a fatty acid amide lubricant and 0.04 parts by weight of zinc stearate as a metal soap lubricant. Then, it used for extrusion to 30 mmphi twin screw extruder (Nippon Steel Works make, brand name TEX30), and obtained the resin composition. The resulting resin composition had a glass transition temperature of 170 ° C.

  Next, the obtained resin composition was subjected to a twin-screw extruder provided with a T die, and extruded under conditions of a T die temperature of 275 ° C. and a cooling roll temperature of 135 ° C. to obtain a film having a thickness of 100 μm. The film was cut into a 200 mm square, and the film thickness, total light transmittance, haze, YI, and Ra were measured. The results are shown in Table 1. The obtained film was excellent in transparency, color tone, and appearance, and was suitable for an optical film.

Comparative Example 1
The cyclic olefin polymer obtained in Synthesis Example 1 was used as a film in the same manner as in Example 1 except that no lubricant was added. The evaluation results of the obtained film are shown in Table 1. The obtained film was excellent in optical isotropy and thickness accuracy, but had a high YI.

Comparative Example 2
The cyclic olefin polymer obtained in Synthesis Example 2 was used as a film in the same manner as in Example 2 except that no lubricant was added. The evaluation results of the obtained film are shown in Table 1. The obtained film was excellent in optical isotropy and thickness accuracy, but had a high YI.

Comparative Example 3
The cyclic olefin polymer obtained in Synthesis Example 3 was used as a film in the same manner as in Example 3 except that no lubricant was added. The evaluation results of the obtained film are shown in Table 1. The obtained film was excellent in optical isotropy and thickness accuracy, but had a high YI.

Comparative Example 4
The cyclic olefin polymer obtained in Synthesis Example 3 was used as a film in the same manner as in Example 4 except that no lubricant was added. The evaluation results of the obtained film are shown in Table 1. The obtained film was excellent in optical isotropy and thickness accuracy, but had a high YI.

Claims (5)

The following general formula (1)

(Here, X and Y independently represent a methylene group, an oxygen atom, a sulfur atom or a tellurium atom, and n represents 0 or a positive integer.)
A transparent resin composition characterized by blending 0.001 to 2 parts by weight of a fatty acid amide-based lubricant and / or a metal soap-based lubricant with 100 parts by weight of a cyclic olefin polymer comprising a repeating unit represented by 2. The transparent resin composition according to claim 1, wherein the fatty acid amide lubricant is at least one fatty acid amide lubricant selected from the group consisting of ethylene bis stearamide and methylene bis stearamide. 2. The transparent resin composition according to claim 1, wherein the metal soap lubricant is at least one metal soap lubricant selected from the group consisting of calcium stearate, magnesium stearate, and zinc stearate. An optical film comprising the transparent resin composition according to claim 1. 5. The optical film according to claim 4, having a haze of 1% or less and a yellow index (YI) of 2 or less.