[go: up one dir, main page]

WO2009139293A1 - Résine d'oléfine cyclique et film comprenant la résine - Google Patents

Résine d'oléfine cyclique et film comprenant la résine Download PDF

Info

Publication number
WO2009139293A1
WO2009139293A1 PCT/JP2009/058352 JP2009058352W WO2009139293A1 WO 2009139293 A1 WO2009139293 A1 WO 2009139293A1 JP 2009058352 W JP2009058352 W JP 2009058352W WO 2009139293 A1 WO2009139293 A1 WO 2009139293A1
Authority
WO
WIPO (PCT)
Prior art keywords
cyclic olefin
mol
film
resin
ratio
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2009/058352
Other languages
English (en)
Japanese (ja)
Inventor
俊雄 塩飽
栄起 國本
左枝 石川
マティアス ブルッフ
アン－マイク シャーヴィノルト
裕之 金井
クラウス－ゲオルグ バーグホイザー
クラウス バーガー
ウド マンフレッド シュテーリング
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Topas Advanced Polymers GmbH
Daicel Corp
Polyplastics Co Ltd
Original Assignee
Topas Advanced Polymers GmbH
Polyplastics Co Ltd
Daicel Chemical Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Topas Advanced Polymers GmbH, Polyplastics Co Ltd, Daicel Chemical Industries Ltd filed Critical Topas Advanced Polymers GmbH
Publication of WO2009139293A1 publication Critical patent/WO2009139293A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings

Definitions

  • the present invention relates to a novel cyclic olefin resin having a characteristic microstructure and a film using the cyclic olefin resin.
  • liquid crystal display devices In recent years, the progress of liquid crystal display devices has been remarkable, and the liquid crystal display devices are being widely used not only for small-sized and medium-sized devices such as mobile phones and personal computer monitors but also for large-sized devices for televisions.
  • Various polymer films are used for liquid crystal display devices, and among them, there are retardation films used for color compensation of liquid crystals.
  • Polycarbonate or the like has been often used as a polymer material used for the retardation film.
  • the retardation film is required to have a uniform retardation over the entire surface, and the optical characteristics do not change even under a severe environment of high temperature and high humidity.
  • a film made by stretching and orienting a film made of polycarbonate (PC) is used as a retardation film, but polycarbonate has a large photoelastic constant over the glass transition temperature and above the glass transition temperature, so that birefringence is high.
  • problems such as being too large, non-uniformity, and the phase difference being changed by a slight stress generated due to assembly or environmental changes.
  • the polycarbonate film has a small surface hardness, there is a problem that the polycarbonate film is easily damaged during film production or device assembly.
  • Cyclic olefin-based resins are polyolefins that have an alicyclic structure to increase heat resistance and are made amorphous, and are characterized by excellent dimensional stability due to high transparency and low water absorption. Furthermore, since it does not contain an aromatic component, it has a feature that the photoelastic constant in the glass region is extremely low, and its excellent physical properties are gradually attracting attention as the size of liquid crystal display devices for television and the like increases. Is the current situation. From such a background, a technique relating to a cyclic olefin resin suitable as a retardation film has been disclosed (Patent Document 1).
  • retardation films are required to have not only high heat resistance but also high tensile properties.
  • the retardation film is usually bonded to a polarizing plate or a liquid crystal cell using an adhesive. When this is exposed to a high temperature, the thermal expansion coefficients of the liquid crystal cell and the retardation film are different from each other. Therefore, stress is inevitably generated at the laminated interface, and the optical properties of the retardation film are impaired.
  • the present invention has been made to solve the above-described problems, and its object is to provide a cyclic olefin-based resin suitable for producing a retardation film having high heat resistance and tensile properties, and the cyclic olefin. Another object is to provide a film using a resin, especially a retardation film.
  • the present inventors have intensively studied to solve the above problems.
  • the cyclic olefin resin has a high glass transition point, and the continuity between the repeating unit derived from the cyclic olefin monomer component and the repeating unit derived from the acyclic olefin monomer is controlled to a specific one.
  • the present inventors have found that the above problems can be solved, and have completed the present invention. More specifically, the present invention provides the following.
  • the cyclic The ratio of the repeating unit derived from the olefin monomer is from 50 mol% to 80 mol%, the ratio of the repeating unit derived from the acyclic olefin monomer is from 20 mol% to 50 mol%, and in the cyclic olefin component
  • the ratio of the repeating unit derived from the cyclic olefin monomer as a dimer is 40 mol% or more, and the repeating unit derived from the cyclic olefin monomer in the cyclic olefin component is present as a trimer.
  • Cyclic olefin resin whose ratio is 20 mol% or more.
  • the ratio of the repeating unit derived from the cyclic olefin monomer is from 50 mol% to 65 mol%, and in the dimer, the ratio of the meso-type double chain site to the racemo-type double chain site (meso-type double chain) Cyclic olefin resin as described in (1) whose site
  • part is 10 or more.
  • a retardation film comprising the cyclic olefin-based resin according to (1) or (2).
  • the cyclic olefin resin of the present invention has a high glass transition point, and the continuity between the repeating unit derived from the cyclic olefin monomer component and the repeating unit derived from the acyclic olefin monomer is controlled to a specific one. Yes.
  • a film having high heat resistance and tensile properties can be obtained.
  • the present invention has a specific continuity between a repeating unit derived from a cyclic olefin monomer component and a repeating unit derived from an acyclic olefin monomer so that a film having high heat resistance and tensile properties can be produced. It is a controlled cyclic olefin resin.
  • a cyclic olefin-based resin and a film produced using the same will be described.
  • the cyclic olefin resin of the present invention has a glass transition point in the range of 150 ° C. or higher, and the continuity between the repeating unit derived from the cyclic olefin monomer component and the repeating unit derived from the acyclic olefin monomer is specified. It is the feature that it was controlled by the thing.
  • the cyclic olefin resin used in the present invention is a polyolefin resin containing a cyclic olefin monomer as a copolymerization component and containing a cyclic olefin monomer in the main chain.
  • A1 Addition copolymers of cyclic olefins and acyclic olefins or hydrogenated products thereof.
  • the above-mentioned resin further grafted and / or copolymerized with an unsaturated compound having a polar group, including.
  • the polar group include a carboxyl group, an acid anhydride group, an epoxy group, an amide group, an ester group, and a hydroxyl group.
  • the unsaturated compound having a polar group include (meth) acrylic acid and maleic acid.
  • Acid maleic anhydride, itaconic anhydride, glycidyl (meth) acrylate, alkyl (meth) acrylate (1 to 10 carbon atoms) ester, alkyl maleate (1 to 10 carbon atoms) ester, (meth) acrylamide, (meta And 2-hydroxyethyl acrylate.
  • an addition copolymer of a cyclic olefin and an ⁇ -olefin or a hydrogenated product thereof can be preferably used.
  • the addition copolymer of cyclic olefin and acyclic olefin preferably used in the composition of the present invention is not particularly limited.
  • Preferable examples include a copolymer containing an acyclic olefin monomer and a cyclic olefin monomer (norbornenes) represented by the following general formula (I).
  • R 1 to R 12 may be the same or different and are selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, etc., and R 9 and R 10 , R 11 And R 12 may be integrated to form a divalent hydrocarbon group, and R 9 or R 10 and R 11 or R 12 may form a ring with each other, and n is , 0 or a positive integer, and when n is 2 or more, R 5 to R 8 may be the same or different in each repeating unit.
  • the acyclic olefin monomer is not particularly limited as long as it can be copolymerized with the above cyclic olefin monomer, but is preferably an ⁇ -olefin, more preferably ethylene.
  • Acyclic olefinic monomers may be used alone or in combination of two or more as required.
  • the cyclic olefin resin of the present invention contains 50 mol% to 80 mol% of repeating units derived from a cyclic olefin monomer and 20 mol% to 50 mol% of repeating units derived from an acyclic olefin monomer.
  • the repeating unit is derived from 50 mol% to 65 mol% derived from a cyclic olefin monomer, and the repeating unit derived from an acyclic olefin monomer is from 35 mol% to 50 mol%. If the content of the cyclic olefin monomer exceeds 80 mol%, the temperature required for processing increases, and coloring during molding cannot be ignored. When the amount is less than 50 mol% of the cyclic olefin monomer, the heat resistance becomes insufficient.
  • the ratio of the cyclic olefin-based resin of the present invention in which the repeating unit derived from the cyclic olefin-based monomer is present as a dimer with respect to the content of the cyclic olefin-based monomer is 40 mol% or more.
  • the ratio of the repeating unit derived from the cyclic olefin-based monomer as a trimer with respect to the content of the cyclic olefin-based monomer is 20 mol% or more.
  • the ratio of the repeating unit derived from the cyclic olefin monomer to the content of the cyclic olefin monomer is 40 mol% or more and the ratio of the trimer to be present is 20 mol% or more, Even when Tg is 150 ° C. or higher, the film properties are improved.
  • the stereoregularity of the dimer includes a meso form of the following formula (II) and a racemo form of the following formula (III).
  • the abundance ratio of the stereoisomer in the cyclic olefin-based resin of the present invention is not particularly limited, but is 10 or more. Preferably it is 15 or more.
  • the meso type has better molecular symmetry and is more likely to be aligned in a straight line, so that the molecular chains are easily oriented, and therefore the phase difference performance can be improved.
  • the cyclic olefin monomers are easily twisted due to steric hindrance between the carbons at the bridgehead positions of the cyclic olefin monomers, and the molecular chain is easily bent.
  • the abundance ratio of the stereoisomer is lower than the preferable range, the retardation development property tends to be lowered, which is not preferable.
  • the content ratio of the meso-type double chain portion is larger than the content of the cyclic olefin monomer.
  • the ratio of the repeating unit derived from the cyclic olefin monomer as a dimer is 40 mol% or more, and in these dimers, the meso-type double chain site and the racemo type
  • the ratio (meso-type double-chain site / rasemo-type double-chain site) to the double-chain site is 10 or more, and the proportion of the repeating unit derived from the cyclic olefin monomer as a trimer is 20 mol% or more Can be obtained.
  • the cyclic olefin resin of the present invention may contain a repeating unit derived from another monomer component copolymerizable with the cyclic olefin monomer or the acyclic olefin monomer.
  • Such other monomer components are not particularly limited.
  • the content of the repeating unit derived from the other monomer is preferably 10 mol% or less, more preferably 5 mol% or less, and further preferably 3 mol% or less. . Exceeding the preferable range is not preferable because the film performance such as heat resistance is affected.
  • the glass transition point of the cyclic olefin resin of the present invention is 150 ° C. or higher.
  • the glass transition point is lower than 150 ° C., the heat resistance of the obtained retardation film is lowered. If the glass transition point exceeds 190 ° C., the toughness of the film tends to decrease, and the melt viscosity of the copolymer becomes too high, making it difficult to melt the film.
  • the preferred glass transition point range is 150 ° C to 190 ° C.
  • the molecular weight of the cyclic olefin resin of the present invention can be determined using Melt Volume Rate (MVR) as an index.
  • MVR can be measured based on ISO 1133, and means the volume of resin discharged in 10 minutes at a temperature of 260 ° C. and a load of 2.16 kg (mL / 10 minutes).
  • the preferable lower limit of MVR of the cyclic olefin resin of the present invention is 0.5 mL / 10 minutes, and the preferable upper limit is 40 mL / 10 minutes. If it is less than 0.5 mL / 10 minutes, the moldability may be inferior, and if it exceeds 40 mL / 10 minutes, a molded article having sufficient strength may not be obtained.
  • a more preferable lower limit is 0.8 mL / 10 minutes, and a more preferable upper limit is 30 mL / 10 minutes.
  • the cyclic olefin resin of the present invention can be produced by optimizing the polymerization catalyst and polymerization conditions.
  • a composite catalyst system of a metallocene catalyst and methylalumoxane as a cocatalyst can be used.
  • the metallocene catalyst include racemic-ethylidene-bis (indenyl) zirconium dichloride, racemic-dimethylsilyl-bis (2-methyl-benzoindenyl) zirconium dichloride, racemic-isopropylidene-bis (tetrahydroindenyl) zirconium.
  • Examples thereof include dichloride and isopropylidene (1-indenyl) (3-isopropyl-cyclopentadienyl) zirconium dichloride. Of these, racemic-isopropylidene-bis (tetrahydroindenyl) zirconium dichloride is preferred.
  • Other catalyst systems can be used for the production of the cyclic olefin-based resin of the present invention as long as the above characteristic microstructure can be obtained.
  • a conventionally known method can be used as a method for producing the above cyclic olefin resin. Specifically, for example, a cyclic olefin monomer and an acyclic olefin monomer are introduced into a reactor, and a catalyst solution or dispersion is added thereto to obtain a predetermined reaction temperature.
  • the ratio of the repeating unit derived from the monomer in the obtained cyclic olefin resin (A) can be controlled by optimally setting the reaction temperature and pressure. Since acyclic olefinic monomers are often gaseous, it is preferable to keep the olefin pressure constant in order to keep the introduction rate of the olefin monomer in the copolymer constant.
  • the catalyst is deactivated by a method such as addition of alcohol and removed from the reaction system.
  • the resin composition may contain other compatible or incompatible polymers. These polymers can form another layer or be mixed with a cyclic olefin resin. Mixing can be performed in a molten state or a solution state.
  • a resin is not particularly limited, and examples thereof include polyethylene, polypropylene, styrene butadiene styrene block copolymer, styrene ethylene butylene styrene block copolymer, and styrene ethylene propylene styrene block polymer.
  • the cyclic olefin-based resin preferably contains a lubricant for the purpose of improving smoothness and moldability.
  • a lubricant for the purpose of improving smoothness and moldability.
  • Lubricant is usually supplied together with resin pellets when added to the molding machine (external addition) or contained inside the resin pellets (internal addition).
  • internal addition it is possible to suppress defects caused by the lubricant remaining at the root of the extruder in the case of external addition and deterioration of the lubricant; in the case of external addition, the production environment is clean due to the scattering of lubricant powder. The reduction in the degree can be suppressed; since the filter can be passed through during pelletization, various effects such as effective removal of foreign matters in the lubricant can be obtained.
  • the polymerization solution is blended with a lubricant such as an antioxidant or a stabilizer, if necessary, and a solvent is removed.
  • a lubricant such as an antioxidant or a stabilizer
  • the lubricant is not particularly limited. From the group consisting of a fatty acid ester compound having a long-chain aliphatic hydrocarbon group, an amide compound having a long-chain aliphatic hydrocarbon group, and a salt having a long-chain aliphatic hydrocarbon group. At least one selected from the above is preferred.
  • the preferable lower limit of the content of the lubricant in the cyclic olefin resin composition is 0.01 part by mass with respect to 100 parts by mass of the cyclic olefin resin (A), and the preferable upper limit is 3 parts by mass.
  • a more preferred lower limit is 0.03 parts by mass, a more preferred upper limit is 2.5 parts by mass, a still more preferred lower limit is 0.05 parts by mass, and a still more preferred upper limit is 2 parts by mass.
  • the resin composition containing the cyclic olefin-based resin of the present invention is an anti-aging agent such as phenol-based or phosphorus-based; an anti-aging agent such as phenol-based; Agents: Conventionally known additives such as ultraviolet absorbers such as benzophenone and benzotriazole may be contained.
  • the retardation film of the present invention can be produced by producing a film from a composition containing the cyclic olefin resin (A) and the cyclic olefin resin (A) and then subjecting it to a stretching treatment.
  • the method for producing the film is not particularly limited, and conventionally known film forming methods such as a melt extrusion film forming method, a calender film forming method, and a solution cast (casting) film forming method can be used. Of these, the melt extrusion film-forming method is preferable because of its excellent productivity and symbiosis with the environment.
  • the temperature was raised to near the glass transition point (Tg) obtained by the DSC method (JIS K7121, or the method described in German Industrial Standards DIN53765 and DIN51007). It is necessary to stretch in a state.
  • the stretching method is not particularly limited, and examples thereof include longitudinal uniaxial stretching, lateral uniaxial stretching, simultaneous biaxial stretching, and sequential biaxial stretching.
  • stretching is not specifically limited, although in-line extending
  • the temperature in the stretching treatment is preferably near the glass transition point (Tg), although it depends on conditions such as the stretching ratio.
  • Tg glass transition point
  • even if whitening does not occur it is difficult to align the axial direction of the phase difference with accuracy, or when a durability test is performed in a high-temperature atmosphere, the phase difference value decreases and sufficient durability cannot be obtained. Such a problem is also likely to occur.
  • the stretching is performed at an excessively higher temperature than the glass transition point (Tg), it becomes difficult to obtain a required retardation value.
  • the retardation film of the present invention produced by the method as described above has high heat resistance. For example, even when the film is exposed to a high temperature of about 150 ° C., the film can be prevented from curling. In addition, it has high tensile properties and can flexibly cope with the force applied during use.
  • the thickness of the retardation film is not particularly limited, but the retardation increases as the thickness increases.
  • technology for reducing the size, thickness, and weight has been demanded, and a thin retardation film has also been demanded.
  • the cyclic olefin resins of Production Examples 1 and 2 synthesized by the following method were used in Examples 1 and 2, and commercially available cyclic olefin resins 6015S-04 (Topas Advanced Polymers), 6013S-04. (Topas Advanced Polymers) was used in Comparative Examples 3 and 4, respectively.
  • the amount of metallocene required for polymerization was calculated so that 10 g to 30 g of polymer was obtained.
  • approximately 10 mg of the metallocene catalyst was accurately weighed and dissolved so as to be a solution similar to the promoter solution.
  • the required amount of catalyst solution was placed in a syringe.
  • the second syringe was then filled with the cocatalyst solution so that a total of 10 ml of MAO solution could be injected into the autoclave.
  • 10 ml of MAO solution Corresponds to 0.884 g MAO (16.4 mmol Al).
  • the autoclave was washed by stirring a mixed solution of 10 ml MAO solution and 1 L Exxol® at 90 ° C. before polymerization. Thereafter, a toluene solution of norbornene and a MAO solution (second syringe) were added to the autoclave under an argon atmosphere. The autoclave was warmed to the set temperature. Thereafter, the catalyst solution was injected into the autoclave using a syringe. The autoclave was first pressurized with hydrogen gas as needed, and then pressurized with ethylene gas. The required ethylene pressure was added with stirring and was kept constant during the polymerization by a pressure reducing valve. The consumption of ethylene was confirmed by a flow meter.
  • the reaction amount was 600 ml and the reaction time was 15 minutes. After polymerization, the ethylene supply was stopped and excess pressure was released. The reaction solution was transferred to a screw bottle. The solution was poured into 3 L of acetone oxidized with 5 ml of concentrated hydrochloric acid (37%) with stirring. The precipitated polymer was separated using a Buchner funnel while stirring with 2 L acetone, then water, and finally acetone. Drying was performed overnight at 80 ° C. in vacuum. The manufacturing conditions are shown in Table 1.
  • the glass transition temperature was measured by DSC (differential scanning calorimetry). It was evaluated by the method based on DIN 53765 and calculated by the method based on DIN 51007. A Mettler DSC820 was used as a measuring instrument. A temperature increase / decrease of 20 ° C./min was applied and the second heating cycle was evaluated.
  • the proportion of repeating units derived from cyclic olefin monomers of these raw materials as dimers, the proportion of repeating units derived from cyclic olefin monomers as trimers, and the cyclic olefin monomers present as dimers The ratio of the repeating unit derived from the above and the content of the repeating unit derived from the cyclic olefin monomer were determined by the following method.
  • the ratio of the chain olefin monomer to the bridged cycloalkene monomer (norbornene monomer), and the biad, triplet, and meso-racemo ratio were observed by 13C-NMR. It can be calculated from the integrated value of the spectrum obtained.
  • the peaks are divided using JEOL's NMR data processing software “ALICE for Windows (registered trademark) Ver. 5”, and the integration of each peak is performed. The value was determined.
  • the composition is an integral value observed at a chemical shift value of 44.5-56.0 ppm in the spectrum chart obtained by 13C-NMR: I C2, C3 (derived from the 2nd and 3rd positions of the norbornene ring), Integral value observed at a chemical shift value of 39.0-44.0 ppm: I C1, C4 (derived from carbons at positions 1 and 4 of the norbornene ring), Integral value observed at a chemical shift value of 33.0-39.0 ppm: I C7 (derived from carbon at the 7-position of the norbornene ring),
  • the integral value observed at a chemical shift value of 27.5-33.0 ppm: I C5, C6 + I E (derived from the carbons at the 5th and 6th positions of the norbornene ring and the carbon of the ethylene part) can be obtained from the following formula: it can.
  • the ratio of the quantity of the bipartite part and the triplet part is six triads (EEE, EEN, NEN, NNN, NNE, described in “Macromol. Chem. Phs. 1999, Vol. 200, Page 1340”). ENE) can be obtained and calculated from the following equation.
  • the abundance ratio of the meso-type double chain site and the racemo-type double chain site that is, the meso / racemo ratio (M / R), and the meso type 2
  • the abundance of chain sites, that is, the meso content (M / (M + R)) was determined from the following peaks derived from ENNE of the spectrum obtained by 13C-NMR.
  • Integral value of peak observed at 28.3 ppm C5-meso isomer: I C5-m Integral value of peak observed at 29.7 ppm (C5-racemo isomer): I C5-r Integrated value of peak observed at 31.6 ppm ( C6- meso isomer): I C6-m Integral value of peak observed at 31.3 ppm ( C6- racemo isomer): I C6-r Integrated value of peak observed at 33.1-33.4 ppm ( C7- meso isomer): I C7-m
  • the integrated value I C7-r of the peak observed at 33.4-33.7 ppm ( C7- racemo isomer) Therefore, it calculated
  • sample preparation conditions and measurement conditions in the present invention is as follows.
  • Solvent 1,1,2,2-tetrachloroethane-d2 (containing 10% by volume hexamethyldisilane) Concentration: 70 mg / mL
  • Apparatus Bruker AVANCE 600 (resonance frequency of hydrogen atom: 600 MHz)
  • Sample tube diameter 10mm
  • Power gate type pulse width 15 ⁇ sec
  • Delay time 2.089sec
  • Data acquisition time 0.911 sec
  • Observation frequency width 35971.22Hz
  • Decoupling Total number of complete decoupling: 18000 times
  • Chemical shift reference Hexamethyldisilane peak is -2.43 ppm.
  • MVR can be measured based on ISO 1133, and the volume of resin discharged in 10 minutes at a temperature of 260 ° C. and a load of 2.16 kg (mL / 10 minutes) was measured.
  • the temperature at which the storage elastic modulus becomes 5 MPa is such that the copolymer composition is formed into a film and a 0.01% strain is applied to the film at 10 Hz using a dynamic viscoelasticity measuring device (RSA3 manufactured by TA Instruments). And estimated from the storage elastic modulus (E ′) obtained when the temperature was raised from 20 to 200 ° C. at a rate of 5 ° C./min.
  • the ratio of the acyclic olefin-based repeating unit is obtained as a value obtained by subtracting the norbornene amount in Table 2 from 100 mol%.
  • the film produced using the cyclic olefin-based resin of the present invention showed tensile properties (stress at break, elongation at break) and heat resistance while showing a retardation value higher than the conventional level. Has been confirmed to improve.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention porte sur une résine d'oléfine cyclique appropriée pour la fabrication d'un film ayant une résistance à la chaleur élevée et des propriétés à la traction élevées. L'invention porte également sur un film obtenu à l'aide de la résine d'oléfine cyclique. La résine d'oléfine cyclique a une température de transition vitreuse supérieure ou égale à 150°C et contient une unité récurrente issue d'un monomère oléfine cyclique en proportion de 50 à 80 % en mole et une unité récurrente issue d'un monomère oléfine non cyclique en proportion de 20 à 50 % en mole. Dans la résine d'oléfine cyclique, la proportion d'un dimère de l'unité récurrente issue du monomère oléfine cyclique dans le composant oléfine cyclique est supérieure ou égale à 40 % en mole, le rapport d'une dyade méso à une dyade racémo [c'est-à-dire un rapport (dyade méso)/(dyade racémo)] dans le dimère est supérieur ou égal à 10 et la proportion d'un trimère de l'unité récurrente issue du monomère oléfine cyclique dans le composant oléfine cyclique est inférieure ou égale à 20 % en mole.
PCT/JP2009/058352 2008-05-12 2009-04-28 Résine d'oléfine cyclique et film comprenant la résine Ceased WO2009139293A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008124910A JP2011063629A (ja) 2008-05-12 2008-05-12 環状オレフィン系樹脂及び当該樹脂を用いたフィルム
JP2008-124910 2008-05-12

Publications (1)

Publication Number Publication Date
WO2009139293A1 true WO2009139293A1 (fr) 2009-11-19

Family

ID=41318664

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/058352 Ceased WO2009139293A1 (fr) 2008-05-12 2009-04-28 Résine d'oléfine cyclique et film comprenant la résine

Country Status (2)

Country Link
JP (1) JP2011063629A (fr)
WO (1) WO2009139293A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011162414A1 (fr) * 2010-06-25 2011-12-29 Gunze Limited Corps plan transparent et panneau tactile transparent

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006011361A (ja) * 2004-05-28 2006-01-12 Sekisui Chem Co Ltd 位相差フィルム
WO2006030797A1 (fr) * 2004-09-15 2006-03-23 Teijin Limited Film a retard de flamme
JP2007010863A (ja) * 2005-06-29 2007-01-18 Teijin Ltd 位相差フィルム及びその製造方法
JP2009003439A (ja) * 2007-05-23 2009-01-08 Daicel Chem Ind Ltd 光学フィルム
JP2009051922A (ja) * 2007-08-27 2009-03-12 Daicel Chem Ind Ltd 環状オレフィン系樹脂フィルム

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006011361A (ja) * 2004-05-28 2006-01-12 Sekisui Chem Co Ltd 位相差フィルム
WO2006030797A1 (fr) * 2004-09-15 2006-03-23 Teijin Limited Film a retard de flamme
JP2007010863A (ja) * 2005-06-29 2007-01-18 Teijin Ltd 位相差フィルム及びその製造方法
JP2009003439A (ja) * 2007-05-23 2009-01-08 Daicel Chem Ind Ltd 光学フィルム
JP2009051922A (ja) * 2007-08-27 2009-03-12 Daicel Chem Ind Ltd 環状オレフィン系樹脂フィルム

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011162414A1 (fr) * 2010-06-25 2011-12-29 Gunze Limited Corps plan transparent et panneau tactile transparent

Also Published As

Publication number Publication date
JP2011063629A (ja) 2011-03-31

Similar Documents

Publication Publication Date Title
KR101567269B1 (ko) 4-메틸-1-펜텐 (공)중합체 조성물, 해당 조성물로 이루어지는 필름 및 중공 성형체
JP6065796B2 (ja) 容器用ポリエチレン樹脂組成物及びそれよりなる成形体
US20130029125A1 (en) Thermoplastic Polyolefin Blends and Films Therefrom
JP6065797B2 (ja) 容器用ポリエチレン樹脂組成物及びそれよりなる成形体
JP2023106053A (ja) ４－メチル－１－ペンテン共重合体樹脂組成物、並びに、これからなる成形体、シート、粘着剤および日用雑貨
JP5776602B2 (ja) 容器用ポリエチレン樹脂組成物及びそれよりなる成形体
JP2011144297A (ja) エチレン重合体、その製造方法および前記重合体を含む成形体。
JP2009258571A (ja) 位相差フィルム
KR20070085246A (ko) 위상차 필름
JP2017186515A (ja) ポリエチレン樹脂組成物、並びにその成形体及び容器
WO2009139293A1 (fr) Résine d'oléfine cyclique et film comprenant la résine
JP4712455B2 (ja) 光学用フィルム
JP7701435B2 (ja) ４－メチル－１－ペンテン重合体
JP4000015B2 (ja) メタクリル系樹脂の製造方法
US20230101204A1 (en) Polyamide composition
WO2023026838A1 (fr) Polymère ramifié à base de propylène
JP2006083266A (ja) 光学用フィルム
EP3950738A1 (fr) Composition de résine
JP2017179300A (ja) ポリエチレン樹脂組成物、並びにその成形体及び容器
JP7392088B2 (ja) エチレン系樹脂組成物及び成形体
CN100489576C (zh) 相位差薄膜
JP2025103666A (ja) ポリアミド樹脂組成物
JP2014101415A (ja) プロピレン系共重合体組成物に極性基含有化合物を付加する方法、該方法を用いて得られた極性基含有プロピレン系共重合体組成物、該共重合体組成物を含む組成物および該方法を含む極性基含有プロピレン系共重合体組成物の製造方法
CN116897172A (zh) 4-甲基-1-戊烯聚合物
TW202337939A (zh) 環狀烯烴系共聚物、環狀烯烴系共聚物組成物、成形體、光學零件、及光學零件的用途

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09746500

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: JP

122 Ep: pct application non-entry in european phase

Ref document number: 09746500

Country of ref document: EP

Kind code of ref document: A1