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WO2015080167A1 - Film à base d'une composition de résine cyclo-oléfinique - Google Patents

Film à base d'une composition de résine cyclo-oléfinique Download PDF

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Publication number
WO2015080167A1
WO2015080167A1 PCT/JP2014/081279 JP2014081279W WO2015080167A1 WO 2015080167 A1 WO2015080167 A1 WO 2015080167A1 JP 2014081279 W JP2014081279 W JP 2014081279W WO 2015080167 A1 WO2015080167 A1 WO 2015080167A1
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Prior art keywords
styrene
cyclic olefin
resin composition
composition film
elastomer
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PCT/JP2014/081279
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English (en)
Japanese (ja)
Inventor
慶 小幡
堀井　明宏
石森　拓
健 細谷
香奈子 橋本
一樹 平田
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Dexerials Corp
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Dexerials Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/08—Copolymers of styrene
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures

Definitions

  • the present invention relates to a cyclic olefin resin composition film in which an elastomer or the like is added and dispersed in a cyclic olefin resin.
  • Cyclic olefin resin is an amorphous and thermoplastic olefin resin that has a cyclic olefin skeleton in its main chain, has excellent optical properties (transparency, low birefringence), low water absorption, It has excellent performance such as dimensional stability and high moisture resistance. Therefore, films or sheets made of cyclic olefin resins are expected to be developed for various optical applications such as retardation films, polarizing plate protective films, light diffusion plates, and moisture proof packaging applications such as pharmaceutical packaging and food packaging. Yes.
  • the film of cyclic olefin resin is inferior in toughness, it is known to improve toughness by adding and dispersing an elastomer having a hard segment and a soft segment (for example, see Patent Document 1).
  • the segment of the elastomer changes phase due to environmental changes, and even if the environment is returned to room temperature, it does not return to the original state. Therefore, the environmental preservation of the cyclic olefin resin film deteriorates due to the change in haze.
  • the present invention has been proposed in view of such a conventional situation, and provides a cyclic olefin-based resin composition film having excellent environmental preservation and toughness.
  • the present inventor has found that by adding a styrene elastomer having a specific melt flow rate to a cyclic olefin resin at a specific dispersion diameter, environmental preservation can be improved while maintaining excellent toughness, The present invention has been completed.
  • the cyclic olefin-based resin composition film according to the present invention has a cyclic flow olefin-based resin and a melt flow rate measured under conditions of 230 ° C. and 2.16 kgf in accordance with ISO 1133 of 4.5 g / 10 min or less.
  • the manufacturing method of the cyclic olefin-type resin composition film which concerns on this invention is based on cyclic olefin-type resin and ISO1133, and the melt flow rate measured on condition of 230 degreeC and 2.16kgf is 4.5 g / A styrene elastomer that is 10 min or less is melted at a temperature in the range of 210 ° C. to 300 ° C., and the molten cyclic olefin resin composition is extruded into a film by an extrusion method.
  • a cyclic olefin resin composition film obtained by dispersing 5 to 35 wt% in an olefin resin and having a short axis dispersion diameter of the styrene elastomer of 2 ⁇ m or less is obtained.
  • the cyclic olefin resin composition film according to the present invention is suitable for application to transparent conductive elements, input devices, display devices, and electronic devices.
  • the short axis dispersion diameter of the styrene elastomer having a specific melt flow rate dispersed in the cyclic olefin resin is 2 ⁇ m or less, excellent environmental preservation and toughness can be obtained.
  • FIG. 1 is a cross-sectional perspective view showing an outline of a cyclic olefin-based resin composition film according to the present embodiment.
  • FIG. 2 is a cross-sectional photograph of a film for explaining an example of a method for measuring the minor axis dispersion diameter.
  • FIG. 3 is a schematic diagram illustrating a configuration example of a film manufacturing apparatus.
  • 4A and 4B are cross-sectional views illustrating an example of a transparent conductive film
  • FIGS. 4C and 4D are cross-sectional views illustrating an example of a transparent conductive film provided with a moth-eye-shaped structure.
  • FIG. 5 is a schematic cross-sectional view illustrating a configuration example of the touch panel.
  • FIG. 1 is a cross-sectional perspective view showing an outline of a cyclic olefin-based resin composition film according to the present embodiment.
  • FIG. 2 is a cross-sectional photograph of a film for explaining an example of a method for measuring the minor
  • FIG. 6 is an external view illustrating an example of a television device as an electronic apparatus.
  • 7A and 7B are external views illustrating an example of a digital camera as an electronic device.
  • FIG. 8 is an external view illustrating an example of a notebook personal computer as an electronic device.
  • FIG. 9 is an external view illustrating an example of a video camera as an electronic apparatus.
  • FIG. 10 is an external view illustrating an example of a mobile phone as an electronic device.
  • FIG. 11 is an external view illustrating an example of a tablet computer as an electronic device.
  • the cyclic olefin-based resin composition film according to the present embodiment has a cyclic flow olefin-based resin and a melt flow rate measured under conditions of 230 ° C. and 2.16 kgf in accordance with ISO 1133 of 4.5 g / 10 min or less.
  • the styrene elastomer contains 5 to 35 wt% in a cyclic olefin resin, and the minor axis dispersion diameter of the styrene elastomer is 2 ⁇ m or less. Thereby, the outstanding environmental preservation property and toughness can be obtained.
  • FIG. 1 is a cross-sectional perspective view showing an outline of a cyclic olefin-based resin composition film according to the present embodiment.
  • the cyclic olefin-based resin composition film is, for example, a short film or sheet, the X-axis direction which is the width direction (TD: Transverse Direction), and the Y-axis direction which is the length direction (MD: Machine Direction), And a Z-axis direction that is a thickness direction.
  • the thickness Z of the cyclic olefin-based resin composition film is preferably 0.1 ⁇ m to 2 mm, more preferably 1 ⁇ m to 1 mm.
  • the cyclic olefin-based resin composition film contains a cyclic olefin-based resin 11 and a styrene-based elastomer 12, and the styrene-based elastomer 12 is dispersed in the cyclic olefin-based resin 12 by 5 to 35 wt%. That is, the mass% ratio of cyclic olefin resin / styrene elastomer is 95/5 to 65/35 (the total of both is 100 mass%). A more preferable mass% ratio of cyclic olefin resin / styrene elastomer is 93/7 to 80/20. If the addition ratio of the styrene-based elastomer 12 is too large, the environmental preservation is reduced, and if it is too small, the toughness is not sufficient.
  • a dispersed phase (island phase) made of styrene elastomer 12 is dispersed in a matrix (sea phase) made of cyclic olefin resin 11.
  • the dispersed phase is dispersed with shape anisotropy in the MD direction by, for example, extrusion molding, has a major axis in the MD direction, and a minor axis in the TD direction.
  • the short axis dispersion diameter of the styrene elastomer 12 is 2 ⁇ m or less, more preferably 1 ⁇ m or less. If the minor axis dispersion diameter is too large, a gap is generated between the styrene elastomer / cyclic olefin resin due to the styrene elastomer phase change under environmental preservation, and the refractive index of the styrene elastomer itself changes, The haze of the entire film is greatly changed.
  • the short axis dispersion diameter means the size in the TD direction of the dispersed phase composed of the styrene elastomer 12 and can be measured as follows. First, the TD-thickness (Z-axis) cross section of the cyclic olefin-based resin composition film is cut. And as shown in FIG. 2, the film cross section is enlarged and observed, the short axis of each disperse phase of the predetermined range of the film cross section center is measured, and the average value is made into a short axis dispersion diameter. Moreover, when a dispersion diameter is small, it is preferable to cut
  • the cyclic olefin-based resin is a polymer compound having a main chain composed of carbon-carbon bonds and having a cyclic hydrocarbon structure in at least part of the main chain.
  • This cyclic hydrocarbon structure is introduced by using a compound (cyclic olefin) having at least one olefinic double bond in the cyclic hydrocarbon structure as represented by norbornene or tetracyclododecene as a monomer. Is done.
  • Cyclic olefin resins include cyclic olefin addition (co) polymers or hydrogenated products thereof (1), cyclic olefin and ⁇ -olefin addition copolymers or hydrogenated products (2), cyclic olefin ring-opening ( Co) polymers or hydrogenated products thereof (3).
  • cyclic olefin examples include: cyclopentene, cyclohexene, cyclooctene; one-ring cyclic olefin such as cyclopentadiene, 1,3-cyclohexadiene; bicyclo [2.2.1] hept-2-ene (common name: norbornene) ), 5-methyl-bicyclo [2.2.1] hept-2-ene, 5,5-dimethyl-bicyclo [2.2.1] hept-2-ene, 5-ethyl-bicyclo [2.2.
  • Tricyclo [4.3.0.1 2,5 ] deca-3,7-diene (common name: dicyclopentadiene), tricyclo [4.3.0.1 2,5 ] dec-3-ene; tricyclo [ 4.4.0.1 2,5 ] undeca-3,7-diene or tricyclo [4.4.0.1 2,5 ] undeca-3,8-diene or a partially hydrogenated product thereof (or cyclopentadiene) Tricyclo [4.4.0.1 2,5 ] undec-3-ene; 5-cyclopentyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexenylbicyclo [2.2.1] hept-2-ene, 5-phenyl-bicyclo [2.2.1] hept-2-ene A cyclic olefin of the ring;
  • Tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene also simply referred to as tetracyclododecene
  • 8-methyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene 8-ethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene
  • 8-methylidenetetracyclo 4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene
  • 8-vinyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene 8-propenyl-tetracyclo [4.4.0.1 2,5 . 1 7,10 ] tetracyclic olefins such as dodec-3-ene;
  • ⁇ -olefin copolymerizable with the cyclic olefin examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3 -Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1- Hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc.
  • Examples thereof include 2 to 8 ethylene or ⁇ -olefin. These ⁇ -olefins can be used alone or in combination of two or more. As these ⁇ -olefins, those contained in the range of 5 to 200% with respect to the cyclic polyolefin can be used.
  • an addition copolymer of ethylene and norbornene is preferably used as the cyclic olefin resin.
  • the structure of the cyclic olefin-based resin is not particularly limited, and may be a chain, branched, or crosslinked, but is preferably a straight chain.
  • the molecular weight of the cyclic olefin-based resin is 5,000 to 300,000, preferably 10,000 to 150,000, and more preferably 15,000 to 100,000 according to the GPC method. If the number average molecular weight is too low, the mechanical strength decreases, and if it is too high, the moldability deteriorates.
  • the cyclic olefin resin has a polar group (for example, a carboxyl group, an acid anhydride group, an epoxy group, an amide group, an ester group, a hydroxyl group, etc.) in the above-mentioned cyclic olefin resins (1) to (3).
  • a polar group for example, a carboxyl group, an acid anhydride group, an epoxy group, an amide group, an ester group, a hydroxyl group, etc.
  • What (4) which grafted and / or copolymerized the unsaturated compound (u) which has can be included. Two or more of the above cyclic olefin resins (1) to (4) may be used in combination.
  • Examples of the unsaturated compound (u) include (meth) acrylic acid, maleic acid, maleic anhydride, itaconic anhydride, glycidyl (meth) acrylate, alkyl (meth) acrylate (carbon number 1 to 10) ester, maleic acid Examples include alkyl (having 1 to 10 carbon atoms) ester, (meth) acrylamide, (2-hydroxyethyl) (meth) acrylate, and the like.
  • Affinity with metals and polar resins can be increased by using a modified cyclic olefin resin (4) obtained by grafting and / or copolymerizing an unsaturated compound (u) having a polar group, so vapor deposition, sputtering, coating It is possible to increase the strength of various secondary processing such as adhesion, and is suitable when secondary processing is required.
  • the presence of the polar group has a drawback of increasing the water absorption rate of the cyclic olefin resin.
  • the content of polar groups is preferably 0 to 1 mol / kg per 1 kg of cyclic olefin resin.
  • the styrene-based elastomer has a melt flow rate of 4.5 g / 10 min or less measured under conditions of 230 ° C. and 2.16 kgf in accordance with ISO 1133. If the melt flow rate is large and the molecular weight is too small, the elastomer itself is likely to undergo a phase change under environmental preservation, a gap is formed between the elastomer / cyclic olefin, and the refractive index of the elastomer itself changes, resulting in the entire film Will greatly change the haze.
  • the melt flow rate of the styrene elastomer is preferably 0.5 g / 10 min or more, and more preferably 1.0 g / 10 min or more.
  • the melt flow rate is small and the molecular weight is too large, the thermal shrinkage of the elastomer itself becomes large under environmental preservation, and as a result, the haze of the entire film is greatly changed.
  • the molecular weight of the styrene elastomer is 5,000 to 300,000, preferably 10,000 to 150,000, more preferably 20,000 to 100,000, as determined by the GPC method. If the number average molecular weight is too low, the mechanical strength decreases, and if it is too high, the moldability deteriorates.
  • the styrene-based elastomer is a copolymer of styrene and a conjugated diene such as butadiene or isoprene and / or a hydrogenated product thereof.
  • the styrene elastomer is a block copolymer having styrene as a hard segment and conjugated diene as a soft segment, and does not require a vulcanization step and is preferably used.
  • the hydrogenated one is more preferable because it has higher thermal stability.
  • styrenic elastomers examples include styrene / butadiene / styrene block copolymers, styrene / isoprene / styrene block copolymers, styrene / ethylene / butylene / styrene block copolymers, and styrene / ethylene / propylene / styrene block copolymers. Examples thereof include styrene and butadiene block copolymers.
  • styrene / ethylene / butylene / styrene block copolymer styrene / ethylene / propylene / styrene block copolymer, styrene / butadiene block copolymer (hydrogenation) in which double bond of conjugated diene component is eliminated by hydrogenation May also be used.
  • the structure of the styrene-based elastomer is not particularly limited, and may be chain-like, branched or cross-linked, but is preferably linear.
  • At least one styrene selected from the group consisting of styrene / ethylene / butylene / styrene block copolymers, styrene / ethylene / propylene / styrene block copolymers, and hydrogenated styrene / butadiene block copolymers.
  • Based elastomers are preferably used.
  • hydrogenated styrene / butadiene block copolymers are more preferably used because of high tear strength and small haze increase after environmental preservation.
  • the ratio of butadiene to styrene in the hydrogenated styrene / butadiene block copolymer is preferably in the range of 10 to 90% so as not to impair the compatibility with the cyclic olefin resin.
  • various compounding agents may be added to the cyclic olefin-based resin composition as necessary as long as the characteristics are not impaired.
  • the various compounding agents are not particularly limited as long as they are usually used in thermoplastic resin materials.
  • antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, lubricants, antistatic agents, difficulty Examples include flame retardants, colorants such as dyes and pigments, near infrared absorbers, compounding agents such as fluorescent brighteners, and fillers.
  • the tear strength can be 60 N / mm or more, preferably 100 N / mm or more, and more preferably 120 N / mm or more.
  • the haze increase after the environmental preservation test can be made 2.0% or less, preferably 1.0% or less. If the tear strength is too smaller than the above range, the film is liable to break during production or use, which is inappropriate. On the other hand, if the change in haze is too worse than the above range, the characteristics will deviate from the initial characteristics in use, and the originally intended characteristics are not satisfied.
  • the production method of the cyclic olefin-based resin composition film according to the present embodiment is based on the cyclic olefin-based resin and ISO 1133, and the melt flow rate measured under the conditions of 230 ° C. and 2.16 kgf is 4.5 g / A styrene elastomer that is 10 min or less is melted at a temperature in the range of 210 ° C. to 300 ° C., and the molten cyclic olefin resin composition is extruded into a film by an extrusion method.
  • a cyclic olefin-based resin composition film having a short axis dispersion diameter of styrene-based elastomer of 2 ⁇ m or less is obtained.
  • the cyclic olefin-based resin composition film may be non-stretched, uniaxially stretched, or biaxially stretched.
  • FIG. 3 is a schematic diagram showing a configuration example of a film manufacturing apparatus.
  • the film manufacturing apparatus includes a die 21 and a roll 22.
  • the die 21 is a die for melt molding, and extrudes the molten resin material 23 into a film shape.
  • the resin material 23 contains the above-mentioned cyclic olefin resin composition, for example.
  • the roll 22 has a role of transporting the resin material 23 extruded from the die 21 into a film shape. Further, the roll 22 has a medium flow path therein, and the surface can be adjusted to an arbitrary temperature by an individual temperature control device.
  • the material of the surface of the roll 22 is not specifically limited, A metal rubber, resin, an elastomer, etc. can be used.
  • a cyclic olefin resin composition containing the above-mentioned cyclic olefin resin and a styrene elastomer is melt-mixed at a temperature in the range of 210 ° C to 300 ° C. As the melting temperature is higher, the minor axis dispersion diameter tends to be smaller.
  • the cyclic olefin-based resin composition film according to the present embodiment can be used for various optical applications, for example, a retardation film, a polarizing plate protective film, a light diffusion plate, etc., particularly a prism sheet and a liquid crystal cell substrate.
  • a retardation film for example, a retardation film, a polarizing plate protective film, a light diffusion plate, etc., particularly a prism sheet and a liquid crystal cell substrate.
  • FIGS. 4A and 4B are cross-sectional views showing an example of a transparent conductive film.
  • This transparent conductive film (transparent conductive element) is constituted by using the above-mentioned cyclic olefin-based resin composition film as a base film (base material).
  • this transparent conductive film includes a retardation film 31 as a base film (base material), and a transparent conductive layer 33 on at least one surface of the retardation film 31.
  • 4A is an example in which the transparent conductive layer 33 is provided on one surface of the retardation film 31
  • FIG. 4B is an example in which the transparent conductive layer 33 is provided on both surfaces of the retardation film 31.
  • a hard coat layer 32 may be further provided between the retardation film 31 and the transparent conductive layer 33.
  • the material of the transparent conductive layer 33 for example, one or more selected from the group consisting of electrically conductive metal oxide materials, metal materials, carbon materials, and conductive polymers can be used.
  • metal oxide materials include indium tin oxide (ITO) zinc oxide, indium oxide, antimony-added tin oxide, fluorine-added tin oxide, aluminum-added zinc oxide, gallium-added zinc oxide, silicon-added zinc oxide, and zinc oxide- Examples thereof include a tin oxide system, an indium oxide-tin oxide system, and a zinc oxide-indium oxide-magnesium oxide system.
  • metal material for example, metal nanofillers such as metal nanoparticles and metal nanowires can be used.
  • these materials include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, titanium, bismuth, Examples thereof include metals such as antimony and lead, and alloys thereof.
  • the carbon material include carbon black, carbon fiber, fullerene, graphene, carbon nanotube, carbon microcoil, and nanohorn.
  • the conductive polymer for example, substituted or unsubstituted polyaniline, polypyrrole, polythiofin, and one or two (co) polymers selected from these can be used.
  • the transparent conductive layer 33 may be a transparent electrode having a predetermined electrode pattern. Examples of the electrode pattern include a stripe shape, but are not limited thereto.
  • a photosensitive resin for example, acrylate resins such as urethane acrylate, epoxy acrylate, polyester acrylate, polyol acrylate, polyether acrylate, and melamine acrylate can be used.
  • the urethane acrylate resin is obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer, and reacting an acrylate or methacrylate monomer having a hydroxyl group with the obtained product.
  • the thickness of the hard coat layer 32 is preferably 1 ⁇ m to 20 ⁇ m, but is not particularly limited to this range.
  • the transparent conductive film has a moth-eye structure 34 as an antireflection layer on at least one surface of the retardation film.
  • a moth-eye-shaped structure 34 is provided on one surface of the retardation film 31
  • FIG. 4D is an example in which a moth-eye-shaped structure is provided on both surfaces of the retardation film.
  • the antireflection layer provided on the surface of the retardation film 11 is not limited to the moth-eye structure described above, and a conventionally known antireflection layer such as a low refractive index layer can also be used. .
  • FIG. 5 is a schematic cross-sectional view showing one configuration example of the touch panel.
  • the touch panel (input device) 40 is a so-called resistive film type touch panel.
  • the resistive film type touch panel may be either an analog resistive film type touch panel or a digital resistive film type touch panel.
  • the touch panel 40 includes a first transparent conductive film 41 and a second transparent conductive film 42 facing the first transparent conductive film 41.
  • the 1st transparent conductive film 41 and the 2nd transparent conductive film 42 are bonded together via the bonding part 45 between those peripheral parts.
  • As the bonding part 45 for example, an adhesive paste, an adhesive tape or the like is used.
  • the touch panel 40 is bonded to the display device 44 through the bonding layer 43, for example.
  • a material of the bonding layer 43 for example, an acrylic, rubber, or silicon adhesive can be used, and an acrylic adhesive is preferable from the viewpoint of transparency.
  • the touch panel 40 further includes a polarizer 48 bonded to the surface on the touch side of the first transparent conductive film 41 via a bonding layer 50 or the like.
  • a polarizer 48 bonded to the surface on the touch side of the first transparent conductive film 41 via a bonding layer 50 or the like.
  • the 1st transparent conductive film 41 and / or the 2nd transparent conductive film 42 the above-mentioned transparent conductive film can be used.
  • the retardation film as the base film (base material) is set to ⁇ / 4.
  • the touch panel 40 is preferably provided with a moth-eye-shaped structure 34 on the opposing surfaces of the first transparent conductive film 41 and the second transparent conductive film 42, that is, on the surface of the transparent conductive layer 33.
  • the optical characteristics for example, a reflection characteristic, a transmission characteristic, etc.
  • the touch panel 40 preferably further includes a single-layer or multi-layer antireflection layer on the surface of the first transparent conductive film 41 on the touch side. Thereby, a reflectance can be reduced and visibility can be improved.
  • the touch panel 40 further includes a hard coat layer on the surface on the touch side of the first transparent conductive film 41 from the viewpoint of improving the scratch resistance.
  • the surface of the hard coat layer is preferably imparted with antifouling properties.
  • the touch panel 40 further includes a front panel (surface member) 49 bonded to the surface on the touch side of the first transparent conductive film 41 via the bonding layer 51. Moreover, it is preferable that the touch panel 40 further includes a glass substrate 46 bonded to the surface of the second transparent conductive film 42 bonded to the display device 44 via a bonding layer 47.
  • the touch panel 40 preferably further includes a plurality of structures on the surface to be bonded to the display device 44 of the second transparent conductive film 42 or the like.
  • the adhesion between the touch panel 40 and the bonding layer 43 can be improved by the anchor effect of the plurality of structures.
  • a moth-eye structure is preferable. Thereby, interface reflection can be suppressed.
  • a liquid crystal display for example, a CRT (Cathode Ray Tube) display, a plasma display (Plasma Display Panel: PDP), an electroluminescence (Electro Luminescence: EL) display, a surface conduction electron-emitting device display (Surface-conduction Various display devices such as Electron-emitter Display (SED) can be used.
  • a CRT Cathode Ray Tube
  • a plasma display Plasma Display Panel: PDP
  • an electroluminescence (Electro Luminescence: EL) display for example, a liquid crystal display, a CRT (Cathode Ray Tube) display, a plasma display (Plasma Display Panel: PDP), an electroluminescence (Electro Luminescence: EL) display, a surface conduction electron-emitting device display (Surface-conduction
  • SED Electron-emitter Display
  • FIG. 6 is an external view illustrating an example of a television device as an electronic apparatus.
  • the television device 100 includes a display unit 101, and the display unit 101 includes a touch panel 40.
  • FIG. 7A and 7B are external views showing examples of a digital camera as an electronic device.
  • 7A is an external view of the digital camera viewed from the front side
  • FIG. 7B is an external view of the digital camera viewed from the back side.
  • the digital camera 110 includes a light emitting unit 111 for flash, a display unit 112, a menu switch 113, a shutter button 114, and the like
  • the display unit 112 includes the touch panel 40 described above.
  • FIG. 8 is an external view showing an example of a notebook personal computer as an electronic device.
  • the notebook personal computer 120 includes a main body 121 including a keyboard 122 for inputting characters, a display unit 123 for displaying images, and the like, and the display unit 123 includes the touch panel 40 described above.
  • FIG. 9 is an external view showing an example of a video camera as an electronic device.
  • the video camera 130 includes a main body 131, a subject shooting lens 132 on the side facing forward, a start / stop switch 133 during shooting, a display unit 134, and the like, and the display unit 134 includes the touch panel 40 described above.
  • FIG. 10 is an external view showing an example of a mobile phone as an electronic device.
  • the mobile phone 140 is a so-called smartphone, and the display unit 141 includes the touch panel 40 described above.
  • FIG. 11 is an external view showing an example of a tablet computer as an electronic device.
  • the tablet computer 150 includes the touch panel 40 described above on the display unit 151.
  • Example> Examples of the present invention will be described in detail below.
  • a cyclic olefin-based resin composition film having a short axis dispersion diameter of a styrene-based elastomer was prepared, and tear strength, initial haze, and haze increase were evaluated.
  • the present invention is not limited to these examples.
  • the short axis dispersion diameter, tear strength, haze, and haze increase were measured as follows.
  • the TD (Transverse Direction) -thickness (Z-axis) section of the cyclic olefin-based resin composition film was cut with a microtome, and the film section was magnified and observed about 2500 times with an optical microscope.
  • the short axis of the styrene elastomer in the range of 20 ⁇ m ⁇ 20 ⁇ m in the center of the cross section was measured, and the average value was defined as the short axis dispersion diameter.
  • the styrene elastomer with a small dispersion diameter is subjected to osmium staining and then sliced with a microtome, and the cross section is magnified and observed at a magnification of about 5000 times with a transmission electron microscope.
  • the minor axis of the styrene elastomer in the range of ⁇ 5 ⁇ m was measured, and the average value was defined as the minor axis dispersion diameter.
  • Tear strength (right-angle tear) A film having a thickness of 80 ⁇ m was measured according to JISK7128. A No. 3 type test piece was used as a test piece, measured at a test speed of 200 mm / min using a tensile tester (AG-X, manufactured by Shimadzu Corporation), and the average value in the MD and TD directions was determined as the tear strength. did. A tear strength of 60 N / mm or more was evaluated as “ ⁇ ”, and a tear strength of less than 60 N / mm was evaluated as “x”. If the tear strength is 60 N / mm or more, practical use is possible in that the risk of breakage in a subsequent process such as a coating process is reduced.
  • cyclic olefin resin and styrene elastomer As the cyclic olefin resin, TOPAS 6013-S04 (manufactured by Polyplastics Co., Ltd., chemical name: addition copolymer of ethylene and norbornene) was used.
  • Tuftec H1051 (Asahi Kasei Chemicals Corporation) is a styrene / ethylene / butylene / styrene block copolymer having a melt flow rate (230 ° C., 2.16 kgf) measured in accordance with ISO 1133 of 0.8 g / 10 min. It is a coalescence. S. O.
  • E S1605 (manufactured by Asahi Kasei Chemicals Corporation) is a hydrogenated styrene / butadiene block copolymer having a melt flow rate (230 ° C., 2.16 kgf) measured in accordance with ISO 1133 of 3.5 g / 10 min. is there.
  • Tuftec H1221 (manufactured by Asahi Kasei Chemicals Corporation) is a styrene / ethylene / butylene / styrene block copolymer having a melt flow rate (230 ° C., 2.16 kgf) measured according to ISO 1133 of 4.5 g / 10 min. It is a coalescence.
  • Tuftec H1517 (Asahi Kasei Chemicals Co., Ltd.) is a styrene / ethylene / butylene / styrene block copolymer having a melt flow rate (230 ° C., 2.16 kgf) measured in accordance with ISO 1133 of 5.0 g / 10 min. It is a coalescence.
  • S. O. E L606 (manufactured by Asahi Kasei Chemicals Corporation) is a hydrogenated styrene / butadiene block copolymer having a melt flow rate (230 ° C., 2.16 kgf) measured according to ISO 1133 of 2.9 g / 10 min. is there.
  • Tuftec H1052 (manufactured by Asahi Kasei Chemicals Corporation) is a styrene / ethylene / butylene / styrene block copolymer having a melt flow rate (230 ° C., 2.16 kgf) measured in accordance with ISO 1133 of 13.0 g / 10 min. It is a coalescence.
  • Example 1 90 parts by weight of cyclic olefin-based resin and 10 parts by weight of Tuftec H1051 as styrene-based elastomer, with a T-die attached to the tip (specifications: 25 mm diameter, length: 26D, T-die width) : 160 mm) at a predetermined temperature in the temperature range of 210 ° C. to 300 ° C., the cyclic olefin resin composition is extruded at a speed of 250 g / min, and a film having a thickness of 80 ⁇ m is wound around a roll. It was.
  • the short axis dispersion diameter of the styrene elastomer was 0.7 ⁇ m.
  • the tear strength was 73 N / mm, which was evaluated as “good”.
  • the initial haze was 2.4%, and the increase in haze after environmental preservation was 0.8%, which was evaluated as ⁇ .
  • Example 2 90 parts by mass of a cyclic olefin-based resin and S.I. O. A film was produced in the same manner as in Example 1 except that 10 parts by mass of ES1605 was blended and kneaded at a predetermined temperature in the temperature range of 210 ° C. to 300 ° C. using a twin screw extruder.
  • the short axis dispersion diameter of the styrene elastomer was 2.0 ⁇ m.
  • tearing strength was evaluation of (circle) in 90 N / mm.
  • the initial haze was 2.9%, and the increase in haze after environmental preservation was 1.4%, which was evaluated as ⁇ .
  • Example 3 Example 1 except that 90 parts by mass of a cyclic olefin resin and 10 parts by mass of Tuftec H1221 as a styrene elastomer were blended and kneaded at a predetermined temperature in the temperature range of 210 ° C. to 300 ° C. using a twin screw extruder. A film was prepared in the same manner as described above.
  • the short axis dispersion diameter of the styrene elastomer was 0.9 ⁇ m.
  • tearing strength was evaluation of (circle) in 78 N / mm.
  • the initial haze was 8.2%, and the increase in haze after environmental preservation was 0.9%, which was evaluated as ⁇ .
  • Example 4 90 parts by mass of a cyclic olefin-based resin and S.I. O. A film was produced in the same manner as in Example 1 except that 10 parts by mass of E L606 was blended and kneaded at a predetermined temperature in the temperature range of 210 ° C. to 300 ° C. using a twin screw extruder.
  • the short axis dispersion diameter of the styrene elastomer was 0.1 ⁇ m.
  • the tear strength was 102 N / mm, which was a good evaluation.
  • the initial haze was 0.4%, and the increase in haze after environmental preservation was 1.1%, which was evaluated as ⁇ .
  • Example 5 Example 1 except that 90 parts by mass of a cyclic olefin resin and 10 parts by mass of Tuftec H1051 as a styrene elastomer were blended and kneaded at a predetermined temperature in the temperature range of 210 ° C. to 300 ° C. using a twin screw extruder. A film was prepared in the same manner as described above.
  • the short axis dispersion diameter of the styrene elastomer was 2.0 ⁇ m.
  • tearing strength was evaluation of (circle) in 82 N / mm.
  • the initial haze was 3.5%, and the increase in haze after environmental preservation was 1.9%, which was evaluated as ⁇ .
  • Example 6 Example 1 except that 95 parts by mass of a cyclic olefin resin and 5 parts by mass of Tuftec H1051 as a styrene elastomer were blended and kneaded at a predetermined temperature in the temperature range of 210 ° C. to 300 ° C. using a twin screw extruder. A film was prepared in the same manner as described above.
  • the short axis dispersion diameter of the styrene elastomer was 0.2 ⁇ m.
  • tearing strength was evaluation of (circle) in 60 N / mm.
  • the initial haze was 1.3%, and the increase in haze after environmental preservation was 0.5%, which was evaluated as ⁇ .
  • Example 7 Example 1 except that 65 parts by mass of a cyclic olefin resin and 35 parts by mass of Tuftec H1051 as a styrene elastomer were blended and kneaded at a predetermined temperature in the temperature range of 210 ° C. to 300 ° C. using a twin screw extruder. A film was prepared in the same manner as described above.
  • the short axis dispersion diameter of the styrene elastomer was 0.4 ⁇ m.
  • tearing strength was evaluation of (circle) in 120 N / mm.
  • the initial haze was 8.1%, and the increase in haze after environmental preservation was 1.9%, which was evaluated as ⁇ .
  • Example 1 A film was prepared in the same manner as in Example 1 except that 100 parts by mass of the cyclic olefin resin without blending with the styrene elastomer was kneaded at a predetermined temperature in the temperature range of 210 ° C. to 300 ° C. using a twin screw extruder. Produced.
  • the tear strength was 57 N / mm and was evaluated as x.
  • the initial haze was 0.3%, and the increase in haze after environmental preservation was 0.3%, which was evaluated as ⁇ .
  • Example 2 Example 1 except that 90 parts by mass of a cyclic olefin resin and 10 parts by mass of Tuftec H1051 as a styrene elastomer were blended and kneaded at a predetermined temperature in the temperature range of 210 ° C. to 300 ° C. using a twin screw extruder. A film was prepared in the same manner as described above.
  • the short axis dispersion diameter of the styrene elastomer was 2.2 ⁇ m. Further, the tear strength was 79 N / mm, which was a good evaluation. The initial haze was 4.2%, and the increase in haze after environmental preservation was 2.7%, which was evaluated as x.
  • Example 1 except that 97 parts by mass of a cyclic olefin resin and 3 parts by mass of Tuftec H1051 as a styrene elastomer were blended and kneaded at a predetermined temperature in the temperature range of 210 ° C. to 300 ° C. using a twin screw extruder. A film was prepared in the same manner as described above.
  • the short axis dispersion diameter of the styrene elastomer was 0.4 ⁇ m.
  • the tear strength was 57 N / mm and was evaluated as x.
  • the initial haze was 1.0%, and the increase in haze after environmental preservation was 0.5%, which was evaluated as ⁇ .
  • Example 1 except that 60 parts by mass of a cyclic olefin resin and 40 parts by mass of Tuftec H1051 as a styrene elastomer were blended and kneaded at a predetermined temperature in the temperature range of 210 ° C. to 300 ° C. using a twin screw extruder. A film was prepared in the same manner as described above.
  • the short axis dispersion diameter of the styrene elastomer was 1.2 ⁇ m.
  • tearing strength was evaluation of (circle) in 131 N / mm.
  • the initial haze was 9.9%, and the increase in haze after environmental preservation was 2.8%, which was evaluated as x.
  • Example 1 except that 90 parts by mass of a cyclic olefin resin and 10 parts by mass of Tuftec H1517 as a styrene elastomer were blended and kneaded at a predetermined temperature in the temperature range of 210 ° C. to 300 ° C. using a twin screw extruder. A film was prepared in the same manner as described above.
  • the short axis dispersion diameter of the styrene elastomer was 1.8 ⁇ m.
  • tearing strength was evaluation of (circle) in 62 N / mm.
  • the initial haze was 1.4%, and the increase in haze after environmental preservation was evaluated as x at 2.2%.
  • Example 1 except that 90 parts by mass of a cyclic olefin resin and 10 parts by mass of Tuftec H1052 as a styrene elastomer were blended and kneaded at a predetermined temperature in the temperature range of 210 ° C. to 300 ° C. using a twin screw extruder. A film was prepared in the same manner as described above.
  • the short axis dispersion diameter of the styrene elastomer was 0.5 ⁇ m. Further, the tear strength was 77 N / mm, which was evaluated as o. The initial haze was 10.1%, and the increase in haze after environmental preservation was evaluated as x at 2.5%.
  • Comparative Example 1 In Comparative Example 1 in which no styrene-based elastomer was added and Comparative Example 3 in which the addition amount was small, the tear strength was less than 60 N / mm and it was easy to break. Moreover, about the comparative example 2 with a large dispersion diameter, and the comparative example 4 with many addition amounts, the haze raise after environmental preservation was larger than 2%. Also in Comparative Examples 5 and 6 in which the MFR of the styrene elastomer was 5.0 g / 10 min or more, the increase in haze after environmental preservation was larger than 2%.
  • a cyclic olefin resin in which 5-35 wt% of a styrene elastomer having an MFR of 4.5 g / 10 min or less was added and the minor axis dispersion diameter of the styrene elastomer was 2 ⁇ m or less.
  • the composition films had good haze increases after environmental preservation of 2% or less and all tear strengths of 60 N / mm or more.
  • Example 1 Example 5 and Comparative Example 2
  • No. 1 was particularly good with a haze increase of less than 1%.
  • Example 2 having an MFR of 1.0 g / 10 min or more was particularly good with a haze increase of less than 1.5%.
  • Example 2 and Example 4 in which the styrene elastomer is a hydrogenated styrene / butadiene block copolymer are different from the other examples in which the styrene elastomer is a styrene / ethylene / butylene / styrene block copolymer. It was found that the tear strength tends to be high.

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Abstract

Cette invention concerne un film à base d'une composition de résine cyclo-oléfinique qui manifeste une excellente stabilité en stockage vis-à-vis d'altérations de l'environnement et une excellente ténacité. Le film selon l'invention comprend à la fois une résine cyclo-oléfinique (11) et un élastomère à base de styrène (12) qui manifeste un indice de fluidité à chaud, déterminé selon la norme ISO 1133 à 230ºC sous une charge de 2,16kgf, de 4,5 g/10 min ou moins. L'élastomère à base de styrène (12) est dispersé dans la résine cyclo-oléfinique (11), la teneur en élastomère (12) étant de 5 à 35 % en poids, et les diamètres des petits axes des particules dispersées de l'élastomère à base de styrène (12) étant de 2 µm ou moins. Ainsi, une excellente stabilité en stockage vis-à-vis d'altérations de l'environnement et une excellente ténacité peuvent être obtenues.
PCT/JP2014/081279 2013-11-26 2014-11-26 Film à base d'une composition de résine cyclo-oléfinique Ceased WO2015080167A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016006683A1 (fr) * 2014-07-11 2016-01-14 デクセリアルズ株式会社 Film de composition de résine à base d'oléfine cyclique
WO2016010019A1 (fr) * 2014-07-15 2016-01-21 デクセリアルズ株式会社 Film de composition de résine d'oléfine cylique
WO2016153038A1 (fr) * 2015-03-26 2016-09-29 デクセリアルズ株式会社 Film à base d'une composition de résine d'oléfine cyclique
WO2017085809A1 (fr) * 2015-11-18 2017-05-26 デクセリアルズ株式会社 Film de composition de résine à base d'oléfine cyclique
JP2017122146A (ja) * 2016-01-05 2017-07-13 デクセリアルズ株式会社 環状オレフィン系樹脂組成物フィルム
WO2019163637A1 (fr) * 2018-02-21 2019-08-29 富士フイルム株式会社 Procédé de production de film de résine d'oléfine cyclique, film de résine d'oléfine cyclique et film composite

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6699133B2 (ja) * 2015-10-30 2020-05-27 コニカミノルタ株式会社 光学フィルム及びその製造方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07238190A (ja) * 1994-03-01 1995-09-12 Sumitomo Bakelite Co Ltd 熱可塑性樹脂組成物
JPH07258504A (ja) * 1994-03-18 1995-10-09 Sumitomo Bakelite Co Ltd 透明高防湿薬品包装用ポリマーアロイシート
JPH09268250A (ja) * 1996-03-29 1997-10-14 Nippon Zeon Co Ltd 熱可塑性ノルボルネン系樹脂組成物
JPH1121413A (ja) * 1997-07-02 1999-01-26 Kanegafuchi Chem Ind Co Ltd シクロオレフィン系共重合体樹脂組成物及びその製造方法
JP2000511582A (ja) * 1996-06-06 2000-09-05 ヘキスト・セラニーズ・コーポレーション 改良された耐衝撃性と優れた透明性を示す環状オレフィンポリマー配合物
JP2004156048A (ja) * 2004-02-09 2004-06-03 Polyplastics Co 環状オレフィン系樹脂組成物フィルム
WO2013179781A1 (fr) * 2012-05-29 2013-12-05 ポリプラスチックス株式会社 Composition de résine d'oléfine cyclique et corps moulé à base de résine
WO2014034200A1 (fr) * 2012-08-31 2014-03-06 ポリプラスチックス株式会社 Film transparent

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009003439A (ja) * 2007-05-23 2009-01-08 Daicel Chem Ind Ltd 光学フィルム
JP2011202085A (ja) * 2010-03-26 2011-10-13 Kaneka Corp シクロオレフィン系共重合体樹脂組成物
JP5805951B2 (ja) * 2010-07-16 2015-11-10 三菱樹脂株式会社 反射材
JP5809276B2 (ja) * 2011-08-30 2015-11-10 株式会社カネカ シクロオレフィン系共重合体樹脂組成物

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07238190A (ja) * 1994-03-01 1995-09-12 Sumitomo Bakelite Co Ltd 熱可塑性樹脂組成物
JPH07258504A (ja) * 1994-03-18 1995-10-09 Sumitomo Bakelite Co Ltd 透明高防湿薬品包装用ポリマーアロイシート
JPH09268250A (ja) * 1996-03-29 1997-10-14 Nippon Zeon Co Ltd 熱可塑性ノルボルネン系樹脂組成物
JP2000511582A (ja) * 1996-06-06 2000-09-05 ヘキスト・セラニーズ・コーポレーション 改良された耐衝撃性と優れた透明性を示す環状オレフィンポリマー配合物
JPH1121413A (ja) * 1997-07-02 1999-01-26 Kanegafuchi Chem Ind Co Ltd シクロオレフィン系共重合体樹脂組成物及びその製造方法
JP2004156048A (ja) * 2004-02-09 2004-06-03 Polyplastics Co 環状オレフィン系樹脂組成物フィルム
WO2013179781A1 (fr) * 2012-05-29 2013-12-05 ポリプラスチックス株式会社 Composition de résine d'oléfine cyclique et corps moulé à base de résine
WO2014034200A1 (fr) * 2012-08-31 2014-03-06 ポリプラスチックス株式会社 Film transparent

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016006683A1 (fr) * 2014-07-11 2016-01-14 デクセリアルズ株式会社 Film de composition de résine à base d'oléfine cyclique
JP2016020412A (ja) * 2014-07-11 2016-02-04 デクセリアルズ株式会社 環状オレフィン系樹脂組成物フィルム
WO2016010019A1 (fr) * 2014-07-15 2016-01-21 デクセリアルズ株式会社 Film de composition de résine d'oléfine cylique
JP2016020458A (ja) * 2014-07-15 2016-02-04 デクセリアルズ株式会社 環状オレフィン系樹脂組成物フィルム
WO2016153038A1 (fr) * 2015-03-26 2016-09-29 デクセリアルズ株式会社 Film à base d'une composition de résine d'oléfine cyclique
WO2017085809A1 (fr) * 2015-11-18 2017-05-26 デクセリアルズ株式会社 Film de composition de résine à base d'oléfine cyclique
JP2017122146A (ja) * 2016-01-05 2017-07-13 デクセリアルズ株式会社 環状オレフィン系樹脂組成物フィルム
WO2019163637A1 (fr) * 2018-02-21 2019-08-29 富士フイルム株式会社 Procédé de production de film de résine d'oléfine cyclique, film de résine d'oléfine cyclique et film composite

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