WO2015198686A1 - Film à base d'une composition de résine oléfinique cyclique - Google Patents

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

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Publication number
WO2015198686A1
WO2015198686A1 PCT/JP2015/061192 JP2015061192W WO2015198686A1 WO 2015198686 A1 WO2015198686 A1 WO 2015198686A1 JP 2015061192 W JP2015061192 W JP 2015061192W WO 2015198686 A1 WO2015198686 A1 WO 2015198686A1
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cyclic olefin
resin composition
styrene
film
olefin resin
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PCT/JP2015/061192
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English (en)
Japanese (ja)
Inventor
慶 小幡
堀井　明宏
健 細谷
石森　拓
一樹 平田
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デクセリアルズ株式会社
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers

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 cyclic olefin-based resin film in which the elastomer is added and dispersed tends to increase the retardation in the in-plane direction, and is difficult to apply as a base material of a polarizing plate, for example.
  • the present invention has been proposed in view of such a conventional situation, and provides a cyclic olefin-based resin composition film having excellent in-plane retardation.
  • the present inventor added a styrene-based elastomer having a value obtained by dividing a melt flow rate measured under conditions of 230 ° C. and 2.16 kgf by an ethylene unit amount to a predetermined value or more in accordance with ISO 1133 to a cyclic olefin-based resin. As a result, it has been found that toughness can be improved and retardation in the in-plane direction can be improved, and the present invention has been completed.
  • the cyclic olefin-based resin composition film according to the present invention has a cyclic olefin-based resin and a value obtained by dividing the melt flow rate measured under the conditions of 230 ° C. and 2.16 kgf by the amount of ethylene units in accordance with ISO 1133. It is characterized by containing 0.18 g / (10 min ⁇ mol%) or more of a styrenic elastomer.
  • the manufacturing method of the cyclic olefin resin composition film according to the present invention is obtained by dividing the melt flow rate measured under the conditions of 230 ° C. and 2.16 kgf by the amount of ethylene units in accordance with ISO 1133 and the cyclic olefin resin.
  • a styrene elastomer having a measured value of 0.18 g / (10 min ⁇ mol%) or more is heated and melted, and the heated and melted cyclic olefin resin composition is extruded into a film by an extrusion method to obtain a cyclic olefin resin.
  • a composition film 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.
  • a styrene-based elastomer having a value obtained by dividing the melt flow rate measured under the conditions of 230 ° C. and 2.16 kgf by the amount of ethylene units in accordance with ISO 1133 is not less than a predetermined value.
  • 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 schematic diagram illustrating a configuration example of a film manufacturing apparatus.
  • 3A and 3B are cross-sectional views illustrating an example of a transparent conductive film
  • FIGS. 3C and 3D are cross-sectional views illustrating an example of a transparent conductive film provided with a moth-eye-shaped structure.
  • FIG. 4 is a schematic cross-sectional view showing a configuration example of the touch panel.
  • FIG. 5 is an external view illustrating an example of a television device as an electronic apparatus.
  • 6A and 6B are external views illustrating examples of a digital camera as an electronic device.
  • FIG. 7 is an external view illustrating an example of a notebook personal computer as an electronic device.
  • FIG. 8 is an external view illustrating an example of a video camera as an electronic device.
  • FIG. 9 is an external view illustrating an example of a mobile phone as an electronic device.
  • FIG. 10 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 olefin-based resin and a value obtained by dividing the melt flow rate measured under the conditions of 230 ° C. and 2.16 kgf by the amount of ethylene units in accordance with ISO 1133. And a styrene elastomer that is 0.18 g / (10 min ⁇ mol%) or more.
  • the melt flow rate When the melt flow rate is small, the flow during melting is small and the stress tends to accumulate inside, resulting in a large in-plane retardation.
  • the amount of ethylene units when the amount of ethylene units is large, the interaction including the cyclic olefin resin and steric hindrance increases, and stress is easily generated, resulting in an increase in retardation in the in-plane direction. Therefore, when the melt flow rate is large and the ethylene unit amount is small, a low retardation film can be obtained. That is, when the value obtained by dividing the melt flow rate by the ethylene unit amount is a predetermined value or more, an increase in retardation in the in-plane direction can be suppressed.
  • 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 resin composition film contains a cyclic olefin resin 11 and a styrene elastomer 12.
  • 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.
  • 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 preferably 2.0 ⁇ m or less, and more preferably 1.0 ⁇ 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. Then, the cross section of the film is magnified, the short axis of each dispersed phase in the predetermined range at the center of the cross section of the film is measured, and the average value is defined as the short axis dispersion diameter. Moreover, when a dispersion diameter is small, it is preferable to cut
  • the addition amount of the styrene-based elastomer is preferably less than 40 wt%, and more preferably 3 wt% or more and 35 wt% or less. If the amount of styrene-based elastomer added is too large, the environmental preservation is reduced, and if it is too small, sufficient toughness cannot be obtained.
  • 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 mol% 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 value obtained by dividing the melt flow rate measured under the conditions of 230 ° C. and 2.16 kgf by the amount of ethylene units in accordance with ISO 1133 is 0.18 g / (10 min ⁇ mol%) or more.
  • the melt flow rate When the melt flow rate is small, the flow during melting is small and the stress tends to accumulate inside, resulting in a large in-plane retardation.
  • the amount of ethylene units when the amount of ethylene units is large, the interaction including the cyclic olefin resin and steric hindrance increases, and stress is easily generated, resulting in an increase in retardation in the in-plane direction. Therefore, when the melt flow rate is large and the ethylene unit amount is small, a low retardation film can be obtained. That is, when the value obtained by dividing the melt flow rate by the ethylene unit amount is a predetermined value or more, an increase in retardation in the in-plane direction can be suppressed.
  • the amount of ethylene units in the styrene-based elastomer is not particularly limited, but is preferably 1 mol% or more and 80 mol% or less, and more preferably 10 mol% or more and 60 mol% or less.
  • the amount of ethylene units in the styrene elastomer can be measured using, for example, H 1 -NMR (nuclear magnetic resonance apparatus).
  • 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.
  • the structure of the soft segment changes the storage elastic modulus of the styrene-based elastomer, and the content of styrene that is the hard segment changes the refractive index and changes the haze of the entire film.
  • the styrene elastomer does not require a vulcanization step and is preferably used. Further, 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 in order to reduce the storage elastic modulus.
  • 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 mol% so as not to impair the compatibility with the cyclic olefin resin.
  • the styrene content of the styrene elastomer is preferably 20 to 40 mol%. By setting the styrene content to 20 to 40 mol%, the haze can be reduced.
  • the molecular weight of the styrene elastomer is 5,000 to 300,000, preferably 10,000 to 150,000, and 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.
  • 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.
  • inorganic oxide fine particles, antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, lubricants examples thereof include antistatic agents, flame retardants, colorants such as dyes and pigments, near infrared absorbers, compounding agents such as fluorescent whitening agents, and fillers.
  • the in-plane retardation R0 can be 10 nm or less, and the tear strength can be 60 N / mm or more.
  • the retardation R0 in the in-plane direction is larger than the above range, it becomes difficult to apply it as a base material for a polarizing plate, for example.
  • the tear strength is smaller than the above range, the film is likely to be broken during production or use.
  • the method for producing a cyclic olefin-based resin composition film according to the present embodiment is obtained by dividing the melt flow rate measured under conditions of 230 ° C. and 2.16 kgf by the amount of ethylene units in accordance with the cyclic olefin-based resin and ISO 1133. Is heated to melt with a styrene elastomer having a value of 0.18 g / (10 min ⁇ mol%) or more, and the heat-melted cyclic olefin resin composition is extruded into a film by an extrusion method to obtain a cyclic olefin resin composition. A product film is obtained.
  • the cyclic olefin-based resin composition film may be non-stretched, uniaxially stretched, or biaxially stretched.
  • FIG. 2 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. The higher the melting temperature, the smaller the short axis dispersion diameter of the styrene elastomer.
  • 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. 3A and 3B 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.
  • FIG. 3A is an example in which the transparent conductive layer 33 is provided on one surface of the retardation film 31
  • FIG. 3B 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.
  • the metal oxide material 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 is provided with a moth-eye structure 34 as an antireflection layer on at least one surface of the above-described retardation film. Also good.
  • FIG. 3C is an example in which a moth-eye structure 34 is provided on one surface of the retardation film 31, and FIG. 3D is an example in which a moth-eye 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. 4 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 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. 5 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. 6A and 6B are external views illustrating examples of a digital camera as an electronic device.
  • 6A is an external view of the digital camera viewed from the front side
  • FIG. 6B 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, and the display unit 112 includes the touch panel 40 described above.
  • FIG. 7 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. 8 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. 9 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. 10 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 was prepared by adding a styrene-based elastomer having a predetermined melt flow rate (MFR) and an ethylene unit to a cyclic olefin-based resin. And the linear thermal expansion coefficient, retardation, and tear strength were evaluated.
  • MFR melt flow rate
  • the present invention is not limited to these examples.
  • the ethylene unit amount of the styrene elastomer, the short axis dispersion diameter, retardation, tear strength, and initial haze of the styrene elastomer of the cyclic olefin resin composition film were measured as follows.
  • the TD (Transverse Direction) -thickness (Z-axis) cross section of the cyclic olefin-based resin composition film was cut with a microtome, and the film cross section was magnified and observed about 2500 times with an optical microscope. And the short axis of the styrene-type elastomer of the range of 20 micrometers x 20 micrometers of the film cross section center was measured, and the average value was made into the short axis dispersion diameter.
  • 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-based resin, TOPAS 6013-S04 (manufactured by Polyplastics Co., Ltd., an addition copolymer of ethylene and norbornene) was used.
  • 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.
  • the measurement result of the amount of ethylene units of Tuftec H1052 was 30 mol%.
  • Tuftec H1041 (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 5.0 g / 10 min. It is a coalescence. Moreover, the measurement result of the amount of ethylene units of Tuftec H1041 (Asahi Kasei Chemicals Corporation) was 28 mol%. 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. . S. O. E.
  • the measurement result of the amount of ethylene units of L606 was 15 mol%.
  • 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. Moreover, the measurement result of the amount of ethylene units of Tuftec H1517 (manufactured by Asahi Kasei Chemicals Corporation) was 55 mol%.
  • Tuftec H1053 (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 ISO1133 of 1.8 g / 10 min. It is a coalescence.
  • the measurement result of the amount of ethylene units of Tuftec H1053 was 30 mol%.
  • Example 1 10 wt. Of Tuftec H1052 (manufactured by Asahi Kasei Chemicals Co., Ltd.) having 90 wt% of cyclic olefin resin and 13 g / 10 min of MFR, 30 mol% of ethylene units and 0.43 of MFR / ethylene units as styrene elastomer. % Blended. This is kneaded at a predetermined temperature in the temperature range of 210 ° C. to 300 ° C.
  • the olefin resin composition was extruded at a speed of 250 g / min, and a film having a thickness of 80 ⁇ m was wound on a roll.
  • the styrene elastomer was dispersed with shape anisotropy in the MD direction of the film, had a major axis in the MD direction, and had a minor axis of about 0.5 ⁇ m on average in the TD direction.
  • the retardation R0 of the film was evaluated as ⁇ at 3 nm, and the tear strength was evaluated as ⁇ at 93 N / mm.
  • Example 2 A cyclic olefin-based resin of 90 wt% and a styrene-based elastomer having an MFR of 2.9 g / 10 min, an ethylene unit amount of 15 mol%, and an MFR / ethylene unit amount of 0.19.
  • E L606 manufactured by Asahi Kasei Chemicals Corporation was blended at 10 wt%. This is kneaded at a predetermined temperature in the temperature range of 210 ° C. to 300 ° C.
  • the olefin resin composition was extruded at a speed of 250 g / min, and a film having a thickness of 80 ⁇ m was wound on a roll.
  • the styrene elastomer was dispersed with shape anisotropy in the MD direction of the film, had a major axis in the MD direction, and a minor axis of about 0.1 ⁇ m on average in the TD direction.
  • the retardation R0 of the film was evaluated as ⁇ at 1 nm, and the tear strength was evaluated as ⁇ at 102 N / mm.
  • Example 3 10 wt. Of Tuftec H1041 (manufactured by Asahi Kasei Chemicals Co., Ltd.) with 90 wt% of cyclic olefin resin and 5 g / 10 min of MFR, 28 mol% of ethylene units and 0.18 of MFR / ethylene units as styrene elastomer. % Blended. This is kneaded at a predetermined temperature in the temperature range of 210 ° C. to 300 ° C.
  • the olefin resin composition was extruded at a speed of 250 g / min, and a film having a thickness of 80 ⁇ m was wound on a roll.
  • the styrene elastomer was dispersed with shape anisotropy in the MD direction of the film, had a major axis in the MD direction, and a minor axis of about 0.8 ⁇ m on average in the TD direction.
  • the retardation R0 of the film was evaluated as ⁇ at 5 nm, and the tear strength was evaluated as ⁇ at 82 N / mm.
  • Example 4 3 wt. Of Tuftec H1052 (manufactured by Asahi Kasei Chemicals Co., Ltd.) having 97 wt% of cyclic olefin resin and 13 g / 10 min of MFR, 30 mol% of ethylene units and 0.43 of MFR / ethylene units as styrene elastomer. % Blended. This is kneaded at a predetermined temperature in the temperature range of 210 ° C. to 300 ° C.
  • the olefin resin composition was extruded at a speed of 250 g / min, and a film having a thickness of 80 ⁇ m was wound on a roll.
  • the styrene elastomer was dispersed with shape anisotropy in the MD direction of the film, had a major axis in the MD direction, and had a minor axis of about 0.5 ⁇ m on average in the TD direction.
  • the retardation R0 of the film was evaluated as ⁇ at 3 nm, and the tear strength was evaluated as ⁇ at 61 N / mm.
  • Example 5 35 wt% of Tuftec H1052 (manufactured by Asahi Kasei Chemicals Corporation) with 65 wt% of cyclic olefin resin and 13 g / 10 min of MFR, 30 mol% of ethylene units and 0.43 of MFR / ethylene units as styrene elastomer. % Blended. This is kneaded at a predetermined temperature in the temperature range of 210 ° C. to 300 ° C.
  • the olefin resin composition was extruded at a speed of 250 g / min, and a film having a thickness of 80 ⁇ m was wound on a roll.
  • the styrene elastomer was dispersed with shape anisotropy in the MD direction of the film, had a major axis in the MD direction, and a minor axis of about 0.8 ⁇ m on average in the TD direction.
  • the retardation R0 of the film was 9 nm and was evaluated as ⁇
  • the tear strength was 132 N / mm and was evaluated as ⁇ .
  • Example 6 2 wt. Of Tuftec H1052 (manufactured by Asahi Kasei Chemicals Corporation) with 98 wt% of cyclic olefin resin and 13 g / 10 min of MFR, 30 mol% of ethylene units and 0.43 of MFR / ethylene units as styrene elastomer. % Blended. This is kneaded at a predetermined temperature in the temperature range of 210 ° C. to 300 ° C.
  • the olefin resin composition was extruded at a speed of 250 g / min, and a film having a thickness of 80 ⁇ m was wound on a roll.
  • the styrene elastomer was dispersed with shape anisotropy in the MD direction of the film, had a major axis in the MD direction, and a minor axis of about 0.8 ⁇ m on average in the TD direction.
  • the film retardation R0 was evaluated as ⁇ at 3 nm, and the tear strength was evaluated as x at 57 N / mm.
  • the cyclic olefin resin was 100 wt%. This is kneaded at a predetermined temperature in the temperature range of 210 ° C. to 300 ° C. using a twin screw extruder (specifications: diameter 25 mm, length: 26 D, T die width: 160 mm) with a T die attached to the tip, and then circular
  • the olefin resin composition was extruded at a speed of 250 g / min, and a film having a thickness of 80 ⁇ m was wound on a roll. As shown in Table 2, the retardation R0 of the film was evaluated as ⁇ at 2 nm, and the tear strength was evaluated as ⁇ at 53 N / mm.
  • the olefin resin composition was extruded at a speed of 250 g / min, and a film having a thickness of 80 ⁇ m was wound on a roll.
  • the styrene elastomer was dispersed with shape anisotropy in the MD direction of the film, had a major axis in the MD direction, and had a minor axis of about 1.8 ⁇ m on average in the TD direction.
  • the retardation R0 of the film was 19 nm and evaluation of x
  • the tear strength was 62 N / mm and evaluation of ⁇ .
  • the olefin resin composition was extruded at a speed of 250 g / min, and a film having a thickness of 80 ⁇ m was wound on a roll.
  • the styrene elastomer was dispersed with shape anisotropy in the MD direction of the film, had a major axis in the MD direction, and had a minor axis of about 0.6 ⁇ m on average in the TD direction.
  • the film retardation R0 was evaluated as x at 12 nm, and the tear strength was evaluated as ⁇ at 70 N / mm.
  • the olefin resin composition was extruded at a speed of 250 g / min, and a film having a thickness of 80 ⁇ m was wound on a roll.
  • the styrene elastomer was dispersed with shape anisotropy in the MD direction of the film, had a major axis in the MD direction, and a minor axis of about 0.8 ⁇ m on average in the TD direction.
  • the retardation R0 of the film was evaluated as x at 11 nm, and the tear strength was evaluated as ⁇ at 138 N / mm.
  • the film containing no styrene-based elastomer had a small tear strength, although the in-plane retardation R0 was small.
  • the value obtained by dividing the melt flow rate measured under the conditions of 230 ° C. and 2.16 kgf according to ISO 1133 by the amount of ethylene units was 0.18 g / (10 min ⁇ mol%).
  • the styrene-based elastomer which is less than the above is compounded, the tear strength is improved, but the in-plane retardation R0 is large.

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Abstract

Cette invention se rapporte à un film à base d'une composition de résine oléfinique cyclique manifestant un excellent retard dans le plan. Le film à base d'une composition de résine oléfinique cyclique comprend une résine oléfinique cyclique (11), et un élastomère de type styrène (12) conforme à la norme ISO 1133 et ayant une valeur d'écoulement à l'état fondu, mesurée dans une condition de 230°C et 2,16 kgf, divisée par la quantité de motifs éthylène qui est de 0,18 g/(10 min·% en mol) ou plus. De ce fait, la résistance à la déchirure peut être améliorée et l'accroissement du retard (R0) dans un sens dans le plan peut être supprimé.
PCT/JP2015/061192 2014-06-25 2015-04-10 Film à base d'une composition de résine oléfinique cyclique WO2015198686A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2020066350A1 (fr) * 2018-09-28 2020-04-02 富士フイルム株式会社 Film de polymère et dispositif d'affichage

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019164678A1 (fr) * 2018-02-21 2019-08-29 3M Innovative Properties Company Filaments à âme-gaine et procédés d'impression d'un adhésif

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JPH06145461A (ja) * 1992-11-13 1994-05-24 Sumitomo Bakelite Co Ltd 熱可塑性樹脂組成物
JPH07238190A (ja) * 1994-03-01 1995-09-12 Sumitomo Bakelite Co Ltd 熱可塑性樹脂組成物
JP2003096168A (ja) * 2001-09-26 2003-04-03 Nippon Zeon Co Ltd ノルボルネン系開環重合体水素添加物の製造方法、その製造方法により得られるノルボルネン系開環重合体水素添加物、及びその水素添加物からなる成形体
WO2004035688A1 (fr) * 2002-10-03 2004-04-29 Sekisui Chemical Co., Ltd. Film de resine a base de norbornene sature thermoplastique et son procede de production
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
JP2007154074A (ja) * 2005-12-06 2007-06-21 Mitsui Chemicals Inc フィルムまたはシート用環状オレフィン系樹脂組成物およびその用途
JP2013018962A (ja) * 2011-06-13 2013-01-31 Polyplastics Co 環状オレフィン系樹脂
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

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06145461A (ja) * 1992-11-13 1994-05-24 Sumitomo Bakelite Co Ltd 熱可塑性樹脂組成物
JPH07238190A (ja) * 1994-03-01 1995-09-12 Sumitomo Bakelite Co Ltd 熱可塑性樹脂組成物
JP2003096168A (ja) * 2001-09-26 2003-04-03 Nippon Zeon Co Ltd ノルボルネン系開環重合体水素添加物の製造方法、その製造方法により得られるノルボルネン系開環重合体水素添加物、及びその水素添加物からなる成形体
WO2004035688A1 (fr) * 2002-10-03 2004-04-29 Sekisui Chemical Co., Ltd. Film de resine a base de norbornene sature thermoplastique et son procede de production
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
JP2007154074A (ja) * 2005-12-06 2007-06-21 Mitsui Chemicals Inc フィルムまたはシート用環状オレフィン系樹脂組成物およびその用途
JP2013018962A (ja) * 2011-06-13 2013-01-31 Polyplastics Co 環状オレフィン系樹脂
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

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2020066350A1 (fr) * 2018-09-28 2020-04-02 富士フイルム株式会社 Film de polymère et dispositif d'affichage
JPWO2020066350A1 (ja) * 2018-09-28 2021-04-30 富士フイルム株式会社 ポリマーフィルム、及び表示装置
JP7016425B2 (ja) 2018-09-28 2022-02-04 富士フイルム株式会社 ポリマーフィルム、及び表示装置

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