WO2017085809A1 - Film de composition de résine à base d'oléfine cyclique - Google Patents

Film de composition de résine à base d'oléfine cyclique Download PDF

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WO2017085809A1
WO2017085809A1 PCT/JP2015/082397 JP2015082397W WO2017085809A1 WO 2017085809 A1 WO2017085809 A1 WO 2017085809A1 JP 2015082397 W JP2015082397 W JP 2015082397W WO 2017085809 A1 WO2017085809 A1 WO 2017085809A1
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cyclic olefin
styrene
resin composition
retardation
based resin
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PCT/JP2015/082397
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English (en)
Japanese (ja)
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石森　拓
堀井　明宏
慶 小幡
健 細谷
香奈子 橋本
一樹 平田
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デクセリアルズ株式会社
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Priority to JP2016513161A priority Critical patent/JPWO2017085809A1/ja
Priority to PCT/JP2015/082397 priority patent/WO2017085809A1/fr
Publication of WO2017085809A1 publication Critical patent/WO2017085809A1/fr

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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
    • C08L25/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

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 resin film with the elastomer added and dispersed has a large difference in linear thermal expansion coefficient between the cyclic olefin resin and the elastomer.
  • the haze change sometimes occurred without returning to the state.
  • the present invention has been proposed in view of such conventional circumstances, and provides a cyclic olefin-based resin composition film having excellent environmental preservation.
  • the present inventor maintains excellent toughness even if the difference in linear thermal expansion coefficient between the cyclic olefin resin and the styrene elastomer is large by adding a styrene elastomer to the cyclic olefin resin and adjusting to a predetermined retardation. As a result, the inventors have found that environmental preservation can be improved, and have completed the present invention.
  • the cyclic olefin-based resin composition film according to the present invention contains a cyclic olefin-based resin and a styrene-based elastomer, and the difference in linear thermal expansion coefficient between the cyclic olefin resin and the styrene-based elastomer is 50 ppm / ° C. or more.
  • the retardation in the thickness direction is 10 nm or more and 25 nm or less, and the ratio of the retardation in the in-plane direction to the retardation in the thickness direction (R 0 / R th ) is 0.1 or more and 0.9 or less.
  • the method for producing a cyclic olefin-based resin composition film according to the present invention comprises melting a cyclic olefin-based resin having a linear thermal expansion coefficient difference of 50 ppm / ° C. or more and a styrene-based elastomer, and then melting the molten cyclic olefin-based film.
  • the resin composition is extruded into a film by an extrusion method, the styrene elastomer is dispersed in the cyclic olefin resin, the thickness direction retardation is 10 nm to 25 nm, and the in-plane direction retardation and thickness are A cyclic olefin-based resin composition film having a ratio (R 0 / R th ) to lateral retardation of 0.1 to 0.9 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.
  • 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 includes a cyclic olefin-based resin and a styrene-based elastomer, and the difference in linear thermal expansion coefficient between the cyclic olefin resin and the styrene-based elastomer is 50 ppm / ° C. or more.
  • the retardation in the thickness direction is 10 nm or more and 25 nm or less, and the ratio (R 0 / R th ) between the in-plane retardation and the thickness direction retardation is 0.1 or more and 0.9 or less.
  • the difference in coefficient of linear thermal expansion between the cyclic olefin resin and the styrene elastomer is 50 ppm / ° C. or more.
  • the linear thermal expansion coefficient of the cyclic olefin resin preferably used is 40 to 80 ppm / ° C.
  • the linear thermal expansion coefficient of the styrenic elastomer preferably used is 130 to 220 ppm / ° C.
  • the linear thermal expansion coefficient represents a rate of change in length at which an object expands and contracts due to a temperature change, and is indicated by a strain per unit temperature.
  • the measurement method is performed in accordance with JISK7197, and is calculated as the average linear thermal expansion coefficient ⁇ (ppm / ° C.) at the test piece temperatures T1 to T2.
  • ⁇ ⁇ L / L0 ⁇ (T2-T1) (Where ⁇ : linear expansion coefficient, ⁇ L: (length of test piece at T2) ⁇ (length of test piece at T1), L0: length of test piece at T1)
  • the retardation R th in the thickness direction is represented by the following formula, and is obtained by multiplying the two refractive indexes ⁇ Nxz and ⁇ Nyz when viewed from the cross section in the film thickness direction by the film thickness d, respectively.
  • ⁇ d ( ⁇ Nxz ⁇ d + ⁇ Nyz ⁇ d) / 2
  • the in-plane retardation R 0 is expressed by the following equation, and is obtained by multiplying the refractive index ⁇ Nxy when viewed from the surface direction by the film thickness d.
  • the thickness direction retardation is 10 nm or more and 25 nm or less, and the ratio of the in-plane direction retardation to the thickness direction retardation (R 0 / R th ) is 0.1 or more and 0.9 or less.
  • R 0 / R th the ratio of the in-plane direction retardation to the thickness direction retardation
  • 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.
  • 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. 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 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 11 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 optical properties (retardation, haze) are lowered, and if it is too small, the toughness becomes insufficient.
  • 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 a 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 styrenic 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.
  • one or more styrenes 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.
  • 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 set to 60 N / mm or more, and the haze increase rate after environmental preservation can be set to 1% or less. If the tear strength is smaller than the above range, the film is liable to be broken at the time of production or use, which is inappropriate. On the other hand, if the haze increase rate is too high, it deviates from the initial characteristics in use and does not satisfy the intended characteristics.
  • the method for producing a cyclic olefin-based resin composition film according to the present embodiment melts a cyclic olefin-based resin having a difference in linear thermal expansion coefficient of 50 ppm / ° C. or more and a styrene-based elastomer, and melted the cyclic olefin-based resin.
  • the composition is extruded into a film by an extrusion method, a styrene elastomer is dispersed in a cyclic olefin resin, the retardation in the thickness direction is 10 nm or more and 25 nm or less, the in-plane direction retardation and the thickness direction retardation
  • a cyclic olefin-based resin composition film having a ratio (R 0 / R th ) of 0.1 to 0.9 is obtained.
  • the desired retardation value can be obtained by controlling with an external stress so that the average value of Nx and Ny is larger than Nz in the theoretical formula of Rth. Examples of the external stress include techniques such as compression, non-stretching, uniaxial stretching, and biaxial stretching.
  • 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. 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. 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.
  • 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.
  • the material of the hard coat layer 32 is preferably an ionizing radiation curable resin that is cured by light or electron beam, or a thermosetting resin that is cured by heat, and most preferably a photosensitive resin that is cured by ultraviolet rays.
  • 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 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)
  • Various display devices such as Electron-emitter Display (SED) can be used.
  • 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 styrene elastomer having a predetermined linear thermal expansion coefficient was added to the cyclic olefin resin to prepare a cyclic olefin resin composition film controlled to a predetermined retardation (R 0 , R th ).
  • R 0 , R th a predetermined retardation
  • the present invention is not limited to these examples.
  • the linear thermal expansion coefficient of the styrene elastomer, the retardation, haze, and tear strength of the cyclic olefin resin composition film were measured as follows.
  • the linear thermal expansion coefficient was calculated based on JISK7197 using a thermomechanical analyzer (TMA: Thermomechanical Analysis, TMA4100SA manufactured by NETZSCH Japan).
  • TMA thermomechanical analyzer
  • a test piece made of a styrene-based elastomer was prepared, and the average linear thermal expansion coefficient (ppm / ° C.) at a temperature of 0 ° C. to 200 ° C. of the test piece was calculated at a temperature increase rate of 2 ° C./min.
  • 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 80 N / mm or more is evaluated as “A”
  • a tear strength of 60 N / mm or more and less than 80 / mm is evaluated as “B”
  • a tear strength of less than 60 N / mm is evaluated as “C”.
  • 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. The linear thermal expansion coefficient of this cyclic olefin resin was 65 ppm / ° C.
  • Tuftec H1272 (Asahi Kasei Chemicals Co., Ltd., styrene content: 35 mol%)
  • Tuftec H1221 (Asahi Kasei Chemicals Co., Ltd., styrene content: 12 mol%) are styrene / ethylene / butylene / styrene block copolymers.
  • S. O. E L606 manufactured by Asahi Kasei Chemicals Corporation, styrene content: 36 mol%) is a hydrogenated styrene / butadiene block copolymer.
  • the linear thermal expansion coefficients of these styrenic elastomers were all in the range of 130 to 220 ppm / ° C.
  • Styrenic elastomers include S.I. O. E L606 was used. The difference in coefficient of linear thermal expansion between the cyclic olefin resin and the styrene elastomer was 50 ppm / ° C. or higher.
  • retardation R 0 in the in-plane direction of the film was 1.9 nm
  • retardation in the thickness direction was 11.2 nm
  • R 0 / R th was 0.17
  • the initial haze was 0.2%
  • the haze increase after environmental preservation was 0.3%, which was evaluated as A.
  • the tear strength was 98 N / mm, which was evaluated as A.
  • Example 2 Tuftec H1272 was used as the styrene elastomer.
  • the difference in coefficient of linear thermal expansion between the cyclic olefin resin and the styrene elastomer was 50 ppm / ° C. or higher.
  • the film was produced in the same manner as in Example 1.
  • retardation R 0 in the in-plane direction of the film was 13.5 nm
  • retardation in the thickness direction was 15.3 nm
  • R 0 / R th was 0.88
  • the initial haze was 15.3%
  • the increase in haze after environmental preservation was 0.4%, which was evaluated as A.
  • the tear strength was 80 N / mm, which was an evaluation of A.
  • Styrenic elastomers include S.I. O. E. L606 was used. The difference in coefficient of linear thermal expansion between the cyclic olefin resin and the styrene elastomer was 50 ppm / ° C. or higher. The film was produced in the same manner as in Example 1.
  • retardation R 0 in the in-plane direction of the film was 18.1 nm
  • retardation in the thickness direction was 20.4 nm
  • R 0 / R th was 0.89.
  • the initial haze was 0.3%
  • the haze increase after environmental preservation was 0.1%, which was evaluated as A.
  • the tear strength was 102 N / mm, which was evaluated as A.
  • Tuftec H1221 was used as the styrene elastomer.
  • the difference in coefficient of linear thermal expansion between the cyclic olefin resin and the styrene elastomer was 50 ppm / ° C. or higher.
  • the film was produced in the same manner as in Example 1.
  • retardation R 0 in the in-plane direction of the film was 2.5 nm
  • retardation in the thickness direction was 7.0 nm
  • R 0 / R th was 0.36
  • the initial haze was 9.0%
  • the haze increase after environmental preservation was 2.8%, which was evaluated as C.
  • the tear strength was 77 N / mm, which was evaluated as B.
  • Tuftec H1272 was used as the styrene elastomer.
  • the difference in coefficient of linear thermal expansion between the cyclic olefin resin and the styrene elastomer was 50 ppm / ° C. or higher.
  • the film was produced in the same manner as in Example 1.
  • retardation R 0 in the in-plane direction of the film was 1.5 nm
  • retardation in the thickness direction was 4.4 nm
  • R 0 / R th was 0.34
  • the initial haze was 17.5%
  • the increase in haze after environmental preservation was 15.2%
  • the tear strength was 78 N / mm, which was evaluated as B.
  • Styrenic elastomers include S.I. O. E. L606 was used. The difference in coefficient of linear thermal expansion between the cyclic olefin resin and the styrene elastomer was 50 ppm / ° C. or higher. The film was produced in the same manner as in Example 1.
  • retardation R 0 in the in-plane direction of the film was 1.3 nm
  • retardation in the thickness direction was 5.9 nm
  • R 0 / R th was 0.22
  • the initial haze was 0.2%
  • the haze increase after environmental preservation was 4.0%, which was evaluated as C.
  • the tear strength was 100 N / mm, which was an evaluation of A.
  • the thickness direction retardation R th is 10 nm to 25 nm, and the ratio of the in-plane direction retardation to the thickness direction retardation (R 0 / R th ) is 0.
  • the haze increase after environmental preservation was less than 1.0%, and good environmental preservation was obtained. This is presumably because the styrene-based elastomer was uniformly dispersed in an appropriate size in the cyclic olefin resin.

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Abstract

L'invention concerne un film de composition de résine à base d'oléfine cyclique qui possède d'excellentes propriétés de préservation de l'environnement. La présente invention contient une résine à base d'oléfine cyclique (11) et un élastomère à base de styrène (12), la différence entre les coefficients de dilatation thermique linéaires de la résine à base d'oléfine cyclique (11) et de l'élastomère à base de styrène (12) n'étant pas inférieure à 50 ppm/°C, le retard dans la direction de l'épaisseur étant de 10 à 25 nm, et le rapport (R0/Rth) de retard dans la direction dans le plan sur le retard dans la direction de l'épaisseur étant de 0,1 à 0,9. D'excellentes propriétés de préservation de l'environnement peuvent ainsi être obtenues.
PCT/JP2015/082397 2015-11-18 2015-11-18 Film de composition de résine à base d'oléfine cyclique WO2017085809A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005272711A (ja) * 2004-03-25 2005-10-06 Sekisui Chem Co Ltd 熱可塑性飽和ノルボルネン系樹脂フィルム、光学フィルム及び偏光子保護フィルム
WO2011135927A1 (fr) * 2010-04-28 2011-11-03 アロン化成株式会社 Composition d'élastomère et bouchon pour récipient médical
JP2015055796A (ja) * 2013-09-12 2015-03-23 富士フイルム株式会社 光学フィルム及び表示装置
WO2015080167A1 (fr) * 2013-11-26 2015-06-04 デクセリアルズ株式会社 Film à base d'une composition de résine cyclo-oléfinique
WO2015083808A1 (fr) * 2013-12-04 2015-06-11 デクセリアルズ株式会社 Film de composition de résine d'oléfine cyclique
WO2015178331A1 (fr) * 2014-05-19 2015-11-26 デクセリアルズ株式会社 Film de composition de résine d'oléfine cyclique

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005272711A (ja) * 2004-03-25 2005-10-06 Sekisui Chem Co Ltd 熱可塑性飽和ノルボルネン系樹脂フィルム、光学フィルム及び偏光子保護フィルム
WO2011135927A1 (fr) * 2010-04-28 2011-11-03 アロン化成株式会社 Composition d'élastomère et bouchon pour récipient médical
JP2015055796A (ja) * 2013-09-12 2015-03-23 富士フイルム株式会社 光学フィルム及び表示装置
WO2015080167A1 (fr) * 2013-11-26 2015-06-04 デクセリアルズ株式会社 Film à base d'une composition de résine cyclo-oléfinique
WO2015083808A1 (fr) * 2013-12-04 2015-06-11 デクセリアルズ株式会社 Film de composition de résine d'oléfine cyclique
WO2015178331A1 (fr) * 2014-05-19 2015-11-26 デクセリアルズ株式会社 Film de composition de résine d'oléfine cyclique

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