WO2015178279A1 - Film de composition de résine d'oléfine cyclique - Google Patents

Film de composition de résine d'oléfine cyclique Download PDF

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Publication number
WO2015178279A1
WO2015178279A1 PCT/JP2015/063844 JP2015063844W WO2015178279A1 WO 2015178279 A1 WO2015178279 A1 WO 2015178279A1 JP 2015063844 W JP2015063844 W JP 2015063844W WO 2015178279 A1 WO2015178279 A1 WO 2015178279A1
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cyclic olefin
resin composition
composition film
styrene
film
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PCT/JP2015/063844
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English (en)
Japanese (ja)
Inventor
健 細谷
堀井　明宏
慶 小幡
石森　拓
一樹 平田
宏士 須賀田
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デクセリアルズ株式会社
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Publication of WO2015178279A1 publication Critical patent/WO2015178279A1/fr

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    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08L25/08—Copolymers of styrene
    • C08L25/10—Copolymers of styrene with conjugated dienes
    • 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

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 is equivalent to general amorphous plastics and has a high coefficient of linear thermal expansion. Internal distortion occurred.
  • the present invention has been proposed in view of such conventional circumstances, and provides a cyclic olefin-based resin composition film having a low linear thermal expansion coefficient and excellent optical characteristics and toughness.
  • the present inventor improves the optical properties and toughness while maintaining a low linear thermal expansion coefficient by adding a styrene elastomer and inorganic oxide fine particles to the cyclic olefin resin and adjusting to a predetermined linear thermal expansion coefficient.
  • the present inventors have found that this can be done and have completed the present invention.
  • the cyclic olefin-based resin composition film according to the present invention contains a cyclic olefin-based resin, a styrene-based elastomer, and inorganic oxide fine particles, and has a linear thermal expansion coefficient of 40 ppm / ° C. or more and 60 ppm / ° C. or less. It is characterized by being.
  • the method for producing a cyclic olefin-based resin composition film according to the present invention includes a cyclic olefin-based resin composition, a styrene-based elastomer, and inorganic oxide fine particles that are heated and melted. Is extruded into a film by an extrusion method to obtain a cyclic olefin-based resin composition film having a linear thermal expansion coefficient of 40 ppm / ° C. or more and 60 ppm / ° C. or less.
  • 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 present invention contains a cyclic olefin-based resin, a styrene-based elastomer, and inorganic oxide fine particles, and the linear thermal expansion coefficient is 40 ppm / ° C. or more and 60 ppm / ° C. or less, so that a low linear thermal expansion coefficient is obtained. Excellent optical properties and toughness can be obtained while maintaining the above.
  • 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.
  • FIG. 11 is a schematic cross-sectional view illustrating a deflection evaluation method.
  • the cyclic olefin-based resin composition film according to the present embodiment contains a cyclic olefin-based resin, a styrene-based elastomer, and inorganic oxide fine particles, and has a linear thermal expansion coefficient of 40 ppm / ° C. or more and 60 ppm / ° C. or less. is there.
  • 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)
  • 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 contains a cyclic olefin-based resin 11, a styrene-based elastomer 12, and inorganic oxide fine particles 13.
  • 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 MD-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 linear thermal expansion coefficient of the cyclic olefin-based resin composition film is 40 ppm / ° C. or more and 60 ppm / ° C. or less. As a result, excellent optical properties and toughness can be obtained while maintaining a low coefficient of linear thermal expansion.
  • the storage elastic modulus of the cyclic olefin-based resin composition film is preferably 1500 MPa or more and 2500 MPa or less, and particularly preferably 2000 MPa or less.
  • the storage elastic modulus of the cyclic olefin-based resin composition film comprising the cyclic olefin-based resin 11 and the styrene-based elastomer 12 is 1800 to 2200 MPa.
  • the addition of the inorganic oxide fine particles 13 decreases the storage elastic modulus. Even so, the tear strength can be maintained.
  • 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 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.
  • 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.
  • the addition amount of the styrene-based elastomer is preferably 5 vol% or more and 30 vol% 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 inorganic oxide fine particles are preferably at least one selected from Al 2 O 3 , SiO 2 , ZrO 2 and TiO 2 . Since these inorganic oxide fine particles have a small linear thermal expansion coefficient, the linear thermal expansion coefficient of the cyclic olefin-based resin composition film can be reduced by addition.
  • the upper limit of the amount of inorganic oxide fine particles added is preferably less than 30 vol%, more preferably 20 vol% or less.
  • fine-particles it is preferable that it is 0.1 vol% or more, More preferably, it is 1.0 vol% or more, More preferably, it is 10 vol% or more. If the addition amount of the inorganic oxide fine particles is too large, the optical properties (haze, retardation) deteriorate, and if the addition amount is too small, it is difficult to reduce the linear expansion coefficient.
  • the average particle diameter of the inorganic oxide fine particles is preferably 50 nm or less, more preferably 5 nm or more and 10 nm or less. If the average particle size is too large, light scattering may occur and the sheet may be whitened, and the intended transparency may not be obtained. Moreover, when an average particle diameter is too small, addition will become substantially difficult.
  • the average particle diameter is, for example, the sum of the long axis length of fine particles (corresponding to the plate surface direction in the case of plate-like fine particles) and the short axis length (corresponding to the plate thickness direction in the case of plate-like fine particles) of 2
  • the divided value ((major axis + minor axis) / 2) is calculated for each particle, and can be an average value of 100 particles.
  • the inorganic oxide particles are produced by a gas phase method or a liquid phase method.
  • the vapor phase method can obtain a powder with relatively good dispersibility because a dry powder can be obtained directly.
  • the chemical flame method it is not suitable for industrial production because of its low mass production and high cost. Absent.
  • the liquid phase method crystal nuclei are generated and grown by a chemical reaction in a solution, followed by drying and firing processes. In order to produce fine particles, it is necessary to strictly control the production conditions so that the grains do not grow in each step.
  • the liquid phase method if the particles are agglomerated tightly at the time of drying, a large energy is required for dispersion, so it is most important not to agglomerate.
  • a method may be used in which the process proceeds directly to the dispersion step while leaving the liquid phase without passing through the drying and firing steps.
  • various compounding agents may be added to the cyclic olefin resin composition as necessary as long as the characteristics thereof 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 in-plane retardation R 0 can be 10 nm or less
  • the tear strength can be 60 N / mm or more
  • the haze can be 1.0% or less. If the tear strength is less than the above range, the film is liable to break during production or use, which is inappropriate. On the other hand, if the haze 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 includes heating and melting a cyclic olefin-based resin composition, a styrene-based elastomer, and inorganic oxide fine particles. Extruded into a film by an extrusion method to obtain a cyclic olefin-based resin composition film having a linear thermal expansion coefficient of 40 ppm / ° C. or more and 60 ppm / ° C. or less.
  • 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.
  • the linear thermal expansion coefficient, retardation, tear strength, and initial haze of the cyclic olefin-based 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 of 4 ⁇ 10 mm was produced from a film having a thickness of 0.2 to 0.3 mm, and the average linear thermal expansion coefficient (ppm / ° C.) at a temperature of 0 ° C. to 200 ° C. was measured. It calculated in.
  • 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, styrene elastomer, and inorganic oxide fine particles As the cyclic olefin-based resin, TOPAS 6013-S04 (manufactured by Polyplastics Co., Ltd., an addition copolymer of ethylene and norbornene) was used.
  • Tuftec H1041 manufactured by Asahi Kasei Chemicals Corporation, styrene / ethylene / butylene / styrene block copolymer was used.
  • Al 2 O 3 (aluminum oxide ( ⁇ type)): coefficient of linear thermal expansion 7.2 ppm / ° C., average particle size 5 nm, manufactured by IoLiTec SiO 2 (silicon dioxide): coefficient of linear thermal expansion 0.7 ppm / ° C., average particle Diameter 15 nm, IoLiTec ZrO 2 (zirconium oxide): linear thermal expansion coefficient 10.5 ppm / ° C., average particle size 40 nm, IoLiTec TiO 2 (titanium oxide): linear thermal expansion coefficient 7.1 ppm / ° C., average particle Diameter 20nm, made by Ishihara Sangyo
  • Example 1 A twin-screw extruder containing 80 vol% of cyclic olefin resin, 10 vol% of Tuftec H1041 as a styrene elastomer and 10 vol% of Al 2 O 3 as inorganic oxide fine particles, and a T-die attached to the tip (specifications: And kneading at a predetermined temperature in the temperature range of 210 ° C. to 300 ° C. using a diameter of 25 mm, length: 26D, T die width: 160 mm), and then extruding the cyclic olefin resin composition at a speed of 250 g / min. A film having a thickness of 80 ⁇ m was wound on a roll.
  • the styrenic elastomer is dispersed with shape anisotropy in the MD direction of the film, has an average major axis of about 4 ⁇ m in the MD direction, and an average minor axis of about 0.2 ⁇ m in the TD direction. Had.
  • the linear thermal expansion coefficient of the film is 47 ppm / ° C.
  • the retardation R 0 is an evaluation of ⁇ at 4.7 nm
  • the tear strength is an evaluation of ⁇ at 81 N / mm
  • the initial haze is The evaluation was ⁇ at 0.5%.
  • Example 2 A film having a thickness of 80 ⁇ m in the same manner as in Example 1 except that 70 vol% of cyclic olefin resin, 10 vol% of Tuftec H1041 as styrene elastomer, and 20 vol% of Al 2 O 3 as inorganic oxide fine particles were blended. Was made.
  • the coefficient of linear thermal expansion of the film is 43 ppm / ° C.
  • the retardation R 0 is 4.7 nm
  • the tear strength is 72 N / mm
  • the initial haze is The evaluation was ⁇ at 0.6%.
  • Example 3 A film having a thickness of 80 ⁇ m was prepared in the same manner as in Example 1 except that 80 vol% of cyclic olefin resin, 10 vol% of tuftec H1041 as styrene elastomer, and 10 vol% of SiO 2 as inorganic oxide fine particles were blended. did.
  • the linear thermal expansion coefficient of the film is 46 ppm / ° C.
  • the retardation R 0 is 4.6 nm
  • the tear strength is 81 N / mm
  • the initial haze is The evaluation was ⁇ at 0.5%.
  • Example 4 A film having a thickness of 80 ⁇ m is prepared in the same manner as in Example 1 except that 70 vol% of cyclic olefin resin, 10 vol% of tuftec H1041 as styrene elastomer, and 20 vol% of SiO 2 as inorganic oxide fine particles are blended. did.
  • the linear thermal expansion coefficient of the film is 41 ppm / ° C.
  • the retardation R 0 is 4.6 nm
  • the tear strength is 72 N / mm
  • the initial haze is The evaluation was ⁇ at 0.6%.
  • Example 5 A film having a thickness of 80 ⁇ m is prepared in the same manner as in Example 1 except that 70 vol% of cyclic olefin resin, 10 vol% of tuftec H1041 as styrene elastomer, and 20 vol% of ZrO 2 as inorganic oxide fine particles are blended. did.
  • the linear thermal expansion coefficient of the film is 43 ppm / ° C.
  • the retardation R 0 is 5.3
  • the evaluation is ⁇ .
  • the tear strength is 72 N / mm
  • the initial haze is The evaluation was ⁇ at 0.6%.
  • Example 6 A film having a thickness of 80 ⁇ m is prepared in the same manner as in Example 1 except that 70 vol% of the cyclic olefin resin, 10 vol% of Tuftec H1041 as the styrene elastomer, and 20 vol% of TiO 2 as the inorganic oxide fine particles are blended. did.
  • the coefficient of linear thermal expansion of the film is 43 ppm / ° C.
  • the retardation R 0 is an evaluation of ⁇ at 5.0 nm
  • the tear strength is an evaluation of ⁇ at 72 N / mm
  • the initial haze is The evaluation was ⁇ at 0.6%.
  • Example 1 A film having a thickness of 80 ⁇ m was produced in the same manner as in Example 1 except that 100 vol% of the cyclic olefin resin was blended.
  • the linear thermal expansion coefficient of the film is 65 ppm / ° C.
  • the retardation R 0 is 0.4 nm
  • the tear strength is 55 N / mm
  • the initial haze is The evaluation was ⁇ at 0.2%.
  • Example 2 A film having a thickness of 80 ⁇ m was prepared in the same manner as in Example 1 except that 90 vol% of the cyclic olefin resin and 10 vol% of Tuftec H1041 as a styrene elastomer were blended.
  • the coefficient of linear thermal expansion of the film is 62 ppm / ° C.
  • the retardation R 0 is 2.0 nm
  • the evaluation is ⁇
  • the tear strength is 90 N / mm
  • the initial haze is The evaluation was ⁇ at 0.5%.
  • Example 3 A film having a thickness of 80 ⁇ m in the same manner as in Example 1 except that 60 vol% of cyclic olefin resin, 10 vol% of Tuftec H1041 as styrene elastomer, and 30 vol% of Al 2 O 3 as inorganic oxide fine particles were blended. Was made.
  • the linear thermal expansion coefficient of the film is 38 ppm / ° C.
  • the retardation R 0 is an evaluation of ⁇ at 4.7 nm
  • the tear strength is an evaluation of ⁇ at 63 N / mm
  • the initial haze is The evaluation was x at 2.8%.
  • Example 4 A film having a thickness of 80 ⁇ m was prepared in the same manner as in Example 1 except that 60 vol% of cyclic olefin resin, 10 vol% of tuftec H1041 as styrene elastomer, and 30 vol% of SiO 2 as inorganic oxide fine particles were blended. did.
  • the linear thermal expansion coefficient of the film is 38 ppm / ° C.
  • the retardation R 0 is 4.5 nm
  • the tear strength is 63 N / mm
  • the initial haze is The evaluation was x at 3.4%.
  • Comparative Example 1 had a tear strength of less than 60 N / mm because no styrene elastomer was added.
  • Comparative Example 2 since the inorganic oxide fine particles are not added, the linear thermal expansion coefficient does not decrease.
  • Comparative Examples 3 and 4 in which the amount of inorganic oxide fine particles added is 30 vol% is very preferable when the linear thermal expansion coefficient is less than 40 ppm / ° C., but the initial haze exceeds 1.5%, It was difficult to use.
  • Examples 1 to 6 contain a cyclic olefin resin, a styrene elastomer, and inorganic oxide fine particles, the linear thermal expansion coefficient is lowered to 40 ppm / ° C. or more and 60 ppm / ° C. or less, and the in-plane direction is reduced.
  • the retardation R 0 was 10 nm or less
  • the tear strength was 60 N / mm or more
  • the haze was 1.0% or less.
  • the addition amount of the inorganic oxide fine particles is less than 30 vol%, thereby suppressing the aggregation of the inorganic oxide fine particles and preventing the initial haze from increasing. I found out that I could do it.
  • the PET film 170 was arrange

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polarising Elements (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention concerne un film de composition de résine d'oléfine cyclique qui présente un faible coefficient de dilatation thermique linéaire, tout en présentant d'excellentes caractéristiques optiques et une excellente ténacité. Ce film de composition de résine d'oléfine cyclique contient une résine d'oléfine cyclique (11), un élastomère de styrène (12) et des particules fines d'oxyde inorganique (13) et présente un coefficient de dilatation thermique linéaire allant de 40 ppm/°C à 60 ppm/°C (inclus). Par conséquent, ce film de composition de résine d'oléfine cyclique permet d'obtenir d'excellentes caractéristiques optiques et une excellente ténacité, tout en maintenant un faible coefficient de dilatation thermique linéaire.
PCT/JP2015/063844 2014-05-22 2015-05-14 Film de composition de résine d'oléfine cyclique WO2015178279A1 (fr)

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JP2014-106001 2014-05-22
JP2015098101A JP2016000805A (ja) 2014-05-22 2015-05-13 環状オレフィン系樹脂組成物フィルム
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WO2017085808A1 (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

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JP2018027617A (ja) * 2016-08-15 2018-02-22 恵和株式会社 樹脂ペレットの製造方法、及び光学用フィルムの製造方法
JP7255738B2 (ja) * 2020-03-31 2023-04-11 三菱ケミカル株式会社 ポリオレフィン系シート、プレススルーパッケージ包装用底材およびプレススルーパッケージ包装材
JP7415743B2 (ja) 2020-03-31 2024-01-17 三菱ケミカル株式会社 ポリオレフィン系シート、プレススルーパッケージ包装用底材およびプレススルーパッケージ包装材

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JPH0232139A (ja) * 1988-07-20 1990-02-01 Mitsui Petrochem Ind Ltd 環状オレフィン系ランダム共重合体組成物
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
WO2008108199A1 (fr) * 2007-03-02 2008-09-12 Jsr Corporation Film de retardement, procédé pour sa fabrication, et polariseur
JP2010241005A (ja) * 2009-04-07 2010-10-28 Mitsubishi Plastics Inc 白色積層シクロオレフィン系樹脂反射材
CN102832347A (zh) * 2012-08-31 2012-12-19 苏州中来光伏新材股份有限公司 一种降冰片烯共聚物太阳电池基膜及其加工工艺
JP2013249329A (ja) * 2012-05-30 2013-12-12 Canon Inc 樹脂組成物、成形体及びミラー

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JPH0232139A (ja) * 1988-07-20 1990-02-01 Mitsui Petrochem Ind Ltd 環状オレフィン系ランダム共重合体組成物
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
WO2008108199A1 (fr) * 2007-03-02 2008-09-12 Jsr Corporation Film de retardement, procédé pour sa fabrication, et polariseur
JP2010241005A (ja) * 2009-04-07 2010-10-28 Mitsubishi Plastics Inc 白色積層シクロオレフィン系樹脂反射材
JP2013249329A (ja) * 2012-05-30 2013-12-12 Canon Inc 樹脂組成物、成形体及びミラー
CN102832347A (zh) * 2012-08-31 2012-12-19 苏州中来光伏新材股份有限公司 一种降冰片烯共聚物太阳电池基膜及其加工工艺

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017085808A1 (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
US11091623B2 (en) 2015-11-18 2021-08-17 Dexerials Corporation Cyclic olefin-based resin composition film

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