WO2023188689A1 - Transparent resin film and display device - Google Patents

Transparent resin film and display device Download PDF

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Publication number
WO2023188689A1
WO2023188689A1 PCT/JP2023/000757 JP2023000757W WO2023188689A1 WO 2023188689 A1 WO2023188689 A1 WO 2023188689A1 JP 2023000757 W JP2023000757 W JP 2023000757W WO 2023188689 A1 WO2023188689 A1 WO 2023188689A1
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WO
WIPO (PCT)
Prior art keywords
resin
resin layer
less
resin film
transparent resin
Prior art date
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PCT/JP2023/000757
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French (fr)
Japanese (ja)
Inventor
寛 岩脇
崇弘 石原
宏司 西岡
Original Assignee
住友化学株式会社
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Priority claimed from JP2022205851A external-priority patent/JP2023152659A/en
Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Publication of WO2023188689A1 publication Critical patent/WO2023188689A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements

Definitions

  • the present invention relates to a transparent resin film containing inorganic particles and a display device including the transparent resin film.
  • Patent Document 1 discloses a quantum dot-containing resin sheet or film in which a plurality of resin layers are laminated and at least one resin layer contains quantum dots, and a wavelength conversion member using the same. is listed.
  • the present invention provides a transparent resin film and a display device shown below.
  • a first resin layer containing a first resin; a second resin layer disposed on the first surface of the first resin layer, the second resin layer containing a second resin; a third resin layer disposed on a second surface of the first resin layer opposite to the first surface, the third resin layer containing a third resin;
  • a transparent resin film comprising: The first resin layer contains inorganic particles, When the thickness of the transparent resin film is T [ ⁇ m], the thickness of the second resin layer is T 2 [ ⁇ m], and the thickness of the third resin layer is T 3 [ ⁇ m], the standard deviation of T 2 /T is and a transparent resin film having a standard deviation of T 3 /T of 0.015 or less.
  • the resin contained in the first resin layer is made of the first resin
  • the resin contained in the second resin layer is made of the second resin
  • the resin contained in the third resin layer is made of the third resin.
  • the transparent resin film according to any one of [1] to [6], wherein the first resin, the second resin, and the third resin are the same.
  • the transparent resin film according to any one of [1] to [7], wherein the inorganic particles include semiconductor particles.
  • a display device comprising the transparent resin film according to any one of [1] to [9].
  • the transparent resin film according to the present invention includes a first resin layer containing inorganic particles and a first resin, a second resin layer containing a second resin, and a second resin layer containing a second resin. It is a resin film with a multilayer structure including a third resin layer containing three resins.
  • Transparent in a transparent resin film means that the total light transmittance measured in accordance with JIS K 7361-1:1997 is 30% or more. The total light transmittance is preferably 35% or more, more preferably 40% or more, even more preferably 45% or more, and may be 100% or less, or 95% or less. It is preferable that each of the resin layers constituting the transparent resin film is "transparent".
  • the term “film” also includes the meaning of the term "sheet”.
  • the transparent resin film can be suitably used as a film for optical applications (optical film).
  • An example of optical use is use as an optical member used in a display device.
  • a transparent resin film has small variations in surface hardness on both sides and has excellent scratch resistance.
  • the transparent resin film may have a good surface appearance due to reduced flow marks (spot patterns, etc.) that may be formed on the film surface during film molding.
  • a transparent resin film is less prone to curling even when rolled (wound), and may have good curl resistance. Moreover, the transparent resin film can have good bending resistance. The transparent resin film will be explained in detail below.
  • FIG. 1 is a schematic cross-sectional view showing an example of a transparent resin film.
  • the transparent resin film shown in FIG. 1 includes a first resin layer 10 containing inorganic particles 15, a second resin layer 20 disposed on the first surface (one surface) of the first resin layer 10, and It is a resin film with a three-layer structure consisting of a first surface of one resin layer 10 and a third resin layer 30 disposed on the opposing second surface (the other surface).
  • first resin layer 10 and the second resin layer 20 are in contact with each other, and it is preferable that the first resin layer 10 and the third resin layer 30 are in contact with each other.
  • the first resin layer 10 is a resin layer containing inorganic particles 15, and the inorganic particles 15 are normally dispersed in the first resin layer 10.
  • the resin contained in the first resin layer 10 includes a first resin, and preferably, the resin contained in the first resin layer 10 is made of the first resin.
  • the first resin layer 10 contains one or more types of inorganic particles 15.
  • the shape of the inorganic particles 15 is not particularly limited, but is preferably granular, more preferably spherical or approximately spherical.
  • the inorganic particles 15 may have a single layer structure or a multilayer structure.
  • the density of the inorganic particles 15 is usually 0.8 g/cm 3 or more, preferably 0.9 g/cm 3 or more, more preferably 1.0 g/cm 3 or more, and still more preferably 1.0 g/cm 3 or more. , still more preferably 2.0 g/cm 3 or more.
  • the density of the inorganic particles 15 is usually 7.0 g/cm 3 or less, preferably 6.0 g/cm 3 or less, more preferably 5.0 g/cm 3 or less, even more preferably 4.5 g/cm 3 It is as follows.
  • the density of the inorganic particles 15 can be measured using a Gerussac type pycnometer in an environment at a temperature of 25°C.
  • the density of the inorganic particles 15 is below the above upper limit, sedimentation of the inorganic particles 15 is easily suppressed, and the distribution of the inorganic particles 15 in the first resin layer 10 tends to be uniform, so that variations in surface hardness are reduced.
  • Cheap Moreover, when the density of the inorganic particles 15 is equal to or higher than the above lower limit, mechanical strength such as surface hardness is easily increased.
  • Examples of the inorganic particles 15 contained in the first resin layer 10 include light scattering agents and luminescent (fluorescent) semiconductor particles (hereinafter also simply referred to as "semiconductor particles").
  • Examples of the light scattering agent include metal or metal oxide particles, glass particles (glass beads, etc.), and the like.
  • the light scattering agent is preferably a particle of a metal oxide, since it is preferable to have only a scattering effect without absorption due to coloring, and examples of the metal oxide include TiO 2 , SiO 2 , BaTiO 3 , ZnO, etc. Among them, TiO 2 particles are preferable because they scatter light efficiently.
  • the volume-based median diameter of the light scattering agent is, for example, about 0.03 ⁇ m or more and 20 ⁇ m or less, preferably 0.05 ⁇ m or more and 1 ⁇ m or less, and more preferably 0.05 ⁇ m or more and 0.5 ⁇ m or less.
  • the first resin layer 10 may contain two or more types of light scattering agents.
  • the semiconductor particles emit light of a different wavelength from the primary light, and preferably convert the wavelength of blue light, which is the primary light, into the wavelength of light of a different color.
  • the semiconductor particles preferably emit green or red light, and more preferably absorb blue light and emit green or red light.
  • blue refers to all light that is visually recognized as blue (general light having an intensity in the blue wavelength range, for example, 380 nm to 495 nm), and is not limited to light of a single wavelength.
  • Green refers to all light that is visually perceived as green (all light having an intensity in the green wavelength range, for example, 495 nm to 585 nm), and is not limited to light of a single wavelength.
  • Red refers to light in general that is visually recognized as red (general light having an intensity in the red wavelength range, for example, 585 nm to 780 nm), and is not limited to light of a single wavelength.
  • yellow refers to all light that is visually perceived as yellow (all light having an intensity in the yellow wavelength range, for example, 560 nm to 610 nm), and is not limited to light of a single wavelength.
  • the emission spectrum of the semiconductor particles that emit green light preferably includes a peak having a maximum value in a wavelength range of 500 nm or more and 560 nm or less, more preferably a peak having a maximum value in a wavelength range of 520 nm or more and 545 nm or less, More preferably, it includes a peak having a maximum value in a wavelength range of 525 nm or more and 540 nm or less.
  • the full width at half maximum of the peak is preferably 15 nm or more and 80 nm or less, more preferably 15 nm or more and 60 nm or less, still more preferably 15 nm or more and 50 nm or less, particularly preferably 15 nm or more and 45 nm or less.
  • the emission spectrum of the semiconductor particles that emit red light preferably includes a peak having a maximum value in a wavelength range of 610 nm or more and 750 nm or less, more preferably a peak having a maximum value in a wavelength range of 615 nm or more and 650 nm or less, More preferably, it includes a peak having a maximum value in a wavelength range of 620 nm or more and 640 nm or less.
  • the full width at half maximum of the peak is preferably 15 nm or more and 80 nm or less, more preferably 15 nm or more and 60 nm or less, still more preferably 15 nm or more and 50 nm or less, particularly preferably 15 nm or more and 45 nm or less.
  • the emission spectrum of the semiconductor particles can be determined using, for example, a spectrofluorophotometer or an absolute PL quantum yield measuring device (“C9920-02” manufactured by Hamamatsu Photonics, excitation light 450 nm, room temperature, in the atmosphere). For example, the measurement is performed using a semiconductor particle dispersion diluted so that the absorbance at a wavelength of 450 nm is 0.4.
  • the emission spectrum of a transparent resin film containing semiconductor particles was determined by placing a measurement sample of the transparent resin film on a blue LED backlight with a peak wavelength of 450 nm, and measuring the transmitted light with a spectroradiometer (“SR- UL1R").
  • the semiconductor particles are particles made of semiconductor crystals, preferably nanoparticles made of semiconductor crystals.
  • Preferred examples of semiconductor particles include semiconductor quantum dots (hereinafter also referred to as “quantum dots”) and particles of compounds having a perovskite crystal structure (hereinafter also referred to as “perovskite compounds”), and more preferably It is a quantum dot.
  • Quantum dots are luminescent semiconductor particles that emit light by absorbing ultraviolet light or visible light (for example, blue light) by utilizing the band gap of the semiconductor.
  • the average particle size of the quantum dots is, for example, 0.5 nm or more and 100 nm or less, preferably 0.5 nm or more and 20 nm or less, and more preferably 1 nm or more and 15 nm or less (for example, 2 nm or more and 15 nm or less).
  • the average particle size of quantum dots can be determined using a transmission electron microscope (TEM). Since the energy state of a quantum dot depends on its size, it is possible to freely select the emission wavelength by changing the particle size.
  • the peak wavelengths of the emission spectrum when the particle diameters are 2.3 nm, 3.0 nm, 3.8 nm, and 4.6 nm are 528 nm, 570 nm, 592 nm, and 637 nm, respectively. It is.
  • quantum dots include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, CdHgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, Hg STe, CdZnS, CdZnSe, CdZnTe , CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSe Compounds of group 12 elements such as Te and HgZnSTe and group 16 elements; GaN
  • quantum dots surface-modified with metal oxides or organic substances may be used.
  • surface-modified quantum dots it is possible to prevent S and Se from being extracted by reactive components that are or may be included in the composition.
  • the quantum dot may form a core-shell structure by combining the above-mentioned compounds. Examples of such combinations include fine particles in which the core is CdSe and the shell is ZnS, and fine particles in which the core is InP and the shell is ZnSeS.
  • quantum dots Since the energy state of a quantum dot depends on its size, it is possible to freely select the emission wavelength by changing the particle size. Furthermore, since the light emitted from the quantum dots has a narrow spectrum width, it is advantageous for widening the color gamut of a display device. Furthermore, since quantum dots have high responsiveness, they are also advantageous in terms of primary light utilization efficiency.
  • quantum dots may have a single layer structure made of a single semiconductor material, or the surface of a nuclear particle (core layer) made of a single semiconductor material may be made of one or two different types. It may be a core-shell structure covered with a covering layer (shell layer) made of one or more semiconductor materials. In the latter case, the semiconductor material constituting the shell layer usually has a larger bandgap energy than the semiconductor material constituting the core layer.
  • the quantum dot may have two or more types of shell layers.
  • the shape of the quantum dots is not particularly limited, and may be, for example, spherical or approximately spherical, rod-shaped, disc-shaped, or the like.
  • a perovskite compound is a compound having a perovskite-type crystal structure containing A, B, and X as components.
  • A is a component located at each vertex of a hexahedron centered on B, and is a monovalent cation.
  • X represents a component located at each vertex of an octahedron centered on B in the perovskite crystal structure, and is at least one ion selected from the group consisting of halide ions and thiocyanate ions.
  • B is a component located at the center of the hexahedron with A at the apex and the octahedron with X at the apex, and is a metal ion.
  • the average particle diameter of the semiconductor particles made of a perovskite compound is preferably 3 nm or more, more preferably 4 nm or more, and still more preferably 5 nm or more, from the viewpoint of maintaining a good crystal structure. Further, from the viewpoint of dispersibility of the semiconductor particles made of a perovskite compound, the average particle size of the semiconductor particles is preferably 5 ⁇ m or less, more preferably 500 nm or less, and even more preferably 100 nm or less.
  • the average particle size of semiconductor particles made of a perovskite compound can be determined using a transmission electron microscope (TEM).
  • the perovskite compound containing A, B, and X as components is not particularly limited, and may be a compound having any structure such as a three-dimensional structure, a two-dimensional structure, or a pseudo-two-dimensional structure.
  • the perovskite compound is represented by ABX (3+ ⁇ ) .
  • the perovskite compound is represented by A 2 BX (4+ ⁇ ) .
  • ⁇ is a number that can be changed as appropriate depending on the charge balance of B, and is ⁇ 0.7 or more and 0.7 or less.
  • Preferred specific examples of perovskite compounds having a two-dimensional perovskite crystal structure represented by A 2 BX (4+ ⁇ ) include: ( C4H9NH3 ) 2PbBr4 , ( C4H9NH3 ) 2PbCl4 , ( C4H9NH3 ) 2PbI4 , ( C7H15NH3 ) 2PbBr4 , ( C 7 H 15 NH 3 ) 2 PbCl 4 , (C 7 H 15 NH 3 ) 2 PbI 4 , (C 4 H 9 NH 3 ) 2 Pb (1-a) Li a Br (4+ ⁇ ) (0 ⁇ a ⁇ 0.7, -0.7 ⁇ 0), (C 4 H 9 NH 3 ) 2 Pb (1-a) Na a Br (4+ ⁇ ) (0 ⁇ a ⁇ 0.
  • the first resin layer may contain two or more types of semiconductor particles.
  • the first resin layer may contain only one type of semiconductor particles that absorb primary light and emit green light, or may contain a combination of two or more types.
  • the first resin layer may contain only one type of semiconductor particles that absorb primary light and emit red light, or may contain a combination of two or more types.
  • the first resin layer 10 may contain only one type of inorganic particles 15, or may contain two or more types of inorganic particles 15.
  • the content of the inorganic particles 15 contained in the first resin layer 10 is determined by the surface hardness, bending resistance, curl resistance, etc. of the transparent resin film. From the viewpoint of increasing the amount, the amount is, for example, 0.05% by mass or more, preferably 0.10% by mass or more, more preferably 0.15% by mass or more, and even more preferably 0.
  • the first resin layer 10 can contain one or more light scattering agents.
  • the first resin layer 10 can contain one or more types of semiconductor particles.
  • the first resin layer 10 can contain red-emitting semiconductor particles and green-emitting semiconductor particles.
  • the first resin layer 10 can contain one or more types of light scattering agents and one or more types of semiconductor particles.
  • the content of the light-scattering agent in the first resin layer 10 (if two or more types of light-scattering agents are included, the total content) is the same as that of the first resin layer 10 Based on the total amount of .15% by weight or more, particularly preferably 0.20% by weight or more, preferably 30% by weight or less, more preferably 20% by weight or less, even more preferably 10% by weight or less, even more preferably 5.0% by weight.
  • the content is particularly preferably 2.0% by mass or less, particularly preferably 1.0% by mass or less, and most preferably 0.5% by mass or less.
  • the content rate of the semiconductor particles in the first resin layer 10 is equal to the total amount of the first resin layer 10.
  • it is 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.10% by mass or more, still more preferably 0.15% by mass or more, even more preferably 0.20% by mass. % or more, particularly preferably 0.25% by mass or more, preferably 30% by mass or less, more preferably 10% by mass or less, still more preferably 5.0% by mass or less, even more preferably 3.0% by mass or less. It is.
  • the content of semiconductor particles in the first resin layer 10 is within the above range, the surface hardness, bending resistance, curl resistance, and luminescence intensity of the transparent resin film can be easily increased.
  • the ratio of the content of the semiconductor particles to the content of the light scattering agent is preferably 0.1 or more and 15 or less, more preferably 0.2 or more and 10 or less, and It is preferably 0.3 or more and 8.0 or less, even more preferably 0.5 or more and 5.0 or less.
  • the ratio of the content of the semiconductor particles to the content of the light scattering agent is within the above range, it is easy to efficiently emit light from the semiconductor particles to the outside, and it is easy to increase the light emission intensity of the transparent resin film.
  • the transparent resin film can be suitably used as a wavelength conversion film that emits white light.
  • the ratio of the content of green-emitting semiconductor particles to the content of red-emitting semiconductor particles is preferably 0.1 or more and 60 or less, more preferably 1 or more and 50 or less, still more preferably 5 or more and 45 or less. Preferably it is 10 or more and 40 or less. When the ratio of the content of green-emitting semiconductor particles to the content of red-emitting semiconductor particles is within the above range, desired white light can be easily obtained.
  • the first resin layer 10 includes a first resin.
  • the resin contained in the first resin layer 10 is made of a first resin.
  • the first resin is preferably a thermoplastic resin.
  • the first resin may contain two or more types of thermoplastic resins.
  • the resin contained in the first resin layer 10 may be made of one type of first resin, or may be made of two or more types of first resin, but is preferably made of one type of first resin. Become.
  • thermoplastic resins include polyolefin resins such as chain polyolefin resins and cyclic polyolefin resins; polyester resins; (meth)acrylic resins such as polymethyl methacrylate (PMMA); cellulose ester resins; polycarbonate.
  • PMMA polymethyl methacrylate
  • Polyvinyl alcohol resin; Polyvinyl acetate resin; Polyarylate resin; Polystyrene resin; Polyethersulfone resin; Polysulfone resin; Polyamide resin; Polyimide resin; and mixtures and copolymers thereof, etc. can be mentioned.
  • (meth)acrylic means at least one selected from acrylic and methacryl.
  • the first resin is preferably a thermoplastic resin that can be melted at a temperature that does not adversely affect the optical properties of the semiconductor particles during molding of the transparent resin film.
  • the first resin is preferably one or more heat-resistant resins selected from polystyrene resins and (meth)acrylic resins. It is a plastic resin, more preferably a polystyrene resin.
  • Polystyrene resin refers to a polymer or copolymer containing a structural unit derived from a styrene monomer.
  • polystyrene resins include polymers or copolymers of one or more styrene monomers; copolymers of rubber polymers (rubber elastic bodies) and one or more styrene monomers; Coalescence (rubber-modified polystyrene resin; also referred to as impact-resistant polystyrene resin); copolymer of one or more styrene monomers and one or more other monomers copolymerizable with the same. (Excluding rubber-modified polystyrene resins).
  • the first resin can include one or more polystyrene resins.
  • styrenic monomers include, in addition to styrene, ⁇ -methylstyrene, pt-butylstyrene, m- or p-methylstyrene, m- or p-ethylstyrene, ⁇ -methyl-p-methylstyrene, , ⁇ -substituted and/or nuclear-substituted styrene such as chlorostyrene, and the like.
  • rubber polymers include natural crepe rubber, polybutadiene, butadiene-styrene copolymer rubber, butadiene-acrylonitrile copolymer rubber, polyisoprene, polyisobutylene, isoprene-isobutylene copolymer rubber, polychloroprene, and ethylene-propylene copolymer rubber.
  • ethylene-propylene-diene monomer rubber styrene-butadiene block copolymer rubber, ethylene-vinyl acetate copolymer rubber, (meth)acrylic acid alkyl ester copolymer rubber, and the like.
  • Examples of other monomers that can be copolymerized with the styrenic monomer include (meth)acrylic acid ester, (meth)acrylic acid, maleic anhydride, vinylnaphthalene, bromostyrene, phenylmaleimide, acrylonitrile, etc. It will be done.
  • HIPS resins polybutadiene-grafted styrene polymers
  • HISMAA resins polybutadiene-grafted styrene-methacrylic acid copolymers
  • ABS resin polybutadiene-grafted styrene-acrylonitrile copolymers.
  • HIPS resin is preferred from the viewpoint of improving the surface hardness, surface appearance, bending resistance, curl resistance, etc. of the transparent resin film.
  • Copolymers of one or more styrene monomers and one or more other monomers include, for example, styrene-methyl methacrylate copolymer (MS resin), styrene-methacrylic acid copolymer (SMAA resin), styrene-acrylic acid copolymer (SAA resin), styrene-acrylonitrile copolymer (AS resin), and the like.
  • MS resin styrene-methyl methacrylate copolymer
  • SMAA resin styrene-methacrylic acid copolymer
  • SAA resin styrene-acrylic acid copolymer
  • AS resin styrene-acrylonitrile copolymer
  • the melt flow rate M1 of the first resin is preferably 0.5 g/10 minutes or more and 10 g/10 minutes or less, and more Preferably from 0.8 g/10 minutes to 8.0 g/10 minutes, more preferably from 1.0 g/10 minutes to 5.0 g/10 minutes, even more preferably from 2.0 g/10 minutes to 5.0 g/10 minutes. It is 10 minutes or less, particularly preferably 2.5 g/10 minutes or more and 5.0 g/10 minutes or less.
  • the melt flow rate of the resin such as the first resin is measured according to the description in the [Example] section below.
  • the content of the first resin in the first resin layer 10 is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably is 80% by mass or more, still more preferably 85% by mass or more, particularly preferably 90% by mass or more, for example 99.9% by mass or less, preferably 99.5% by mass or less, more preferably 99.0% by mass or less. % by mass or less.
  • the content of the first resin in the first resin layer 10 is within the above range, it is easy to improve the surface hardness, surface appearance, bending resistance, curl resistance, etc. of the transparent resin film.
  • the first resin layer 10 may contain other components other than the inorganic particles 15 and the first resin. Examples of other components include additives such as ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, color inhibitors, flame retardants, nucleating agents, and antistatic agents.
  • the first resin layer 10 may contain two or more types of additives.
  • Antioxidants are not particularly limited as long as they are commonly used industrially, and include phenolic antioxidants, phosphorus antioxidants, phosphorus/phenol complex antioxidants, and sulfur antioxidants. etc. can be used. Two or more kinds of antioxidants may be used.
  • a phosphorus/phenol composite antioxidant is, for example, a compound that has one or more phosphorus atoms and one or more phenol structures in its molecule. Among these, from the viewpoint of the luminescence intensity of the transparent resin film, it is preferable that the antioxidant includes a phosphorus/phenol composite type antioxidant.
  • phenolic antioxidant examples include Irganox (registered trademark) 1010 (Irganox 1010: pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Corporation) ), 1076 (Irganox 1076: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, manufactured by BASF Corporation), 1330 (Irganox 1330: 3,3',3) '',5,5',5''-hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol, manufactured by BASF Corporation) , 3114 (Irganox 3114: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2
  • phenolic antioxidant an antioxidant having a hindered phenol structure in which a bulky organic group is bonded to at least one ortho position of a phenolic hydroxy group is preferable.
  • the bulky organic group is preferably a secondary or tertiary alkyl group, and specific examples include isopropyl group, s-butyl group, t-butyl group, s-amyl group, and t-amyl group. Among these, a tertiary alkyl group is preferred, and a t-butyl group or a t-amyl group is particularly preferred.
  • Examples of the phosphorus antioxidant include Irgafos (registered trademark) 168 (Irgafos 168: tris(2,4-di-tert-butylphenyl) phosphite, manufactured by BASF Corporation) and Irgafos 12 (Irgafos 12: tris).
  • Examples of the phosphorus/phenol complex antioxidant include Sumilizer (registered trademark) GP (6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8, Examples include 10-tetra-tert-butyldibenz[d,f][1.3.2]dioxaphosphepine (manufactured by Sumitomo Chemical Co., Ltd.).
  • sulfur-based antioxidants include dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl or distearyl thiodipropionate, and ⁇ -alkylmercaptopropionate esters of polyols such as tetrakis[methylene(3-dodecylthio)propionate]methane. Examples include compounds.
  • the content of the antioxidant in the first resin layer 10 is, for example, 0.001% by mass or more and 10% by mass or less with respect to the total amount of the first resin layer 10. From the viewpoint of the luminescence intensity of the transparent resin film, preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.05% by mass or more and 2% by mass or less, even more preferably 0.1% by mass or more and 1% by mass. % or less.
  • ultraviolet absorbers examples include 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(5 -Methyl-2-hydroxyphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis( ⁇ , ⁇ -dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-dimethylbenzyl)phenyl -tert-butyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3,5 -di-tert-butyl-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3,5-di-tert-amyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2 Benzotriazole
  • Salicylic acid phenyl ester type UV absorber such as p-tert-butylphenyl salicylic acid ester, p-octylphenyl salicylic acid ester; 2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3 ,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-ethoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-propoxyphenyl)-1 , 3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-he
  • the ultraviolet absorber commercially available products may be used.
  • Kemisorb 102 manufactured by ChemiPro Kasei Co., Ltd.
  • ADEKA STAB LA46 ADEKA STAB LAF70
  • BASF Corporation ADEKA STAB LAF70
  • BASF Corporation ADEKA STAB LAF70
  • TINUVIN 460 manufactured by BASF Corporation.
  • TINUVIN 405, TINUVIN 400 and TINUVIN 477, and CYASORB UV-1164 manufactured by Sun Chemical Co., Ltd. all of the above are product names).
  • benzotriazole ultraviolet absorbers examples include ADEKA STAB LA31 and ADEKA STAB LA36 manufactured by ADEKA Co., Ltd., SUMISORB 200, SUMISORB 250, SUMISORB 300, SUMISORB 340 and SUMISORB 350 manufactured by Sumika Chemtex Co., Ltd., and Kemisorb manufactured by ChemiPro Kasei Co., Ltd. 74 , Kemisorb 79 and Kemisorb 279, TINUVIN 99-2, TINUVIN 360, TINUVIN 900 and TINUVIN 928 manufactured by BASF, JF-77, JF-79, JF-80, JF manufactured by Johoku Kagaku Kogyo Co., Ltd. -83, JF- 832, JAST-500, JF-90G, JF-95 (all of the above are trade names).
  • the content of the ultraviolet absorber in the first resin layer 10 is, for example, 0.001% by mass or more and 10% by mass or less with respect to the total amount of the first resin layer 10. Yes, from the viewpoint of improving the weather resistance of the transparent resin film, preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.05% by mass or more and 2% by mass or less, even more preferably 0.1% by mass or more. It is 1% by mass or less.
  • the average thickness T 1AV of the first resin layer 10 is preferably 50 ⁇ m. 500 ⁇ m or less, more preferably 70 ⁇ m or more and 400 ⁇ m or less, even more preferably 80 ⁇ m or more and 350 ⁇ m or less, even more preferably 100 ⁇ m or more and 300 ⁇ m or less, particularly preferably 150 ⁇ m or more and 250 ⁇ m or less.
  • the average thickness T 1AV of the first resin layer is the average value of the thickness T 1 of the first resin layer measured at three measurement points, and the details of the measurement method will be described in detail in the [Example] section.
  • the thickness T 1 of the first resin layer is also preferably within the above range.
  • the second resin layer 20 is a resin layer disposed on the first surface of the first resin layer 10.
  • the resin contained in the second resin layer 20 includes a second resin, and preferably the resin contained in the second resin layer 20 is made of the second resin.
  • the third resin layer 30 is a resin layer disposed on the second surface of the first resin layer 10 that faces the first surface.
  • the resin contained in the third resin layer 30 includes a third resin, and preferably, the resin contained in the third resin layer 30 is made of the third resin.
  • the first resin layer 10 contains a light scattering agent and inorganic particles 15 selected from luminescent semiconductor particles
  • the second resin layer 20 and the third resin layer 30 contain a light scattering agent and semiconductor particles. Contains no. This makes it easier to achieve both optical properties based on the inorganic particles 15 and mechanical strength in the transparent resin film.
  • the light scattering agent can be present near the semiconductor particles, which may be advantageous in improving the luminescence intensity of the transparent resin film.
  • the second resin layer 20 and the third resin layer 30 may each contain inorganic particles. However, the second resin layer 20 and the third resin layer 30 preferably do not contain luminescent semiconductor particles, and more preferably do not contain luminescent semiconductor particles and light scattering agents.
  • the second resin layer 20 and the third resin layer 30 contains an anti-blocking agent, and more preferably, both resin layers contain an anti-blocking agent. Contains an agent. Thereby, it is possible to suppress adhesion (blocking) of the films when the transparent resin films are made into a roll or when the transparent resin films in the sheet state are laminated. Furthermore, by containing an anti-blocking agent in one or both resin layers, the surface hardness of the transparent resin film can be increased.
  • the second resin layer 20 and the third resin layer 30 may each contain two or more types of anti-blocking agents.
  • the first resin layer 10 may contain an anti-blocking agent, it is preferable that the first resin layer 10 does not contain an anti-blocking agent since this tends to increase the luminescence intensity of the transparent resin film.
  • anti-blocking agents examples include inorganic particles made of silica, alumina, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, kaolin, hydrophobically treated products of these, etc.; (meth)acrylic resin, urethane resin, phenol resin. , silicone resin, fluororesin, polyamide, polyolefin such as polypropylene, polycarbonate, and the like.
  • a preferable example of the resin particles is (meth)acrylic resin particles.
  • the anti-blocking agent is preferably resin particles.
  • the anti-blocking agent is a resin particle
  • the anti-blocking agent present on the surface of the transparent resin film can improve not only the surface hardness of the transparent resin film but also the impact resistance. Furthermore, scattering of light emitted from the inside of the transparent resin film, preferably from the first resin layer, can be suppressed, and the transparency of the transparent resin film can be increased compared to the case where, for example, inorganic particles are included. Therefore, a decrease in the intensity of light emitted from the transparent resin film can be suppressed.
  • the anti-blocking agent is preferably a particle that has a small refractive index difference with the second resin or third resin in which it is dispersed.
  • the anti-blocking agent is preferably resin particles, more preferably (meth)acrylic resin particles.
  • the average particle size of the anti-blocking agent is preferably 1 ⁇ m or more and 45 ⁇ m or less, more preferably 2 ⁇ m or more and 30 ⁇ m or less, and even more preferably 3 ⁇ m, considering the surface hardness, impact resistance, bending resistance, and curl resistance of the transparent resin film.
  • the thickness is preferably 4 ⁇ m or more and 10 ⁇ m or less, and more preferably 4 ⁇ m or more and 10 ⁇ m or less.
  • the content of the anti-blocking agent in the resin layer is, for example, 0.01% by mass or more and 50% by mass or more with respect to the total amount of the resin layer. mass% or less, preferably 0.1 mass% or more and 30 mass% or less, more preferably 0.5 mass% or more and 20 mass% or less, still more preferably 1.0 mass% or more and 15 mass% or less, even more preferably is 3.0% by mass or more and 12% by mass or less, particularly preferably 5.0% by mass or more and 12% by mass or less.
  • the content of the anti-blocking agent in the resin layer is within the above range, adhesion (blocking) of the film can be suppressed when the transparent resin film is made into a roll or when the transparent resin films in the sheet state are laminated. In addition, it is easy to increase the luminous intensity of the transparent resin film. Furthermore, when the content of the anti-blocking agent in the resin layer is within the above range, the impact resistance of the transparent resin film can be improved.
  • the second resin and the third resin are each preferably a thermoplastic resin.
  • the second resin and the third resin may each contain two or more types of thermoplastic resins.
  • thermoplastic resins the description in (2-2) above is cited.
  • the resin contained in the second resin layer 20 may be made of one type of second resin, or may be made of two or more types of second resin, but is preferably made of one type of second resin.
  • the resin contained in the third resin layer 30 may be made of one type of third resin, or may be made of two or more types of third resin, but is preferably made of one type of third resin. Become.
  • the second resin and the third resin are respectively thermoplastic resins that can be melted at a temperature that does not adversely affect the optical properties of the semiconductor particles during molding of the transparent resin film. It is preferable that
  • the second resin and the third resin are preferably selected from polystyrene resins and (meth)acrylic resins from the viewpoint of improving the surface hardness, surface appearance, bending resistance, curl resistance, etc. of the transparent resin film, respectively.
  • One or more thermoplastic resins more preferably polystyrene resins.
  • the second resin and the third resin can each contain one or more polystyrene resins.
  • each of the second resin and the third resin is preferably a HIPS resin from the viewpoint of improving the surface hardness, surface appearance, bending resistance, curl resistance, etc. of the transparent resin film.
  • the first resin and the second resin may be the same or different.
  • the first resin and the third resin may be the same or different.
  • the second resin and the third resin may be the same or different.
  • the first resin, the second resin, and the third resin are preferably all thermoplastic resins, more preferably the same thermoplastic resin.
  • the transparent resin film has a first resin layer 10, a second resin layer 20, and a third resin layer 30, and the first resin, second resin, and third resin are HIPS resins.
  • the melt flow rate M 2 of the second resin and the melt flow rate M 3 of the third resin are each preferably 0.5 g. /10 minutes or more and 10 g/10 minutes or less, more preferably 0.8 g/10 minutes or more and 8.0 g/10 minutes or less, even more preferably 1.0 g/10 minutes or more and 5.0 g/10 minutes or less, even more preferably It is 2.0 g/10 minutes or more and 5.0 g/10 minutes or less, particularly preferably 2.5 g/10 minutes or more and 5.0 g/10 minutes or less.
  • the ratio M 3 /M 2 of the melt flow rate M 3 of the third resin to the melt flow rate M 2 of the second resin is preferably 0.5 or more and 2 or less, more preferably 0.7 or more and 1.5 or less, and It is preferably 0.9 or more and 1.2 or less, particularly preferably 1.
  • the content rate of the second resin in the second resin layer 20 and the content rate of the third resin in the third resin layer 30 are each, for example, 50% by mass or more, preferably 60% by mass, based on the total amount of the resin layer.
  • the above content is more preferably 70% by mass or more, still more preferably 80% by mass, even more preferably 85% by mass or more, particularly preferably 90% by mass or more, and, for example, 99.9% by mass or less, preferably 99. It is 5% by mass or less, more preferably 99.0% by mass or less, even more preferably 98.0% or less, even more preferably 96.0% or less.
  • the surface hardness, surface appearance, bending resistance, and curl resistance of the transparent resin film are etc. is easy to increase.
  • the second resin layer 20 and the third resin layer 30 can contain components other than the anti-blocking agent and the second resin or third resin. Examples of other components are the same as the additives described in (2-3) above.
  • the average thickness of the second resin layer 20 is T 2AV
  • the average thickness T 3AV of the third resin layer 30 is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, even more preferably 15 ⁇ m or more, even more preferably 20 ⁇ m or more, and preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less. , more preferably 100 ⁇ m or less, even more preferably 50 ⁇ m or less, particularly preferably 45 ⁇ m or less.
  • the average thickness T 2AV of the second resin layer and the average thickness T 3AV of the third resin layer are the average value of the thickness T 2 of the second resin layer measured at three measurement points, and the thickness T 2 of the third resin layer, respectively.
  • the details of the measurement method are described in the [Example] section. It is also preferable that the thickness T 2 of the second resin layer and the thickness T 3 of the third resin layer are each within the above ranges.
  • the standard deviation of the ratio T 2 /T of the thickness T 2 [ ⁇ m] of the second resin layer to the thickness (total thickness) T [ ⁇ m] of the transparent resin film is 0
  • the standard deviation of the ratio T 3 /T of the thickness T 3 [ ⁇ m] of the third resin layer to the thickness T [ ⁇ m] of the transparent resin film is 0.015 or less.
  • the standard deviation of T 2 /T and the standard deviation of T 3 /T are each preferably 0.0145 or less, more preferably 0.012 or less, and It is preferably 0.010 or less, even more preferably 0.008 or less, particularly preferably 0.005 or less.
  • the standard deviation of T 2 /T and the standard deviation of T 3 /T are each, for example, 0.0005 or more, and may be 0.001 or more.
  • the thickness T of the transparent resin film, the thicknesses T 1 , T 2 and T 3 of each resin layer, and the above standard deviation can be measured according to the description in the [Example] section below.
  • the measurement points within the plane of the transparent resin film when measuring the thickness T of the transparent resin film and the thicknesses T 1 , T 2 and T 3 of each resin layer are usually the same.
  • the sum of the standard deviation of T 2 /T and the standard deviation of T 3 /T is preferably 0.020 or less, and the sum is more It is preferably 0.018 or less, more preferably 0.015 or less, even more preferably 0.010 or less, particularly preferably 0.008 or less.
  • the sum is, for example, 0.001 or more, and may be 0.002 or more.
  • the average thickness T AV of the transparent resin film is preferably 55 ⁇ m or more and 900 ⁇ m or less, more preferably 75 ⁇ m or more and 700 ⁇ m or less, and even more preferably 95 ⁇ m or more, from the viewpoint of handling the film and making the display device to which the film is applied thinner. It is 550 ⁇ m or less, still more preferably 120 ⁇ m or more and 400 ⁇ m or less, particularly preferably 150 ⁇ m or more and 300 ⁇ m or less.
  • the average thickness T AV of the transparent resin film is the average value of the thickness T of the transparent resin film measured at three measurement points, and the details of the measurement method will be described in detail in the [Example] section.
  • the thickness T of the transparent resin film is also preferably within the above range.
  • the ratio T 1AV / T 2AV of the average thickness T 1AV [ ⁇ m] of the first resin layer to the average thickness T 2AV [ ⁇ m] of the second resin layer, and the ratio T 1AV /T 2AV of the average thickness T 3AV [ ⁇ m] of the third resin layer is preferably 30 or less, more preferably 20 or less, even more preferably 15 or less, even more preferably 12 or less, particularly preferably 10 Below, it is most preferably 7.0 or less, preferably 0.5 or more, more preferably 1.0 or more, still more preferably 2.0 or more, and even more preferably 3.0 or more.
  • the ratio T 3AV /T 2AV of the average thickness T 3AV of the third resin layer 30 to the average thickness T 2AV of the second resin layer 20 is preferably 0.5 or more and 2 or less, more preferably 0.7 or more and 1.5 or less. , more preferably 0.8 or more and 1.2 or less.
  • melt flow rate M1 and melt flow rate M2 are melt flow rates measured under the same conditions, specifically, in accordance with JIS K 7210, at 200 ° C. and under a load of 5 kg. Melt flow rate [g/10 minutes].
  • the value of A ⁇ B is more preferably 15 or less, still more preferably 12 or less, still more preferably 10 or less, especially Preferably it is 8 or less, most preferably 6 or less.
  • the value of A ⁇ B is preferably 1 or more, 2 or more, 3 or more, or 4 or more, since it is easy to improve the surface hardness, surface appearance, bending resistance, curl resistance, and luminescent properties of the transparent resin film. It's okay.
  • the value of B is determined because it becomes easier to achieve both optical properties based on the inorganic particles 15 and mechanical strength in the transparent resin film, and also depends on the surface hardness, surface appearance, bending resistance, curl resistance, etc. of the transparent resin film. From the viewpoint of increasing the .0, preferably 0.5 or more, more preferably 0.7 or more, even more preferably 0.9 or more, even more preferably 0.95 or more. Furthermore, by setting the value of B within the above range, the adhesion between the first resin layer 10 and the second resin layer 20 can be improved.
  • the ratio T 1AV /T 3AV of the average thickness T 1AV [ ⁇ m] of the first resin layer 10 to the average thickness T 3AV [ ⁇ m] of the third resin layer 30 is defined as A', and the melt flow rate M 3 of the third resin is
  • the transparent resin film has the formula (ii): A' ⁇ B' ⁇ 18 (ii) It is preferable to satisfy the following. Satisfying formula (ii) is further advantageous in improving the surface hardness, surface appearance, bending resistance, and curl resistance of the transparent resin film.
  • melt flow rate M1 and melt flow rate M3 are melt flow rates measured under the same conditions, specifically, in accordance with JIS K 7210, at 200 ° C. and under a load of 5 kg. Melt flow rate [g/10 minutes].
  • the value of A' ⁇ B' is more preferably 15 or less, still more preferably 12 or less, and even more preferably 10 or less. , particularly preferably 8 or less, most preferably 6 or less.
  • the value of A' ⁇ B' is preferably 1 or more, 2 or more, 3 or more, or 4 or more because it is easy to improve the surface hardness, surface appearance, bending resistance, curl resistance, and luminescent properties of the transparent resin film. It may be.
  • the value of B' is determined because it becomes easier to achieve both optical properties based on the inorganic particles 15 and mechanical strength in the transparent resin film. From the viewpoint of increasing the 1.0, preferably 0.5 or more, more preferably 0.7 or more, even more preferably 0.9 or more, even more preferably 0.95 or more. Furthermore, by setting the value of B' within the above range, the adhesion between the first resin layer 10 and the third resin layer 30 can be improved.
  • the transparent resin film includes a second resin layer 20, a first resin layer 10, and a third resin layer 30 in this order, and preferably satisfies any of the following, more preferably satisfies two or more of the following. and more preferably all of the following.
  • the ratio T 3 /T 2 is 0.8 or more and 1.2 or less.
  • the ratio M 3 /M 2 is 0.9 or more and 1.2 or less, preferably 1.
  • the first resin and the second or third resin are the same.
  • the second resin and the third resin are the same.
  • the second resin layer and the third resin layer have the same material composition.
  • Both A and A' are 30 or less, preferably 20 or less, more preferably 15 or less, still more preferably 12 or less, even more preferably 10 or less.
  • B and B' are the same.
  • Both A ⁇ B and A′ ⁇ B′ are 18 or less, preferably 15 or less, more preferably 12 or less, still more preferably 10 or less. In [g] above, "being the same” includes the case where one value is within the range of ⁇ 5% of the other value.
  • a transparent resin film has small variations in surface hardness on both sides. Further, the transparent resin film may have high surface hardness on both sides.
  • the pencil hardness of the surface of the second resin layer of the transparent resin film opposite to the first resin layer and the surface of the third resin layer opposite to the first resin layer are preferably HB or higher. . Pencil hardness can be measured according to the method described in the [Examples] section below.
  • the transparent resin film may have good surface appearance and curl resistance.
  • a transparent resin film with a good surface appearance has reduced or no flow marks (spotted patterns, etc.) that may be formed on the film surface during film molding.
  • a transparent resin film with good curl resistance is resistant to curling even when rolled. Furthermore, when the first resin layer contains luminescent semiconductor fine particles, flow marks are reduced, and the in-plane uniformity of light emission from the transparent resin film is likely to be improved.
  • the appearance of the surface of the transparent resin film can be visually confirmed.
  • the curl resistance of the transparent resin film can be evaluated by the distance [mm] measured by the method described in the [Examples] section below.
  • the distance is preferably 15 mm or less, more preferably 12 mm or less, even more preferably 10 mm or less.
  • the transparent resin film may have good bending resistance.
  • a transparent resin film with good bending resistance is unlikely to crack when folded in at least one direction, even if the film is folded with a radius of curvature of 4 mm.
  • the transparent resin film is not particularly limited, it is preferably manufactured by extrusion molding, and more preferably manufactured by coextrusion molding.
  • the transparent resin film is an extrusion molded product, preferably a coextrusion molded product.
  • HIPS resin HIPS resin as each of the first resin, second resin, and third resin from the viewpoint of easily making the thickness of each layer uniform.
  • a method for manufacturing a transparent resin film by coextrusion molding may include, for example, the following steps. Step (X) of preparing a first resin composition for the first resin layer; Step (Y-1) of preparing a second resin composition for the second resin layer; Step (Y-2) of preparing a third resin composition for the third resin layer; Step (Z) of manufacturing a transparent resin film by coextrusion molding using the first resin composition, the second resin composition, and the third resin composition.
  • the second resin composition and the third resin composition have the same composition, there is no need to provide a step (Y-2) separately from the step (Y-1), and the second resin composition is used as the third resin composition.
  • a composition may be used.
  • Step (X) is a step of preparing a first resin composition containing inorganic particles, a first resin, optional additives, etc. at a desired content, preferably through heating and melt-kneading. Step (X) may consist of a plurality of steps.
  • step (X) is a step of preparing a masterbatch (MB) containing a light scattering agent, which is an inorganic particle, and a first resin by heating and melt-kneading them;
  • the method may include a step of heating and melt-kneading each MB and a first resin to prepare an MB containing them; and a step of heating and melt-kneading each MB and a first resin to prepare a first resin composition containing them.
  • the additive can be contained in any or all of the multiple MBs.
  • Each MB may be prepared in pellet form. According to the method using MB, it is easy to prepare a first resin composition with uniform concentrations of inorganic particles and additives.
  • Preparation of the first resin composition and preparation of each MB by heating and melt-kneading can be carried out by a method in which predetermined components are put into an extruder such as a twin-screw extruder and then heated and melt-kneaded.
  • the temperature during heating and melt-kneading is, for example, 150°C or higher, preferably 180°C or higher, more preferably 200°C or higher, and, for example, 350°C or lower, preferably 320°C or lower, more preferably 300°C or lower, and still more preferably 280°C or lower.
  • the temperature is preferably 260°C or lower, particularly preferably 260°C or lower.
  • the mixture of predetermined components contains a solvent or water
  • a devolatilization treatment is performed to remove these during or after heating and melting and kneading. be able to.
  • a solvent is included in the mixture of predetermined components
  • semiconductor particles are introduced in the form of a dispersion liquid in which semiconductor particles are dispersed in a dispersion medium.
  • step (Y-1) and step (Y-2) can also be prepared in the same manner as the first resin composition.
  • step (Y-1) is a step of melt-kneading an anti-blocking agent and a second resin to prepare a MB containing them; and a step of melt-kneading an MB and a second resin to prepare a second resin containing them.
  • the method may include a step of preparing a resin composition. Additives can be included in the MB.
  • Coextrusion molding in step (Z) may be performed by a conventionally known method.
  • a first resin composition in a molten state prepared in a first extruder in step (X) and a second extruder different from the first extruder in steps (Y-1) and (Y-2) The second resin composition (and the third resin composition) in a molten state prepared in the above are supplied to a three-layer feedblock, and further coextruded from a T-die to form the first resin layer and the third resin composition.
  • a transparent resin film having two resin layers and a third resin layer can be manufactured.
  • the temperature of each resin composition during coextrusion is, for example, 150°C or higher, preferably 180°C or higher, more preferably 200°C or higher, and, for example, 350°C or lower, preferably 320°C or lower, more preferably 300°C or lower, The temperature is more preferably 280°C or lower, particularly preferably 260°C or lower.
  • a transparent resin film as a long product is obtained by passing the molten laminate extruded from the T-die through a forming/cooling roll.
  • coextrusion molding controlling the viscosity, extrusion speed and/or amount of each resin composition, controlling the pressing pressure between the molding and cooling rolls, and maintaining the temperature of the molding and cooling rolls uniformly. This makes it easy to obtain a transparent resin film with small variations in surface hardness on both sides.
  • the value of A (ratio T 1 /T 2 ) and the value of A' (ratio T 1 /T 3 ) of the transparent resin film can be adjusted, for example, by adjusting the supply speed ratio (extrusion amount ratio) of the resin composition to the feed block. It can be controlled by The thickness of each resin layer of the transparent resin film can be adjusted, for example, by adjusting the supply rate of the resin composition to the feed block, the opening width of the T-die discharge port, the gap between the rolls in the forming/cooling roll, etc. can be controlled by If the second resin layer and the third resin layer are different in composition or thickness, a third extruder for preparing the third resin composition may be separately prepared.
  • the method for producing a transparent resin film may include steps other than those described above.
  • the other steps include a step of trimming the longitudinal ends of the long transparent resin film, a step of winding up the long transparent resin film into a roll, and a step of winding the long transparent resin film into a roll. Examples include a step of cutting the film into sheets of predetermined size.
  • a display device includes the transparent resin film described above.
  • the display device include a liquid crystal display device, an organic EL display device, an inorganic EL display device, and the like.
  • the transparent resin film By placing the transparent resin film over the light source (the backlight of a liquid crystal display device, the EL display element of an organic EL display device or an inorganic EL display device) (on the viewing side), it can diffuse the light from the light source and change the wavelength. It can be suitably used as a film that performs conversion (ie, a diffusion film or a wavelength conversion film).
  • Measurement of thickness of transparent resin film and resin layer The cross section of the manufactured transparent resin film was exposed using a microtome. Three measurement points are randomly selected within the plane of the transparent resin film (hereinafter referred to as "measurement points 1 to 3"), and at each of measurement points 1 to 3, the first resin layer and the second resin layer are selected at random. And the thickness of the third resin layer was measured by cross-sectional observation using a laser microscope ("LEXT OLS4000" manufactured by Olympus Corporation). As a result, three measured values were obtained for each of the thickness T 1 of the first resin layer, the thickness T 2 of the second resin layer, and the thickness T 3 of the third resin layer.
  • the average value of the thickness T 1 of the first resin layer obtained for measurement points 1 to 3 is taken as the average value of the first resin layer thickness T 1AV
  • the thickness T 2 of the second resin layer obtained for measurement points 1 to 3 is The average value was taken as the average thickness T 2AV of the second resin layer
  • the average value of the thickness T 3 of the third resin layer obtained at measurement points 1 to 3 was taken as the average thickness T 3AV of the third resin layer.
  • the thickness T of the transparent resin film can be determined by calculating the sum of the thickness T 1 of the first resin layer, the thickness T 2 of the second resin layer, and the thickness T 3 of the third resin layer for each of measurement points 1 to 3. Three measurements were taken. The average value of the thickness T of the transparent resin film obtained for measurement points 1 to 3 was defined as the average thickness T AV of the transparent resin film.
  • test piece of 150 mm x 100 mm size was cut out from the manufactured transparent resin film so that the longitudinal direction was in the MD direction.
  • This test piece was wound around a resin core rod having a diameter of 16 mm, the ends were fixed with tape, and the test piece was left standing for 1 minute in an environment of a temperature of 25° C. and a relative humidity of 50% RH.
  • the test piece was removed from the core rod, placed on a horizontal stand with the convex surface of the curled test piece facing up, and the distance [mm] from the surface of the horizontal stand to the highest point of the test piece's convex portion was measured.
  • ⁇ Manufacture example 1 Preparation of glass beads MB for the first resin layer> HIPS resin pellets, glass beads (light scattering agent), antioxidant, and ultraviolet absorber were dry blended in a tumbler at the following blending ratio, and kneaded at a molding temperature of 200 to 260°C using a twin-screw extruder. The strand obtained from the extruder was cooled in a water bath and then cut with a pelletizer to obtain glass beads MB for the first resin layer in which glass beads were dispersed in the resin.
  • HIPS resin pellets (“SX100” manufactured by PS Japan, melt flow rate (MFR): 3.3 g/10 minutes) 76.0% by mass Glass beads (“UBS-0010E” manufactured by Unitika, main particle size: ⁇ 10 ⁇ m, density: 2.6 g/cm 3 ) 20.0% by mass Antioxidant (“Sumilyzer GP” manufactured by Sumitomo Chemical Co., Ltd.) 2.0% by mass Ultraviolet absorber (JF-77 manufactured by Johoku Kagaku Kogyo Co., Ltd.) 2.0% by mass
  • TiO 2 titanium oxide particles (TiO 2 ) particles (light scattering agent), antioxidant, and ultraviolet absorber were dry blended in a tumbler at the following blending ratio, and molded at a temperature of 200 to 260°C using a twin-screw extruder. It was kneaded with The strand obtained from the extruder was cooled in a water bath and then cut with a pelletizer to obtain titanium oxide particles MB for the first resin layer in which titanium oxide particles were dispersed in the resin.
  • HIPS resin pellets (“SX100” manufactured by PS Japan, melt flow rate (MFR): 3.3 g/10 minutes) 91.0% by mass Titanium oxide particles (median diameter based on volume: 0.2 ⁇ m, density: 4.2 g/cm 3 ) 5.0% by mass Antioxidant (“Sumilyzer GP” manufactured by Sumitomo Chemical Co., Ltd.) 2.0% by mass Ultraviolet absorber (JF-77 manufactured by Johoku Kagaku Kogyo Co., Ltd.) 2.0% by mass
  • ⁇ Production Example 3 Preparation of MB for second and third resin layers> HIPS resin pellets, an anti-blocking agent, an antioxidant, and an ultraviolet absorber were dry blended in a tumbler at the following blending ratio, and kneaded using a twin-screw extruder at a molding temperature of 200 to 260°C. After cooling the strand obtained from the extruder in a water bath, it was cut with a pelletizer to obtain MB for the second and third resin layers.
  • HIPS resin pellets (“SX100” manufactured by PS Japan, melt flow rate (MFR): 3.3 g/10 minutes) 77.0% by mass Anti-blocking agent (crosslinked PMMA particles “Gantz Pearl GM-0806S” manufactured by Aica Kogyo Co., Ltd. Average particle size: 8 ⁇ m) 20.0% by mass Antioxidant (“Sumilyzer GP” manufactured by Sumitomo Chemical Co., Ltd.) 2.0% by mass Ultraviolet absorber (JF-77 manufactured by Johoku Kagaku Kogyo Co., Ltd.) 1.0% by mass
  • Anti-blocking agent crosslinked PMMA particles “Gantz Pearl GM-0806S” manufactured by Aica Kogyo Co., Ltd. Average particle size: 8 ⁇ m
  • Antioxidant (“Sumilyzer GP” manufactured by Sumitomo Chemical Co., Ltd.) 2.0% by mass Ultraviolet absorber (JF-77 manufactured by Johoku Kagaku Kogyo Co., Ltd.) 1.
  • Example 1 Glass beads MB for the first resin layer prepared in Production Example 1, titanium oxide particles MB for the first resin layer prepared in Production Example 2, and HIPS resin pellets (same as those used for preparing MB) A predetermined amount of the mixture was put into a twin-screw extruder and heated and melted and kneaded at a temperature of 200 to 260°C to obtain a resin composition for the first resin layer in a molten state.
  • the composition of the resin composition is shown below.
  • composition of resin composition for first resin layer HIPS resin: 94.57% by mass Glass beads: 4.00% by mass Titanium oxide particles: 0.35% by mass Antioxidant: 0.54% by mass Ultraviolet absorber: 0.54% by mass
  • HIPS resin 91.26% by mass
  • Anti-blocking agent 7.60% by mass
  • Antioxidant 0.76% by mass
  • Ultraviolet absorber 0.38% by mass
  • the molten resin composition for the first resin layer and the resin compositions for the second and third resin layers obtained above were sent to a three-layer feed block, and further coextruded from a T-die.
  • the extruded molten laminate was passed through three forming/cooling rolls to obtain a transparent resin film having a second resin layer, a first resin layer, and a third resin layer in this order.
  • the total light transmittance was measured using a haze meter (HM-150) manufactured by Murakami Color Research Institute Co., Ltd. in accordance with JIS K 7361-1:1997, and it was found to be 56. It was 8%.
  • Example 2 By adjusting the feeding rate of the resin composition for the first resin layer and the resin composition for the second and third resin layers to the feed block, the thickness of the transparent resin film and the resin layers constituting it can be adjusted.
  • a transparent resin film was obtained as shown in Table 1 and by changing the conditions of the pressing pressure between the rolls from Example 1. The total light transmittance of the transparent resin film obtained by the above method was 56.6%.
  • Example 3 By adjusting the feeding rate of the resin composition for the first resin layer and the resin composition for the second and third resin layers to the feed block, the thickness of the transparent resin film and the resin layers constituting it can be adjusted.
  • a transparent resin film was obtained as shown in Table 1 and by changing the conditions of the pressing pressure between the rolls from Example 1. The total light transmittance of the transparent resin film obtained by the above method was 56.6%.
  • Example 4 A predetermined amount of titanium oxide particles MB for the first resin layer prepared in Production Example 2 and HIPS resin pellets (same as those used for preparing MB) were put into a twin screw extruder, and heated at 200 to 260°C. The resin composition was heated, melted and kneaded at a temperature of 1, to obtain a resin composition for the first resin layer in a molten state.
  • the composition of the resin composition is shown below.
  • composition of resin composition for first resin layer HIPS resin: 99.37% by mass Titanium oxide particles: 0.35% by mass Antioxidant: 0.14% by mass Ultraviolet absorber: 0.14% by mass
  • HIPS resin 91.26% by mass
  • Anti-blocking agent 7.60% by mass
  • Antioxidant 0.76% by mass
  • Ultraviolet absorber 0.38% by mass
  • the molten resin composition for the first resin layer and the resin compositions for the second and third resin layers obtained above were sent to a three-layer feed block, and further coextruded from a T-die.
  • the extruded molten laminate was passed through three forming/cooling rolls to obtain a transparent resin film having a second resin layer, a first resin layer, and a third resin layer in this order.
  • the total light transmittance of the transparent resin film obtained by the above method was 51.9%.
  • Example 5 By adjusting the feeding rate of the resin composition for the first resin layer and the resin composition for the second and third resin layers to the feed block, the thickness of the transparent resin film and the resin layers constituting it can be adjusted.
  • a transparent resin film was obtained as shown in Table 1 and by changing the conditions of the pressing pressure between the rolls from Example 4. The total light transmittance of the transparent resin film obtained by the above method was 51.9%.
  • Example 6> By adjusting the feeding rate of the resin composition for the first resin layer and the resin composition for the second and third resin layers to the feed block, the thickness of the transparent resin film and the resin layers constituting it can be adjusted.
  • a transparent resin film was obtained as shown in Table 1 and by changing the conditions of the pressing pressure between the rolls from Example 4. The total light transmittance of the transparent resin film obtained by the above method was 51.9%.
  • ⁇ Comparative example 1> By adjusting the feeding rate of the resin composition for the first resin layer and the resin composition for the second and third resin layers to the feed block, the thickness of the transparent resin film and the resin layers constituting it can be adjusted.
  • a transparent resin film was obtained as shown in Table 1 and by changing the conditions of the pressing pressure between the rolls from Example 4. The total light transmittance of the transparent resin film obtained by the above method was 51.9%.
  • Table 1 shows the measurement results and evaluation results according to the above ⁇ Measurement and Evaluation>.
  • a ⁇ B
  • A' ⁇ B The values of ' are also shown in Table 1.

Abstract

Provided is a transparent resin film including a first resin layer that contains a first resin, a second resin layer that is disposed on a first surface of the first resin layer and contains a second resin, and a third resin layer that is disposed on a second surface of the first resin layer opposite to the first surface and contains a third resin, wherein the first resin layer contains inorganic particles, and the standard deviation of T2/T and the standard deviation of T3/T are both equal to or less than 0.015, where T (μm) is the thickness of the transparent resin film, T2 (μm) is the thickness of the second resin layer, and T3 (μm) is the thickness of the third resin layer.

Description

透明樹脂フィルム及び表示装置Transparent resin film and display device
　本発明は、無機粒子を含有する透明樹脂フィルム、及び該透明樹脂フィルムを含む表示装置に関する。 The present invention relates to a transparent resin film containing inorganic particles and a display device including the transparent resin film.
　国際公開第２０１９／０７８１３５号（特許文献１）には、複数の樹脂層が積層され、少なくとも一層の樹脂層に量子ドットを含有する量子ドット含有樹脂シート又はフィルム、及びこれを用いた波長変換部材が記載されている。 International Publication No. 2019/078135 (Patent Document 1) discloses a quantum dot-containing resin sheet or film in which a plurality of resin layers are laminated and at least one resin layer contains quantum dots, and a wavelength conversion member using the same. is listed.
国際公開第２０１９／０７８１３５号International Publication No. 2019/078135
　本発明の１つの目的は、複数の樹脂層から構成され、無機粒子を含有する透明樹脂フィルムであって、表面硬度のバラツキが小さい透明樹脂フィルムを提供することにある。本発明の他の目的は、該透明樹脂フィルムを含む表示装置を提供することにある。 One object of the present invention is to provide a transparent resin film that is composed of a plurality of resin layers, contains inorganic particles, and has small variations in surface hardness. Another object of the present invention is to provide a display device including the transparent resin film.
　本発明は、以下に示される透明樹脂フィルム及び表示装置を提供する。
　［１］　第１樹脂を含有する第１樹脂層と、
　前記第１樹脂層の第１表面上に配置される樹脂層であって、第２樹脂を含有する第２樹脂層と、
　前記第１樹脂層の前記第１表面と対向する第２表面上に配置される樹脂層であって、第３樹脂を含有する第３樹脂層と、
を含む透明樹脂フィルムであって、
　前記第１樹脂層は、無機粒子を含有し、
　前記透明樹脂フィルムの厚みをＴ［μｍ］、前記第２樹脂層の厚みをＴ２［μｍ］、前記第３樹脂層の厚みをＴ３［μｍ］とするとき、Ｔ２／Ｔの標準偏差及びＴ３／Ｔの標準偏差がいずれも０．０１５以下である、透明樹脂フィルム。
　［２］　Ｔ２／Ｔの標準偏差とＴ３／Ｔの標準偏差との和が０．０２０以下である、［１］に記載の透明樹脂フィルム。
　［３］　前記第１樹脂層の平均厚みをＴ１ＡＶ［μｍ］、前記第２樹脂層の平均厚みをＴ２ＡＶ［μｍ］、前記第３樹脂層の平均厚みをＴ３ＡＶ［μｍ］とするとき、Ｔ１ＡＶ／Ｔ２ＡＶ及びＴ１ＡＶ／Ｔ３ＡＶがいずれも３０以下である、［１］又は［２］に記載の透明樹脂フィルム。
　［４］　前記無機粒子が光散乱剤を含む、［１］～［３］のいずれかに記載の透明樹脂フィルム。
　［５］　前記第１樹脂、前記第２樹脂及び前記第３樹脂がそれぞれ熱可塑性樹脂である、［１］～［４］のいずれかに記載の透明樹脂フィルム。
　［６］　前記第１樹脂層に含まれる樹脂は前記第１樹脂からなり、前記第２樹脂層に含まれる樹脂は前記第２樹脂からなり、前記第３樹脂層に含まれる樹脂は前記第３樹脂からなる、［１］～［５］のいずれかに記載の透明樹脂フィルム。
　［７］　前記第１樹脂と前記第２樹脂と前記第３樹脂とが同一である、［１］～［６］のいずれかに記載の透明樹脂フィルム。
　［８］　前記無機粒子が半導体粒子を含む、［１］～［７］のいずれかに記載の透明樹脂フィルム。
　［９］　押出成形品である、［１］～［８］のいずれかに記載の透明樹脂フィルム。
　［１０］　［１］～［９］のいずれかに記載の透明樹脂フィルムを含む表示装置。 The present invention provides a transparent resin film and a display device shown below.
[1] A first resin layer containing a first resin;
a second resin layer disposed on the first surface of the first resin layer, the second resin layer containing a second resin;
a third resin layer disposed on a second surface of the first resin layer opposite to the first surface, the third resin layer containing a third resin;
A transparent resin film comprising:
The first resin layer contains inorganic particles,
When the thickness of the transparent resin film is T [μm], the thickness of the second resin layer is T 2 [μm], and the thickness of the third resin layer is T 3 [μm], the standard deviation of T 2 /T is and a transparent resin film having a standard deviation of T 3 /T of 0.015 or less.
[2] The transparent resin film according to [1], wherein the sum of the standard deviation of T 2 /T and the standard deviation of T 3 /T is 0.020 or less.
[3] When the average thickness of the first resin layer is T 1AV [μm], the average thickness of the second resin layer is T 2AV [μm], and the average thickness of the third resin layer is T 3AV [μm]. , T 1AV /T 2AV and T 1AV /T 3AV are all 30 or less, the transparent resin film according to [1] or [2].
[4] The transparent resin film according to any one of [1] to [3], wherein the inorganic particles contain a light scattering agent.
[5] The transparent resin film according to any one of [1] to [4], wherein the first resin, the second resin, and the third resin are each thermoplastic resins.
[6] The resin contained in the first resin layer is made of the first resin, the resin contained in the second resin layer is made of the second resin, and the resin contained in the third resin layer is made of the third resin. The transparent resin film according to any one of [1] to [5], which is made of a resin.
[7] The transparent resin film according to any one of [1] to [6], wherein the first resin, the second resin, and the third resin are the same.
[8] The transparent resin film according to any one of [1] to [7], wherein the inorganic particles include semiconductor particles.
[9] The transparent resin film according to any one of [1] to [8], which is an extrusion molded product.
[10] A display device comprising the transparent resin film according to any one of [1] to [9].
　複数の樹脂層から構成され、無機粒子を含有する透明樹脂フィルムであって、表面硬度のバラツキが小さい透明樹脂フィルム、及びこれを含む表示装置を提供することができる。 It is possible to provide a transparent resin film that is composed of a plurality of resin layers, contains inorganic particles, and has small variations in surface hardness, and a display device including the same.
透明樹脂フィルムの一例を示す模式断面図である。It is a schematic cross-sectional view showing an example of a transparent resin film.
　＜透明樹脂フィルム＞
　本発明に係る透明樹脂フィルム（以下、単に「透明樹脂フィルム」ともいう。）は、無機粒子及び第１樹脂を含有する第１樹脂層と、第２樹脂を含有する第２樹脂層と、第３樹脂を含有する第３樹脂層とを含む多層構造の樹脂フィルムである。透明樹脂フィルムにおける「透明」とは、ＪＩＳ　Ｋ　７３６１－１：１９９７に準拠して測定される全光線透過率が３０％以上であることを意味する。全光線透過率は、好ましくは３５％以上、より好ましくは４０％以上、さらに好ましくは４５％以上であり、また、１００％以下であってもよく、９５％以下であってもよい。透明樹脂フィルムを構成する樹脂層のそれぞれが「透明」であることが好ましい。
　なお、本明細書において用語「フィルム」は、用語「シート」の意味をも包含する。 <Transparent resin film>
The transparent resin film according to the present invention (hereinafter also simply referred to as "transparent resin film") includes a first resin layer containing inorganic particles and a first resin, a second resin layer containing a second resin, and a second resin layer containing a second resin. It is a resin film with a multilayer structure including a third resin layer containing three resins. "Transparent" in a transparent resin film means that the total light transmittance measured in accordance with JIS K 7361-1:1997 is 30% or more. The total light transmittance is preferably 35% or more, more preferably 40% or more, even more preferably 45% or more, and may be 100% or less, or 95% or less. It is preferable that each of the resin layers constituting the transparent resin film is "transparent".
In addition, in this specification, the term "film" also includes the meaning of the term "sheet".
　透明樹脂フィルムは、光学用途のフィルム（光学フィルム）として好適に用いることができる。光学用途の例は、表示装置に用いられる光学部材としての用途である。 The transparent resin film can be suitably used as a film for optical applications (optical film). An example of optical use is use as an optical member used in a display device.
　透明樹脂フィルムは、その両面について表面硬度のバラツキが小さく、耐擦傷性に優れている。透明樹脂フィルムは、フィルム成形時にフィルム表面に形成され得るフローマーク（斑点模様等）が低減されていることにより表面の外観が良好なフィルムであり得る。透明樹脂フィルムは、ロール（巻回物）状態にしても巻癖が付きにくく、耐カール性が良好であり得る。また、透明樹脂フィルムは、良好な曲げ耐性を有し得る。
　以下、透明樹脂フィルムについて詳細に説明する。 A transparent resin film has small variations in surface hardness on both sides and has excellent scratch resistance. The transparent resin film may have a good surface appearance due to reduced flow marks (spot patterns, etc.) that may be formed on the film surface during film molding. A transparent resin film is less prone to curling even when rolled (wound), and may have good curl resistance. Moreover, the transparent resin film can have good bending resistance.
The transparent resin film will be explained in detail below.
　（１）透明樹脂フィルムの構成
　図１は、透明樹脂フィルムの一例を示す模式断面図である。図１に示される透明樹脂フィルムは、無機粒子１５を含有する第１樹脂層１０と、第１樹脂層１０の第１表面（一方の表面）上に配置される第２樹脂層２０と、第１樹脂層１０の第１表面と対向する第２表面（他方の表面）上に配置される第３樹脂層３０とからなる３層構造の樹脂フィルムである。 (1) Structure of transparent resin film FIG. 1 is a schematic cross-sectional view showing an example of a transparent resin film. The transparent resin film shown in FIG. 1 includes a first resin layer 10 containing inorganic particles 15, a second resin layer 20 disposed on the first surface (one surface) of the first resin layer 10, and It is a resin film with a three-layer structure consisting of a first surface of one resin layer 10 and a third resin layer 30 disposed on the opposing second surface (the other surface).
　第１樹脂層１０と第２樹脂層２０とは接していることが好ましく、第１樹脂層１０と第３樹脂層３０とは接していることが好ましい。 It is preferable that the first resin layer 10 and the second resin layer 20 are in contact with each other, and it is preferable that the first resin layer 10 and the third resin layer 30 are in contact with each other.
　（２）第１樹脂層
　第１樹脂層１０は、無機粒子１５を含有する樹脂層であり、無機粒子１５は通常、第１樹脂層１０中に分散されている。第１樹脂層１０に含まれる樹脂は第１樹脂を含み、好ましくは、第１樹脂層１０に含まれる樹脂は第１樹脂からなる。 (2) First Resin Layer The first resin layer 10 is a resin layer containing inorganic particles 15, and the inorganic particles 15 are normally dispersed in the first resin layer 10. The resin contained in the first resin layer 10 includes a first resin, and preferably, the resin contained in the first resin layer 10 is made of the first resin.
　（２－１）無機粒子
　第１樹脂層１０は、無機粒子１５を１種又は２種以上含有する。無機粒子１５の形状は特に制限されないが、好ましくは粒状であり、より好ましくは球状又は略球状である。無機粒子１５は単層構造であってもよいし、多層構造であってもよい。無機粒子１５の密度は、通常０．８ｇ／ｃｍ３以上であり、好ましくは０．９ｇ／ｃｍ３以上、より好ましくは１．０ｇ／ｃｍ３以上、さらに好ましくは１．０ｇ／ｃｍ３より大きく、なおさらに好ましくは２．０ｇ／ｃｍ３以上である。また、無機粒子１５の密度は、通常７．０ｇ／ｃｍ３以下であり、好ましくは６．０ｇ／ｃｍ３以下、より好ましくは５．０ｇ／ｃｍ３以下、さらに好ましくは４．５ｇ／ｃｍ３以下である。無機粒子１５の密度は、温度２５℃の環境下、ゲーリュサック型比重瓶を用いて測定することができる。無機粒子１５の密度が上記上限以下であると、無機粒子１５の沈降を抑制しやすく、第１樹脂層１０中での無機粒子１５の分布が均一になりやすいため、表面硬度のバラツキが小さくなりやすい。また、無機粒子１５の密度が上記下限以上であると、表面硬度等の機械的強度を高めやすい。 (2-1) Inorganic Particles The first resin layer 10 contains one or more types of inorganic particles 15. The shape of the inorganic particles 15 is not particularly limited, but is preferably granular, more preferably spherical or approximately spherical. The inorganic particles 15 may have a single layer structure or a multilayer structure. The density of the inorganic particles 15 is usually 0.8 g/cm 3 or more, preferably 0.9 g/cm 3 or more, more preferably 1.0 g/cm 3 or more, and still more preferably 1.0 g/cm 3 or more. , still more preferably 2.0 g/cm 3 or more. Further, the density of the inorganic particles 15 is usually 7.0 g/cm 3 or less, preferably 6.0 g/cm 3 or less, more preferably 5.0 g/cm 3 or less, even more preferably 4.5 g/cm 3 It is as follows. The density of the inorganic particles 15 can be measured using a Gerussac type pycnometer in an environment at a temperature of 25°C. When the density of the inorganic particles 15 is below the above upper limit, sedimentation of the inorganic particles 15 is easily suppressed, and the distribution of the inorganic particles 15 in the first resin layer 10 tends to be uniform, so that variations in surface hardness are reduced. Cheap. Moreover, when the density of the inorganic particles 15 is equal to or higher than the above lower limit, mechanical strength such as surface hardness is easily increased.
　第１樹脂層１０に含有される無機粒子１５としては、光散乱剤及び発光性（蛍光発光性）の半導体粒子（以下、単に「半導体粒子」ともいう。）等が挙げられる。
　光散乱剤としては、金属又は金属酸化物の粒子、ガラス粒子（ガラスビーズ等）等が挙げられる。光散乱剤は、着色による吸収が無く、散乱効果のみを有する方が好ましいことから、好ましくは金属酸化物の粒子であり、該金属酸化物としては、ＴｉＯ２、ＳｉＯ２、ＢａＴｉＯ３、ＺｎＯ等が挙げられ、効率的に光を散乱することから、好ましくはＴｉＯ２の粒子である。光散乱剤の体積基準のメディアン径は、例えば０．０３μｍ以上２０μｍ以下程度であり、好ましくは０．０５μｍ以上１μｍ以下であり、より好ましくは０．０５μｍ以上０．５μｍ以下である。第１樹脂層１０は、光散乱剤を２種以上含有していてもよい。 Examples of the inorganic particles 15 contained in the first resin layer 10 include light scattering agents and luminescent (fluorescent) semiconductor particles (hereinafter also simply referred to as "semiconductor particles").
Examples of the light scattering agent include metal or metal oxide particles, glass particles (glass beads, etc.), and the like. The light scattering agent is preferably a particle of a metal oxide, since it is preferable to have only a scattering effect without absorption due to coloring, and examples of the metal oxide include TiO 2 , SiO 2 , BaTiO 3 , ZnO, etc. Among them, TiO 2 particles are preferable because they scatter light efficiently. The volume-based median diameter of the light scattering agent is, for example, about 0.03 μm or more and 20 μm or less, preferably 0.05 μm or more and 1 μm or less, and more preferably 0.05 μm or more and 0.5 μm or less. The first resin layer 10 may contain two or more types of light scattering agents.
　半導体粒子は、一次光とは異なる波長の光を発し、好ましくは、一次光である青色の光の波長を、これとは異なる色の光の波長に変換する。半導体粒子は、緑色又は赤色を発光することが好ましく、青色光を吸収して緑色又は赤色を発光することがより好ましい。 The semiconductor particles emit light of a different wavelength from the primary light, and preferably convert the wavelength of blue light, which is the primary light, into the wavelength of light of a different color. The semiconductor particles preferably emit green or red light, and more preferably absorb blue light and emit green or red light.
　本明細書において「青色」とは、青色として視認される光全般（青色の波長域、例えば３８０ｎｍ～４９５ｎｍに強度を有する光全般）を指し、単一波長の光に限定されない。「緑色」とは、緑色として視認される光全般（緑色の波長域、例えば４９５ｎｍ～５８５ｎｍに強度を有する光全般）を指し、単一波長の光に限定されない。「赤色」とは、赤色として視認される光全般（赤色の波長域、例えば５８５ｎｍ～７８０ｎｍに強度を有する光全般）を指し、単一波長の光に限定されない。「黄色」とは、黄色として視認される光全般（黄色の波長域、例えば５６０ｎｍ～６１０ｎｍに強度を有する光全般）を指し、単一波長の光に限定されない。 In this specification, "blue" refers to all light that is visually recognized as blue (general light having an intensity in the blue wavelength range, for example, 380 nm to 495 nm), and is not limited to light of a single wavelength. "Green" refers to all light that is visually perceived as green (all light having an intensity in the green wavelength range, for example, 495 nm to 585 nm), and is not limited to light of a single wavelength. "Red" refers to light in general that is visually recognized as red (general light having an intensity in the red wavelength range, for example, 585 nm to 780 nm), and is not limited to light of a single wavelength. "Yellow" refers to all light that is visually perceived as yellow (all light having an intensity in the yellow wavelength range, for example, 560 nm to 610 nm), and is not limited to light of a single wavelength.
　緑色を発光する半導体粒子の発光スペクトルは、好ましくは、５００ｎｍ以上５６０ｎｍ以下の波長域に極大値を有するピークを含み、より好ましくは、５２０ｎｍ以上５４５ｎｍ以下の波長域に極大値を有するピークを含み、さらに好ましくは、５２５ｎｍ以上５４０ｎｍ以下の波長域に極大値を有するピークを含む。これにより、表示装置の緑色光の表示可能色域を拡大させることができる。該ピークは、好ましくは、半値全幅が１５ｎｍ以上８０ｎｍ以下、より好ましくは１５ｎｍ以上６０ｎｍ以下、さらに好ましくは１５ｎｍ以上５０ｎｍ以下、特に好ましくは１５ｎｍ以上４５ｎｍ以下である。これにより、表示装置の緑色光の表示可能色域を拡大させることができる。 The emission spectrum of the semiconductor particles that emit green light preferably includes a peak having a maximum value in a wavelength range of 500 nm or more and 560 nm or less, more preferably a peak having a maximum value in a wavelength range of 520 nm or more and 545 nm or less, More preferably, it includes a peak having a maximum value in a wavelength range of 525 nm or more and 540 nm or less. Thereby, the displayable color gamut of green light of the display device can be expanded. The full width at half maximum of the peak is preferably 15 nm or more and 80 nm or less, more preferably 15 nm or more and 60 nm or less, still more preferably 15 nm or more and 50 nm or less, particularly preferably 15 nm or more and 45 nm or less. Thereby, the displayable color gamut of green light of the display device can be expanded.
　赤色を発光する半導体粒子の発光スペクトルは、好ましくは、６１０ｎｍ以上７５０ｎｍ以下の波長域に極大値を有するピークを含み、より好ましくは、６１５ｎｍ以上６５０ｎｍ以下の波長域に極大値を有するピークを含み、さらに好ましくは、６２０ｎｍ以上６４０ｎｍ以下の波長域に極大値を有するピークを含む。これにより、表示装置の赤色光の表示可能色域を拡大させることができる。該ピークは、好ましくは、半値全幅が１５ｎｍ以上８０ｎｍ以下、より好ましくは１５ｎｍ以上６０ｎｍ以下、さらに好ましくは１５ｎｍ以上５０ｎｍ以下、特に好ましくは１５ｎｍ以上４５ｎｍ以下である。これにより、表示装置の赤色光の表示可能色域を拡大させることができる。 The emission spectrum of the semiconductor particles that emit red light preferably includes a peak having a maximum value in a wavelength range of 610 nm or more and 750 nm or less, more preferably a peak having a maximum value in a wavelength range of 615 nm or more and 650 nm or less, More preferably, it includes a peak having a maximum value in a wavelength range of 620 nm or more and 640 nm or less. Thereby, the displayable color gamut of red light of the display device can be expanded. The full width at half maximum of the peak is preferably 15 nm or more and 80 nm or less, more preferably 15 nm or more and 60 nm or less, still more preferably 15 nm or more and 50 nm or less, particularly preferably 15 nm or more and 45 nm or less. Thereby, the displayable color gamut of red light of the display device can be expanded.
　半導体粒子の発光スペクトルは、例えば、分光蛍光光度計や絶対ＰＬ量子収率測定装置（浜松ホトニクス製の「Ｃ９９２０－０２」、励起光４５０ｎｍ、室温、大気下）を用いて求めることができる。例えば、波長４５０ｎｍにおける吸光度が０．４となるように希釈した半導体粒子分散液を測定サンプルとして測定される。 The emission spectrum of the semiconductor particles can be determined using, for example, a spectrofluorophotometer or an absolute PL quantum yield measuring device (“C9920-02” manufactured by Hamamatsu Photonics, excitation light 450 nm, room temperature, in the atmosphere). For example, the measurement is performed using a semiconductor particle dispersion diluted so that the absorbance at a wavelength of 450 nm is 0.4.
　また、半導体粒子を含有する透明樹脂フィルムの発光スペクトルは、ピーク波長４５０ｎｍの青色ＬＥＤバックライト上に透明樹脂フィルムの測定サンプルを置き、透過光を分光放射計（トプコンテクノハウス社製の「ＳＲ－ＵＬ１Ｒ」）を用いて測定することで求めることができる。 In addition, the emission spectrum of a transparent resin film containing semiconductor particles was determined by placing a measurement sample of the transparent resin film on a blue LED backlight with a peak wavelength of 450 nm, and measuring the transmitted light with a spectroradiometer (“SR- UL1R").
　半導体粒子は、半導体結晶からなる粒子、好ましくは半導体結晶からなるナノ粒子である。半導体粒子の好ましい例としては、半導体量子ドット（以下、「量子ドット」ともいう。）及びペロブスカイト型結晶構造を有する化合物（以下、「ペロブスカイト化合物」ともいう。）の粒子が挙げられ、より好ましくは量子ドットである。量子ドットは、発光性半導体微粒子であり、半導体のバンドギャップを利用し、紫外光又は可視光（例えば青色光）を吸収して発光する微粒子である。 The semiconductor particles are particles made of semiconductor crystals, preferably nanoparticles made of semiconductor crystals. Preferred examples of semiconductor particles include semiconductor quantum dots (hereinafter also referred to as "quantum dots") and particles of compounds having a perovskite crystal structure (hereinafter also referred to as "perovskite compounds"), and more preferably It is a quantum dot. Quantum dots are luminescent semiconductor particles that emit light by absorbing ultraviolet light or visible light (for example, blue light) by utilizing the band gap of the semiconductor.
　量子ドットの平均粒径は、例えば０．５ｎｍ以上１００ｎｍ以下、好ましくは０．５ｎｍ以上２０ｎｍ以下、より好ましくは１ｎｍ以上１５ｎｍ以下（例えば２ｎｍ以上１５ｎｍ以下）である。量子ドットの平均粒径は、透過型電子顕微鏡（ＴＥＭ）を用いて求めることができる。量子ドットのエネルギー状態はその大きさに依存するため、粒子径を変えることにより自由に発光波長を選択することが可能である。例えば、ＣｄＳｅのみから構成される量子ドットの場合、粒子径が２．３ｎｍ、３．０ｎｍ、３．８ｎｍ、４．６ｎｍであるときの発光スペクトルのピーク波長は、それぞれ５２８ｎｍ、５７０ｎｍ、５９２ｎｍ、６３７ｎｍである。 The average particle size of the quantum dots is, for example, 0.5 nm or more and 100 nm or less, preferably 0.5 nm or more and 20 nm or less, and more preferably 1 nm or more and 15 nm or less (for example, 2 nm or more and 15 nm or less). The average particle size of quantum dots can be determined using a transmission electron microscope (TEM). Since the energy state of a quantum dot depends on its size, it is possible to freely select the emission wavelength by changing the particle size. For example, in the case of quantum dots made only of CdSe, the peak wavelengths of the emission spectrum when the particle diameters are 2.3 nm, 3.0 nm, 3.8 nm, and 4.6 nm are 528 nm, 570 nm, 592 nm, and 637 nm, respectively. It is.
　量子ドットとしては、例えば、ＣｄＳ、ＣｄＳｅ、ＣｄＴｅ、ＺｎＳ、ＺｎＳｅ、ＺｎＴｅ、ＨｇＳ、ＨｇＳｅ、ＨｇＴｅ、ＣｄＨｇＴｅ、ＣｄＳｅＳ、ＣｄＳｅＴｅ、ＣｄＳＴｅ、ＺｎＳｅＳ、ＺｎＳｅＴｅ、ＺｎＳＴｅ、ＨｇＳｅＳ、ＨｇＳｅＴｅ、ＨｇＳＴｅ、ＣｄＺｎＳ、ＣｄＺｎＳｅ、ＣｄＺｎＴｅ、ＣｄＨｇＳ、ＣｄＨｇＳｅ、ＣｄＨｇＴｅ、ＨｇＺｎＳ、ＨｇＺｎＳｅ、ＨｇＺｎＴｅ、ＣｄＺｎＳｅＳ、ＣｄＺｎＳｅＴｅ、ＣｄＺｎＳＴｅ、ＣｄＨｇＳｅＳ、ＣｄＨｇＳｅＴｅ、ＣｄＨｇＳＴｅ、ＨｇＺｎＳｅＳ、ＨｇＺｎＳｅＴｅ、ＨｇＺｎＳＴｅ等の１２族元素と１６族元素との化合物；ＧａＮ、ＧａＰ、ＧａＡｓ、ＡｌＮ、ＡｌＰ、ＡｌＡｓ、ＩｎＮ、ＩｎＰ、ＩｎＡｓ、ＧａＮＰ、ＧａＮＡｓ、ＧａＰＡｓ、ＡｌＮＰ、ＡｌＮＡｓ、ＡｌＰＡｓ、ＩｎＮＰ、ＩｎＮＡｓ、ＩｎＰＡｓ、ＧａＡｌＮＰ、ＧａＡｌＮＡｓ、ＧａＡｌＰＡｓ、ＧａＩｎＮＰ、ＧａＩｎＮＡｓ、ＧａＩｎＰＡｓ、ＩｎＡｌＮＰ、ＩｎＡｌＮＡｓ、ＩｎＡｌＰＡｓ等の１３族元素と１５族元素との化合物；ＰｄＳ、ＰｂＳｅ等の１４族元素と１６族元素との化合物等が挙げられる。 Examples of quantum dots include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, CdHgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, Hg STe, CdZnS, CdZnSe, CdZnTe , CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSe Compounds of group 12 elements such as Te and HgZnSTe and group 16 elements; GaN, GaP, GaAs, AlN , AlP, AlAs, InN, InP, InAs, GaNP, GaNAs, GaPAs, AlNP, AlNAs, AlPAs, InNP, InNAs, InPAs, GaAlNP, GaAlNAs, GaAlPAs, GaInNP, GaInNAs, GaInPAs, I Group 13 such as nAlNPs, InAlNAs, InAlPAs, etc. Compounds of elements and Group 15 elements; compounds of Group 14 elements and Group 16 elements, such as PdS and PbSe.
　量子ドットがＳやＳｅを含む場合、金属酸化物や有機物で表面修飾した量子ドットを使用してもよい。表面修飾した量子ドットを使用することで、組成物に含まれる又は含まれ得る反応成分によってＳやＳｅが引き抜かれることを防止することができる。
　また量子ドットは、上記の化合物を組み合わせてコアシェル構造を形成していてもよい。このような組み合わせとしては、コアがＣｄＳｅであり、シェルがＺｎＳである微粒子、コアがＩｎＰであり、シェルがＺｎＳｅＳである微粒子等が挙げられる。 When the quantum dots contain S or Se, quantum dots surface-modified with metal oxides or organic substances may be used. By using surface-modified quantum dots, it is possible to prevent S and Se from being extracted by reactive components that are or may be included in the composition.
Moreover, the quantum dot may form a core-shell structure by combining the above-mentioned compounds. Examples of such combinations include fine particles in which the core is CdSe and the shell is ZnS, and fine particles in which the core is InP and the shell is ZnSeS.
　量子ドットのエネルギー状態はその大きさに依存するため、粒子径を変えることにより自由に発光波長を選択することが可能である。また、量子ドットからの発光光はスペクトル幅が狭いため、表示装置の広色域化に有利である。さらに、量子ドットは応答性が高いため、一次光の利用効率の面でも有利である。 Since the energy state of a quantum dot depends on its size, it is possible to freely select the emission wavelength by changing the particle size. Furthermore, since the light emitted from the quantum dots has a narrow spectrum width, it is advantageous for widening the color gamut of a display device. Furthermore, since quantum dots have high responsiveness, they are also advantageous in terms of primary light utilization efficiency.
　量子ドットは、前述のとおり、単一の半導体材料からなる単層構造であってもよいし、単一の半導体材料からなる核粒子（コア層）の表面が、これとは異なる１種又は２種以上の半導体材料からなる被覆層（シェル層）によって被覆されたコアシェル構造であってもよい。後者の場合、シェル層を構成する半導体材料としては通常、コア層を構成する半導体材料よりもバンドギャップエネルギーが大きいものを用いる。量子ドットは、シェル層を２種以上有していてもよい。量子ドットの形状は特に限定されず、例えば、球状又は略球状、棒状、円盤状等であり得る。 As mentioned above, quantum dots may have a single layer structure made of a single semiconductor material, or the surface of a nuclear particle (core layer) made of a single semiconductor material may be made of one or two different types. It may be a core-shell structure covered with a covering layer (shell layer) made of one or more semiconductor materials. In the latter case, the semiconductor material constituting the shell layer usually has a larger bandgap energy than the semiconductor material constituting the core layer. The quantum dot may have two or more types of shell layers. The shape of the quantum dots is not particularly limited, and may be, for example, spherical or approximately spherical, rod-shaped, disc-shaped, or the like.
　ペロブスカイト化合物は、Ａ、Ｂ及びＸを成分とする、ペロブスカイト型結晶構造を有する化合物である。
　Ａは、ペロブスカイト型結晶構造において、Ｂを中心とする６面体の各頂点に位置する成分であって、１価の陽イオンである。
　Ｘは、ペロブスカイト型結晶構造において、Ｂを中心とする８面体の各頂点に位置する成分を表し、ハロゲン化物イオン及びチオシアン酸イオンからなる群より選ばれる少なくとも一種のイオンである。
　Ｂは、ペロブスカイト型結晶構造において、Ａを頂点に配置する６面体及びＸを頂点に配置する８面体の中心に位置する成分であって、金属イオンである。 A perovskite compound is a compound having a perovskite-type crystal structure containing A, B, and X as components.
In the perovskite crystal structure, A is a component located at each vertex of a hexahedron centered on B, and is a monovalent cation.
X represents a component located at each vertex of an octahedron centered on B in the perovskite crystal structure, and is at least one ion selected from the group consisting of halide ions and thiocyanate ions.
In the perovskite crystal structure, B is a component located at the center of the hexahedron with A at the apex and the octahedron with X at the apex, and is a metal ion.
　ペロブスカイト化合物からなる半導体粒子の平均粒径は、良好に結晶構造を維持させる観点から、好ましくは３ｎｍ以上、より好ましくは４ｎｍ以上、さらに好ましくは５ｎｍ以上である。また、ペロブスカイト化合物からなる半導体粒子の分散性の観点から、該半導体粒子の平均粒径は、好ましくは５μｍ以下、より好ましくは５００ｎｍ以下、さらに好ましくは１００ｎｍ以下である。ペロブスカイト化合物からなる半導体粒子の平均粒径は、透過型電子顕微鏡（ＴＥＭ）を用いて求めることができる。 The average particle diameter of the semiconductor particles made of a perovskite compound is preferably 3 nm or more, more preferably 4 nm or more, and still more preferably 5 nm or more, from the viewpoint of maintaining a good crystal structure. Further, from the viewpoint of dispersibility of the semiconductor particles made of a perovskite compound, the average particle size of the semiconductor particles is preferably 5 μm or less, more preferably 500 nm or less, and even more preferably 100 nm or less. The average particle size of semiconductor particles made of a perovskite compound can be determined using a transmission electron microscope (TEM).
　Ａ、Ｂ及びＸを成分とするペロブスカイト化合物としては、特に限定されず、３次元構造、２次元構造、疑似２次元構造のいずれの構造を有する化合物であってもよい。
　３次元構造の場合には、ペロブスカイト化合物は、ＡＢＸ（３＋δ）で表される。
　２次元構造の場合には、ペロブスカイト化合物は、Ａ２ＢＸ（４＋δ）で表される。
　ここで、δは、Ｂの電荷バランスに応じて適宜変更が可能な数であり、－０．７以上０．７以下である。 The perovskite compound containing A, B, and X as components is not particularly limited, and may be a compound having any structure such as a three-dimensional structure, a two-dimensional structure, or a pseudo-two-dimensional structure.
In the case of a three-dimensional structure, the perovskite compound is represented by ABX (3+δ) .
In the case of a two-dimensional structure, the perovskite compound is represented by A 2 BX (4+δ) .
Here, δ is a number that can be changed as appropriate depending on the charge balance of B, and is −0.7 or more and 0.7 or less.
　ペロブスカイト化合物であって、ＡＢＸ（３＋δ）で表される、３次元構造のペロブスカイト型の結晶構造を有する化合物の好ましい具体例としては、
　ＣＨ３ＮＨ３ＰｂＢｒ３、ＣＨ３ＮＨ３ＰｂＣｌ３、ＣＨ３ＮＨ３ＰｂＩ３、ＣＨ３ＮＨ３ＰｂＢｒ（３－ｙ）Ｉｙ（０＜ｙ＜３）、ＣＨ３ＮＨ３ＰｂＢｒ（３－ｙ）Ｃｌｙ（０＜ｙ＜３）、（Ｈ２Ｎ＝ＣＨ－ＮＨ２）ＰｂＢｒ３、（Ｈ２Ｎ＝ＣＨ－ＮＨ２）ＰｂＣｌ３、（Ｈ２Ｎ＝ＣＨ－ＮＨ２）ＰｂＩ３、
　ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＣａａＢｒ３（０＜ａ≦０．７）、ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＳｒａＢｒ３（０＜ａ≦０．７）、ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＬａａＢｒ（３＋δ）（０＜ａ≦０．７，０＜δ≦０．７）、ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＢａａＢｒ３（０＜ａ≦０．７）、ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＤｙａＢｒ（３＋δ）（０＜ａ≦０．７
，０＜δ≦０．７）、
　ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＮａａＢｒ（３＋δ）（０＜ａ≦０．７，－０．７≦δ＜０）、ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＬｉａＢｒ（３＋δ）（０＜ａ≦０．７，－０．７≦δ＜０）、
　ＣｓＰｂ（１－ａ）ＮａａＢｒ（３＋δ）（０＜ａ≦０．７，－０．７≦δ＜０）、ＣｓＰｂ（１－ａ）ＬｉａＢｒ（３＋δ）（０＜ａ≦０．７，－０．７≦δ＜０）、
　ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＮａａＢｒ（３＋δ－ｙ）Ｉｙ（０＜ａ≦０．７，－０．７≦δ＜０，０＜ｙ＜３）、ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＬｉａＢｒ（３＋δ－ｙ）Ｉｙ（０＜ａ≦０．７，－０．７≦δ＜０，０＜ｙ＜３）、ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＮａａＢｒ（３＋δ－ｙ）Ｃｌｙ（０＜ａ≦０．７，－０．７≦δ＜０，０＜ｙ＜３）、ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＬｉａＢｒ（３＋δ－ｙ）Ｃｌｙ（０＜ａ≦０．７，－０．７≦δ＜０，０＜ｙ＜３）、
　（Ｈ２Ｎ＝ＣＨ－ＮＨ２）Ｐｂ（１－ａ）ＮａａＢｒ（３＋δ）（０＜ａ≦０．７，－０．７≦δ＜０）、（Ｈ２Ｎ＝ＣＨ－ＮＨ２）Ｐｂ（１－ａ）ＬｉａＢｒ（３＋δ）（０＜ａ≦０．７，－０．７≦δ＜０）、（Ｈ２Ｎ＝ＣＨ－ＮＨ２）Ｐｂ（１－ａ）ＮａａＢｒ（３＋δ－ｙ）Ｉｙ（０＜ａ≦０．７，－０．７≦δ＜０，０＜ｙ＜３）、（Ｈ２Ｎ＝ＣＨ－ＮＨ２）Ｐｂ（１－ａ）ＮａａＢｒ（３＋δ－ｙ）Ｃｌｙ（０＜ａ≦０．７，－０．７≦δ＜０，０＜ｙ＜３）、
　ＣｓＰｂＢｒ３、ＣｓＰｂＣｌ３、ＣｓＰｂＩ３、ＣｓＰｂＢｒ（３－ｙ）Ｉｙ（０＜ｙ＜３）、ＣｓＰｂＢｒ（３－ｙ）Ｃｌｙ（０＜ｙ＜３）、ＣＨ３ＮＨ３ＰｂＢｒ（３－ｙ）Ｃｌｙ（０＜ｙ＜３）、
　ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＺｎａＢｒ３（０＜ａ≦０．７）、ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＡｌａＢｒ（３＋δ）（０＜ａ≦０．７，０≦δ≦０．７）、ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＣｏａＢｒ３（０＜ａ≦０．７）、ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＭｎａＢｒ３（０＜ａ≦０．７）、ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＭｇａＢｒ３（０＜ａ≦０．７）、
　ＣｓＰｂ（１－ａ）ＺｎａＢｒ３（０＜ａ≦０．７）、ＣｓＰｂ（１－ａ）ＡｌａＢｒ（３＋δ）（０＜ａ≦０．７，０＜δ≦０．７）、ＣｓＰｂ（１－ａ）ＣｏａＢｒ３（０＜ａ≦０．７）、ＣｓＰｂ（１－ａ）ＭｎａＢｒ３（０＜ａ≦０．７）、ＣｓＰｂ（１－ａ）ＭｇａＢｒ３（０＜ａ≦０．７）、
　ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＺｎａＢｒ（３－ｙ）Ｉｙ（０＜ａ≦０．７，０＜ｙ＜３）、ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＡｌａＢｒ（３＋δ－ｙ）Ｉｙ（０＜ａ≦０．７，０＜δ≦０．７，０＜ｙ＜３）、ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＣｏａＢｒ（３－ｙ）Ｉｙ（０＜ａ≦０．７，０＜ｙ＜３）、ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＭｎａＢｒ（３－ｙ）Ｉｙ（０＜ａ≦０．７，０＜ｙ＜３）、ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＭｇａＢｒ（３－ｙ）Ｉｙ（０＜ａ≦０．７，０＜ｙ＜３）、ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＺｎａＢｒ（３－ｙ）Ｃｌｙ（０＜ａ≦０．７，０＜ｙ＜３）、ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＡｌａＢｒ（３＋δ－ｙ）Ｃｌｙ（０＜ａ≦０．７，０＜δ≦０．７，０＜ｙ＜３）、ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＣｏａＢｒ（３＋δ－ｙ）Ｃｌｙ（０＜ａ≦０．７，０＜ｙ＜３）、ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＭｎａＢｒ（３－ｙ）Ｃｌｙ（０＜ａ≦０．７，０＜ｙ＜３）、ＣＨ３ＮＨ３Ｐｂ（１－ａ）ＭｇａＢｒ（３－ｙ）Ｃｌｙ（０＜ａ≦０．７，０＜ｙ＜３）、
　（Ｈ２Ｎ＝ＣＨ－ＮＨ２）ＺｎａＢｒ３（０＜ａ≦０．７）、（Ｈ２Ｎ＝ＣＨ－ＮＨ２）ＭｇａＢｒ３（０＜ａ≦０．７）、（Ｈ２Ｎ＝ＣＨ－ＮＨ２）Ｐｂ（１－ａ）ＺｎａＢｒ（３－ｙ）Ｉｙ（０＜ａ≦０．７，０＜ｙ＜３）、（Ｈ２Ｎ＝ＣＨ－ＮＨ２）Ｐｂ（１－ａ）ＺｎａＢｒ（３－ｙ）Ｃｌｙ（０＜ａ≦０．７，０＜ｙ＜３）等が挙げられる。 Preferred specific examples of perovskite compounds having a three-dimensional perovskite crystal structure represented by ABX (3+δ) include:
CH 3 NH 3 PbBr 3 , CH 3 NH 3 PbCl 3 , CH 3 NH 3 PbI 3 , CH 3 NH 3 PbBr (3-y) I y (0<y<3), CH 3 NH 3 PbBr (3-y ) Cl y (0<y<3), (H 2 N=CH-NH 2 )PbBr 3 , (H 2 N=CH-NH 2 )PbCl 3 , (H 2 N=CH-NH 2 )PbI 3 ,
CH 3 NH 3 Pb (1-a) Ca a Br 3 (0<a≦0.7), CH 3 NH 3 Pb (1-a) Sr a Br 3 (0<a≦0.7), CH 3 NH 3 Pb (1-a) La a Br (3+δ) (0<a≦0.7, 0<δ≦0.7), CH 3 NH 3 Pb (1-a) Ba a Br 3 (0<a ≦0.7), CH 3 NH 3 Pb (1-a) Dy a Br (3+δ) (0<a≦0.7
,0<δ≦0.7),
CH 3 NH 3 Pb (1-a) Na a Br (3+δ) (0<a≦0.7, -0.7≦δ<0), CH 3 NH 3 Pb (1-a) Li a Br (3+δ ) (0<a≦0.7, -0.7≦δ<0),
CsPb (1-a) Na a Br (3+δ) (0<a≦0.7, -0.7≦δ<0), CsPb (1-a) Li a Br (3+δ) (0<a≦0. 7, -0.7≦δ<0),
CH 3 NH 3 Pb (1-a) Na a Br (3+δ-y) I y (0<a≦0.7, -0.7≦δ<0, 0<y<3), CH 3 NH 3 Pb (1-a) Li a Br (3+δ-y) I y (0<a≦0.7, -0.7≦δ<0, 0<y<3), CH 3 NH 3 Pb (1-a) Na a Br (3+δ-y) Cl y (0<a≦0.7, -0.7≦δ<0, 0<y<3), CH 3 NH 3 Pb (1-a) Li a Br (3+δ -y) Cl y (0<a≦0.7, -0.7≦δ<0, 0<y<3),
(H 2 N=CH-NH 2 )Pb (1-a) Na a Br (3+δ) (0<a≦0.7, -0.7≦δ<0), (H 2 N=CH-NH 2 )Pb (1-a) Li a Br (3+δ) (0<a≦0.7, -0.7≦δ<0), (H 2 N=CH-NH 2 )Pb (1-a) Na a Br (3+δ-y) I y (0<a≦0.7, -0.7≦δ<0, 0<y<3), (H 2 N=CH-NH 2 )Pb (1-a) Na a Br (3+δ-y) Cl y (0<a≦0.7, -0.7≦δ<0, 0<y<3),
CsPbBr 3 , CsPbCl 3 , CsPbI 3 , CsPbBr (3-y) I y (0<y<3), CsPbBr (3-y) Cl y (0<y<3), CH 3 NH 3 PbBr (3-y ) Cl y (0<y<3),
CH 3 NH 3 Pb (1-a) Zna Br 3 (0<a≦0.7), CH 3 NH 3 Pb (1-a) Al a Br (3+δ) (0<a≦0.7,0 ≦δ≦0.7), CH 3 NH 3 Pb (1-a) Co a Br 3 (0<a≦0.7), CH 3 NH 3 Pb (1-a) Mn a Br 3 (0<a ≦0.7), CH 3 NH 3 Pb (1-a) Mga Br 3 (0<a≦0.7),
CsPb (1-a) Zn a Br 3 (0<a≦0.7), CsPb (1-a) Al a Br (3+δ) (0<a≦0.7, 0<δ≦0.7), CsPb (1-a) Co a Br 3 (0<a≦0.7), CsPb (1-a) Mna Br 3 (0<a≦0.7), CsPb (1-a) Mg a Br 3 (0<a≦0.7),
CH 3 NH 3 Pb (1-a) Zna Br (3-y) I y (0<a≦0.7, 0<y<3), CH 3 NH 3 Pb (1-a) Al a Br ( 3+δ-y) I y (0<a≦0.7, 0<δ≦0.7, 0<y<3), CH 3 NH 3 Pb (1-a) Co a Br (3-y) I y (0<a≦0.7, 0<y<3), CH 3 NH 3 Pb (1-a) Mn a Br (3-y) I y (0<a≦0.7, 0<y<3 ), CH 3 NH 3 Pb (1-a) Mga Br (3-y) I y (0<a≦0.7, 0<y<3), CH 3 NH 3 Pb (1-a) Zn a Br (3-y) Cl y (0<a≦0.7, 0<y<3), CH 3 NH 3 Pb (1-a) Al a Br (3+δ-y) Cl y (0<a≦0 .7,0<δ≦0.7,0<y<3), CH 3 NH 3 Pb (1-a) Co a Br (3+δ-y) Cl y (0<a≦0.7, 0<y <3), CH 3 NH 3 Pb (1-a) Mna Br (3-y) Cl y (0<a≦0.7, 0<y<3), CH 3 NH 3 Pb (1-a) Mg a Br (3-y) Cl y (0<a≦0.7, 0<y<3),
(H 2 N=CH-NH 2 )Zna Br 3 (0<a≦0.7), (H 2 N=CH-NH 2 )Mg a Br 3 (0<a≦0.7), (H 2 N=CH-NH 2 ) Pb (1-a) Zna Br (3-y) I y (0<a≦0.7, 0<y<3), (H 2 N=CH-NH 2 ) Examples include Pb (1-a) Zn a Br (3-y) Cl y (0<a≦0.7, 0<y<3).
　ペロブスカイト化合物であって、Ａ２ＢＸ（４＋δ）で表される、２次元構造のペロブスカイト型の結晶構造を有する化合物の好ましい具体例としては、
　（Ｃ４Ｈ９ＮＨ３）２ＰｂＢｒ４、（Ｃ４Ｈ９ＮＨ３）２ＰｂＣｌ４、（Ｃ４Ｈ９ＮＨ３）２ＰｂＩ４、（Ｃ７Ｈ１５ＮＨ３）２ＰｂＢｒ４、（Ｃ７Ｈ１５ＮＨ３）２ＰｂＣｌ４、（Ｃ７Ｈ１５ＮＨ３）２ＰｂＩ４、（Ｃ４Ｈ９ＮＨ３）２Ｐｂ（１－ａ）ＬｉａＢｒ
（４＋δ）（０＜ａ≦０．７，－０．７≦δ＜０）、（Ｃ４Ｈ９ＮＨ３）２Ｐｂ（１－ａ）ＮａａＢｒ（４＋δ）（０＜ａ≦０．７，－０．７≦δ＜０）、（Ｃ４Ｈ９ＮＨ３）２Ｐｂ（１－ａ）ＲｂａＢｒ（４＋δ）（０＜ａ≦０．７，－０．７≦δ＜０）、
　（Ｃ７Ｈ１５ＮＨ３）２Ｐｂ（１－ａ）ＮａａＢｒ（４＋δ）（０＜ａ≦０．７，－０．７≦δ＜０）、（Ｃ７Ｈ１５ＮＨ３）２Ｐｂ（１－ａ）ＬｉａＢｒ（４＋δ）（０＜ａ≦０．７，－０．７≦δ＜０）、（Ｃ７Ｈ１５ＮＨ３）２Ｐｂ（１－ａ）ＲｂａＢｒ（４＋δ）（０＜ａ≦０．７，－０．７≦δ＜０）、
　（Ｃ４Ｈ９ＮＨ３）２Ｐｂ（１－ａ）ＮａａＢｒ（４＋δ－ｙ）Ｉｙ（０＜ａ≦０．７，－０．７≦δ＜０，０＜ｙ＜４）、（Ｃ４Ｈ９ＮＨ３）２Ｐｂ（１－ａ）ＬｉａＢｒ（４＋δ－ｙ）Ｉｙ（０＜ａ≦０．７，－０．７≦δ＜０，０＜ｙ＜４）、（Ｃ４Ｈ９ＮＨ３）２Ｐｂ（１－ａ）ＲｂａＢｒ（４＋δ－ｙ）Ｉｙ（０＜ａ≦０．７，－０．７≦δ＜０，０＜ｙ＜４）、
　（Ｃ４Ｈ９ＮＨ３）２Ｐｂ（１－ａ）ＮａａＢｒ（４＋δ－ｙ）Ｃｌｙ（０＜ａ≦０．７，－０．７≦δ＜０，０＜ｙ＜４）、（Ｃ４Ｈ９ＮＨ３）２Ｐｂ（１－ａ）ＬｉａＢｒ（４＋δ－ｙ）Ｃｌｙ（０＜ａ≦０．７，－０．７≦δ＜０，０＜ｙ＜４）、（Ｃ４Ｈ９ＮＨ３）２Ｐｂ（１－ａ）ＲｂａＢｒ（４＋δ－ｙ）Ｃｌｙ（０＜ａ≦０．７，－０．７≦δ＜０，０＜ｙ＜４）、
　（Ｃ４Ｈ９ＮＨ３）２ＰｂＢｒ４、（Ｃ７Ｈ１５ＮＨ３）２ＰｂＢｒ４、
　（Ｃ４Ｈ９ＮＨ３）２ＰｂＢｒ（４－ｙ）Ｃｌｙ（０＜ｙ＜４）、（Ｃ４Ｈ９ＮＨ３）２ＰｂＢｒ（４－ｙ）Ｉｙ（０＜ｙ＜４）、
　（Ｃ４Ｈ９ＮＨ３）２Ｐｂ（１－ａ）ＺｎａＢｒ４（０＜ａ≦０．７）、（Ｃ４Ｈ９ＮＨ３）２Ｐｂ（１－ａ）ＭｇａＢｒ４（０＜ａ≦０．７）、（Ｃ４Ｈ９ＮＨ３）２Ｐｂ（１－ａ）ＣｏａＢｒ４（０＜ａ≦０．７）、（Ｃ４Ｈ９ＮＨ３）２Ｐｂ（１－ａ）ＭｎａＢｒ４（０＜ａ≦０．７）、
　（Ｃ７Ｈ１５ＮＨ３）２Ｐｂ（１－ａ）ＺｎａＢｒ４（０＜ａ≦０．７）、（Ｃ７Ｈ１５ＮＨ３）２Ｐｂ（１－ａ）ＭｇａＢｒ４（０＜ａ≦０．７）、（Ｃ７Ｈ１５ＮＨ３）２Ｐｂ（１－ａ）ＣｏａＢｒ４（０＜ａ≦０．７）、（Ｃ７Ｈ１５ＮＨ３）２Ｐｂ（１－ａ）ＭｎａＢｒ４（０＜ａ≦０．７）、
　（Ｃ４Ｈ９ＮＨ３）２Ｐｂ（１－ａ）ＺｎａＢｒ（４－ｙ）Ｉｙ（０＜ａ≦０．７，０＜ｙ＜４）、（Ｃ４Ｈ９ＮＨ３）２Ｐｂ（１－ａ）ＭｇａＢｒ（４－ｙ）Ｉｙ（０＜ａ≦０．７，０＜ｙ＜４）、（Ｃ４Ｈ９ＮＨ３）２Ｐｂ（１－ａ）ＣｏａＢｒ（４－ｙ）Ｉｙ（０＜ａ≦０．７，０＜ｙ＜４）、（Ｃ４Ｈ９ＮＨ３）２Ｐｂ（１－ａ）ＭｎａＢｒ（４－ｙ）Ｉｙ（０＜ａ≦０．７，０＜ｙ＜４）、
　（Ｃ４Ｈ９ＮＨ３）２Ｐｂ（１－ａ）ＺｎａＢｒ（４－ｙ）Ｃｌｙ（０＜ａ≦０．７，０＜ｙ＜４）、（Ｃ４Ｈ９ＮＨ３）２Ｐｂ（１－ａ）ＭｇａＢｒ（４－ｙ）Ｃｌｙ（０＜ａ≦０．７，０＜ｙ＜４）、（Ｃ４Ｈ９ＮＨ３）２Ｐｂ（１－ａ）ＣｏａＢｒ（４－ｙ）Ｃｌｙ（０＜ａ≦０．７，０＜ｙ＜４）、（Ｃ４Ｈ９ＮＨ３）２Ｐｂ（１－ａ）ＭｎａＢｒ（４－ｙ）Ｃｌｙ（０＜ａ≦０．７，０＜ｙ＜４）等が挙げられる。 Preferred specific examples of perovskite compounds having a two-dimensional perovskite crystal structure represented by A 2 BX (4+δ) include:
( C4H9NH3 ) 2PbBr4 , ( C4H9NH3 ) 2PbCl4 , ( C4H9NH3 ) 2PbI4 , ( C7H15NH3 ) 2PbBr4 , ( C 7 H 15 NH 3 ) 2 PbCl 4 , (C 7 H 15 NH 3 ) 2 PbI 4 , (C 4 H 9 NH 3 ) 2 Pb (1-a) Li a Br
(4+δ) (0<a≦0.7, -0.7≦δ<0), (C 4 H 9 NH 3 ) 2 Pb (1-a) Na a Br (4+δ) (0<a≦0. 7, -0.7≦δ<0), (C 4 H 9 NH 3 ) 2 Pb (1-a) Rb a Br (4+δ) (0<a≦0.7, -0.7≦δ<0 ),
(C 7 H 15 NH 3 ) 2 Pb (1-a) Na a Br (4+δ) (0<a≦0.7, -0.7≦δ<0), (C 7 H 15 NH 3 ) 2 Pb (1-a) Li a Br (4+δ) (0<a≦0.7, -0.7≦δ<0), (C 7 H 15 NH 3 ) 2 Pb (1-a) RbaBr (4+δ) ( 0<a≦0.7, -0.7≦δ<0),
(C 4 H 9 NH 3 ) 2 Pb (1-a) Na a Br (4+δ-y) I y (0<a≦0.7, -0.7≦δ<0, 0<y<4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Li a Br (4+δ-y) I y (0<a≦0.7, -0.7≦δ<0, 0<y<4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Rb a Br (4+δ-y) I y (0<a≦0.7, -0.7≦δ<0, 0<y<4),
(C 4 H 9 NH 3 ) 2 Pb (1-a) Na a Br (4+δ-y) Cl y (0<a≦0.7, -0.7≦δ<0, 0<y<4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Li a Br (4+δ-y) Cl y (0<a≦0.7, -0.7≦δ<0, 0<y<4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Rb a Br (4+δ-y) Cl y (0<a≦0.7, -0.7≦δ<0, 0<y<4),
(C 4 H 9 NH 3 ) 2 PbBr 4 , (C 7 H 15 NH 3 ) 2 PbBr 4 ,
(C 4 H 9 NH 3 ) 2 PbBr (4-y) Cl y (0<y<4), (C 4 H 9 NH 3 ) 2 PbBr (4-y) I y (0<y<4),
(C 4 H 9 NH 3 ) 2 Pb (1-a) Zna Br 4 (0<a≦0.7), (C 4 H 9 NH 3 ) 2 Pb (1-a) Mg a Br 4 (0 <a≦0.7), (C 4 H 9 NH 3 ) 2 Pb (1-a) Co a Br 4 (0<a≦0.7), (C 4 H 9 NH 3 ) 2 Pb (1- a) Mn a Br 4 (0<a≦0.7),
(C 7 H 15 NH 3 ) 2 Pb (1-a) Zna Br 4 (0<a≦0.7), (C 7 H 15 NH 3 ) 2 Pb (1-a) Mg a Br 4 (0 <a≦0.7), (C 7 H 15 NH 3 ) 2 Pb (1-a) Co a Br 4 (0< a≦0.7), (C 7 H 15 NH 3 ) 2 Pb (1- a) Mn a Br 4 (0<a≦0.7),
(C 4 H 9 NH 3 ) 2 Pb (1-a) Zna Br (4-y) I y (0<a≦0.7, 0<y<4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Mg a Br (4-y) I y (0<a≦0.7, 0<y<4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Co a Br (4-y) I y (0<a≦0.7, 0<y<4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Mn a Br (4-y) I y (0 <a≦0.7, 0<y<4),
(C 4 H 9 NH 3 ) 2 Pb (1-a) Zna Br (4-y) Cl y (0<a≦0.7, 0<y<4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Mg a Br (4-y) Cl y (0<a≦0.7, 0<y<4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Co a Br (4-y) Cl y (0<a≦0.7, 0<y<4), (C 4 H 9 NH 3 ) 2 Pb (1-a) Mn a Br (4-y) Cl y (0 <a≦0.7, 0<y<4), etc.
　第１樹脂層は、半導体粒子を２種以上含有していてもよい。例えば、第１樹脂層は、一次光を吸収して緑色を発光する半導体粒子を１種のみ含有していてもよく、２種以上組み合わせて含有していてもよい。第１樹脂層は、一次光を吸収して赤色を発光する半導体粒子を１種のみ含有していてもよく、２種以上組み合わせて含有していてもよい。 The first resin layer may contain two or more types of semiconductor particles. For example, the first resin layer may contain only one type of semiconductor particles that absorb primary light and emit green light, or may contain a combination of two or more types. The first resin layer may contain only one type of semiconductor particles that absorb primary light and emit red light, or may contain a combination of two or more types.
　第１樹脂層１０は、無機粒子１５を１種のみ含有していてもよいし、２種以上の無機粒子１５を含有していてもよい。第１樹脂層１０に含まれる無機粒子１５の含有率（２種以上の無機粒子１５が含まれる場合にはそれらの合計含有率）は、透明樹脂フィルムの表面硬度、曲げ耐性及び耐カール性等を高める観点から、第１樹脂層１０の総量に対して、例えば、０．０５質量％以上であり、好ましくは０．１０質量％以上、より好ましくは０．１５質量％以上、さらに好ましくは０．２０質量％以上、なおさらに好ましくは０．２５質量％以上、特に好ましくは０．３０質量％以上であり、好ましくは５０質量％以下、より好ましくは３０質量％以下、さらに好ましくは２０質量％以下、なおさらに好ましくは１０質量％以下、特に好ましくは７質量％以下である。 The first resin layer 10 may contain only one type of inorganic particles 15, or may contain two or more types of inorganic particles 15. The content of the inorganic particles 15 contained in the first resin layer 10 (if two or more types of inorganic particles 15 are included, the total content) is determined by the surface hardness, bending resistance, curl resistance, etc. of the transparent resin film. From the viewpoint of increasing the amount, the amount is, for example, 0.05% by mass or more, preferably 0.10% by mass or more, more preferably 0.15% by mass or more, and even more preferably 0. .20% by mass or more, even more preferably 0.25% by mass or more, particularly preferably 0.30% by mass or more, preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass. The content is still more preferably 10% by mass or less, particularly preferably 7% by mass or less.
　第１樹脂層１０は、光散乱剤を１種又は２種以上含有することができる。第１樹脂層１０は、半導体粒子を１種又は２種以上含有することができる。例えば、第１樹脂層１０は、赤色発光性の半導体粒子と緑色発光性の半導体粒子とを含有することができる。また、第１樹脂層１０は、１種又２種以上の光散乱剤と１種又２種以上の半導体粒子とを含有することができる。第１樹脂層１０に光散乱剤及び発光性の半導体粒子の両方を含有させることにより、半導体粒子の近傍に光散乱剤を存在させることができるため、透明樹脂フィルムの発光強度向上に有利となり得る。 The first resin layer 10 can contain one or more light scattering agents. The first resin layer 10 can contain one or more types of semiconductor particles. For example, the first resin layer 10 can contain red-emitting semiconductor particles and green-emitting semiconductor particles. Moreover, the first resin layer 10 can contain one or more types of light scattering agents and one or more types of semiconductor particles. By containing both the light scattering agent and the luminescent semiconductor particles in the first resin layer 10, the light scattering agent can be present in the vicinity of the semiconductor particles, which may be advantageous in improving the luminescence intensity of the transparent resin film. .
　無機粒子１５が光散乱剤を含む場合、第１樹脂層１０における光散乱剤の含有率（２種以上の光散乱剤が含まれる場合にはそれらの合計含有率）は、第１樹脂層１０の総量に対して、例えば０．０１質量％以上であり、好ましくは０．０５質量％以上、より好ましくは０．０８質量％以上、さらに好ましくは０．１０質量％以上、なおさらに好ましくは０．１５質量％以上、特に好ましくは０．２０質量％以上であり、好ましくは３０質量％以下、より好ましくは２０質量％以下、さらに好ましくは１０質量％以下、なおさらに好ましくは５．０質量％以下、特に好ましくは２．０質量％以下、特により好ましくは１．０質量％以下、最も好ましくは０．５質量％以下である。第１樹脂層１０における光散乱剤の含有率が上記範囲であると、透明樹脂フィルムの表面硬度、曲げ耐性、耐カール性、光散乱性能及び／又は発光強度を高めやすい。 When the inorganic particles 15 include a light-scattering agent, the content of the light-scattering agent in the first resin layer 10 (if two or more types of light-scattering agents are included, the total content) is the same as that of the first resin layer 10 Based on the total amount of .15% by weight or more, particularly preferably 0.20% by weight or more, preferably 30% by weight or less, more preferably 20% by weight or less, even more preferably 10% by weight or less, even more preferably 5.0% by weight. The content is particularly preferably 2.0% by mass or less, particularly preferably 1.0% by mass or less, and most preferably 0.5% by mass or less. When the content of the light scattering agent in the first resin layer 10 is within the above range, the surface hardness, bending resistance, curl resistance, light scattering performance, and/or emission intensity of the transparent resin film can be easily improved.
　無機粒子１５が半導体粒子を含む場合、第１樹脂層１０における半導体粒子の含有率（２種以上の半導体粒子が含まれる場合にはそれらの合計含有率）は、第１樹脂層１０の総量に対して、例えば０．０１質量％以上であり、好ましくは０．０５質量％以上、より好ましくは０．１０質量％以上、さらに好ましくは０．１５質量％以上、なおさらに好ましくは０．２０質量％以上、特に好ましくは０．２５質量％以上であり、好ましくは３０質量％以下、より好ましくは１０質量％以下、さらに好ましくは５．０質量％以下、なおさらに好ましくは３．０質量％以下である。第１樹脂層１０における半導体粒子の含有率が上記範囲であると、透明樹脂フィルムの表面硬度、曲げ耐性、耐カール性及び発光強度を高めやすい。 When the inorganic particles 15 include semiconductor particles, the content rate of the semiconductor particles in the first resin layer 10 (if two or more types of semiconductor particles are included, the total content rate) is equal to the total amount of the first resin layer 10. For example, it is 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.10% by mass or more, still more preferably 0.15% by mass or more, even more preferably 0.20% by mass. % or more, particularly preferably 0.25% by mass or more, preferably 30% by mass or less, more preferably 10% by mass or less, still more preferably 5.0% by mass or less, even more preferably 3.0% by mass or less. It is. When the content of semiconductor particles in the first resin layer 10 is within the above range, the surface hardness, bending resistance, curl resistance, and luminescence intensity of the transparent resin film can be easily increased.
　無機粒子１５が半導体粒子及び光散乱剤を含む場合、光散乱剤の含有量に対する半導体粒子の含有量の比は、好ましくは０．１以上１５以下、より好ましくは０．２以上１０以下、さらに好ましくは０．３以上８．０以下、なおさらに好ましくは０．５以上５．０以下である。光散乱剤の含有量に対する半導体粒子の含有量の比が上記範囲であると、半導体粒子の発光を効率よく外部に射出しやすく、透明樹脂フィルムの発光強度を高めやすい。 When the inorganic particles 15 include semiconductor particles and a light scattering agent, the ratio of the content of the semiconductor particles to the content of the light scattering agent is preferably 0.1 or more and 15 or less, more preferably 0.2 or more and 10 or less, and It is preferably 0.3 or more and 8.0 or less, even more preferably 0.5 or more and 5.0 or less. When the ratio of the content of the semiconductor particles to the content of the light scattering agent is within the above range, it is easy to efficiently emit light from the semiconductor particles to the outside, and it is easy to increase the light emission intensity of the transparent resin film.
　無機粒子１５が赤色発光性の半導体粒子と緑色発光性の半導体粒子とを含有する場合、該透明樹脂フィルムは白色光を発する波長変換フィルムとして好適に用いることができる。赤色発光性の半導体粒子の含有量に対する緑色発光性の半導体粒子の含有量の比は、好ましくは０．１以上６０以下、より好ましくは１以上５０以下、さらに好ましくは５以上４５以下、なおさらに好ましくは１０以上４０以下である。赤色発光性の半導体粒子の含有量に対する緑色発光性の半導体粒子の含有量の比が上記範囲であると、所望の白色光を得やすい。 When the inorganic particles 15 contain red-emitting semiconductor particles and green-emitting semiconductor particles, the transparent resin film can be suitably used as a wavelength conversion film that emits white light. The ratio of the content of green-emitting semiconductor particles to the content of red-emitting semiconductor particles is preferably 0.1 or more and 60 or less, more preferably 1 or more and 50 or less, still more preferably 5 or more and 45 or less. Preferably it is 10 or more and 40 or less. When the ratio of the content of green-emitting semiconductor particles to the content of red-emitting semiconductor particles is within the above range, desired white light can be easily obtained.
　（２－２）第１樹脂
　第１樹脂層１０は、第１樹脂を含む。好ましくは、第１樹脂層１０に含まれる樹脂は第１樹脂からなる。第１樹脂は、好ましくは熱可塑性樹脂である。第１樹脂は、２種以上の熱可塑性樹脂を含んでいてもよい。
　第１樹脂層１０に含まれる樹脂は、１種の第１樹脂からなっていてもよいし、２種以上の第１樹脂からなっていてもよいが、好ましくは、１種の第１樹脂からなる。 (2-2) First Resin The first resin layer 10 includes a first resin. Preferably, the resin contained in the first resin layer 10 is made of a first resin. The first resin is preferably a thermoplastic resin. The first resin may contain two or more types of thermoplastic resins.
The resin contained in the first resin layer 10 may be made of one type of first resin, or may be made of two or more types of first resin, but is preferably made of one type of first resin. Become.
　熱可塑性樹脂としては、例えば、鎖状ポリオレフィン系樹脂、環状ポリオレフィン系樹脂等のポリオレフィン系樹脂；ポリエステル系樹脂；ポリメタクリル酸メチル（ＰＭＭＡ）等の（メタ）アクリル系樹脂；セルロースエステル系樹脂；ポリカーボネート系樹脂；ポリビニルアルコール系樹脂；ポリ酢酸ビニル系樹脂；ポリアリレート系樹脂；ポリスチレン系樹脂；ポリエーテルスルホン系樹脂；ポリスルホン系樹脂；ポリアミド系樹脂；ポリイミド系樹脂；及びこれらの混合物、共重合物等が挙げられる。本明細書において「（メタ）アクリル」とは、アクリル及びメタクリルから選択される少なくとも一方を意味する。 Examples of thermoplastic resins include polyolefin resins such as chain polyolefin resins and cyclic polyolefin resins; polyester resins; (meth)acrylic resins such as polymethyl methacrylate (PMMA); cellulose ester resins; polycarbonate. Polyvinyl alcohol resin; Polyvinyl acetate resin; Polyarylate resin; Polystyrene resin; Polyethersulfone resin; Polysulfone resin; Polyamide resin; Polyimide resin; and mixtures and copolymers thereof, etc. can be mentioned. In this specification, "(meth)acrylic" means at least one selected from acrylic and methacryl.
　無機粒子１５が半導体粒子を含む場合、第１樹脂は、透明樹脂フィルムの成形時に、半導体粒子の光学特性等に悪影響が与えない程度の温度で溶融可能な熱可塑性樹脂であることが好ましい。 When the inorganic particles 15 include semiconductor particles, the first resin is preferably a thermoplastic resin that can be melted at a temperature that does not adversely affect the optical properties of the semiconductor particles during molding of the transparent resin film.
　第１樹脂は、透明樹脂フィルムの表面硬度、表面の外観、曲げ耐性及び耐カール性等を高める観点から、好ましくは、ポリスチレン系樹脂及び（メタ）アクリル系樹脂から選択される１種以上の熱可塑性樹脂であり、より好ましくはポリスチレン系樹脂である。ポリスチレン系樹脂とは、スチレン系単量体から誘導される構成単位を含む重合体又は共重合体をいう。ポリスチレン系樹脂としては、例えば、１種又は２種以上のスチレン系単量体の重合体又は共重合体；ゴム重合体（ゴム弾性体）と１種以上のスチレン系単量体との共重合体（ゴム変性ポリスチレン系樹脂。耐衝撃性ポリスチレン系樹脂ともいう。）；１種以上のスチレン系単量体と、これと共重合可能な１種以上の他の単量体との共重合体（ゴム変性ポリスチレン系樹脂は除く。）等が挙げられる。第１樹脂は、１種又は２種以上のポリスチレン系樹脂を含むことができる。 From the viewpoint of improving the surface hardness, surface appearance, bending resistance, curl resistance, etc. of the transparent resin film, the first resin is preferably one or more heat-resistant resins selected from polystyrene resins and (meth)acrylic resins. It is a plastic resin, more preferably a polystyrene resin. Polystyrene resin refers to a polymer or copolymer containing a structural unit derived from a styrene monomer. Examples of polystyrene resins include polymers or copolymers of one or more styrene monomers; copolymers of rubber polymers (rubber elastic bodies) and one or more styrene monomers; Coalescence (rubber-modified polystyrene resin; also referred to as impact-resistant polystyrene resin); copolymer of one or more styrene monomers and one or more other monomers copolymerizable with the same. (Excluding rubber-modified polystyrene resins). The first resin can include one or more polystyrene resins.
　スチレン系単量体としては、例えば、スチレンの他、α－メチルスチレン、ｐ－ｔ－ブチルスチレン、ｍ－又はｐ－メチルスチレン、ｍ－又はｐ－エチルスチレン、α－メチル－ｐ－メチルスチレン、クロロスチレン等のα置換及び／又は核置換スチレン等が挙げられる。 Examples of styrenic monomers include, in addition to styrene, α-methylstyrene, pt-butylstyrene, m- or p-methylstyrene, m- or p-ethylstyrene, α-methyl-p-methylstyrene, , α-substituted and/or nuclear-substituted styrene such as chlorostyrene, and the like.
　ゴム重合体としては、例えば、天然クレープゴム、ポリブタジエン、ブタジエン－スチレン共重合ゴム、ブタジエン－アクリロニトリル共重合ゴム、ポリイソプレン、ポリイソブチレン、イソプレン－イソブチレン共重合ゴム、ポリクロロプレン、エチレン－プロピレン共重合ゴム、エチレン－プロピレン－ジエン単量体ゴム、スチレン－ブタジエンブロック共重合ゴム、エチレン－酢酸ビニル共重合ゴム、（メタ）アクリル酸アルキルエステル共重合ゴム等が挙げられる。 Examples of rubber polymers include natural crepe rubber, polybutadiene, butadiene-styrene copolymer rubber, butadiene-acrylonitrile copolymer rubber, polyisoprene, polyisobutylene, isoprene-isobutylene copolymer rubber, polychloroprene, and ethylene-propylene copolymer rubber. , ethylene-propylene-diene monomer rubber, styrene-butadiene block copolymer rubber, ethylene-vinyl acetate copolymer rubber, (meth)acrylic acid alkyl ester copolymer rubber, and the like.
　スチレン系単量体と共重合可能な他の単量体としては、例えば、（メタ）アクリル酸エステル、（メタ）アクリル酸、無水マレイン酸、ビニルナフタレン、ブロモスチレン、フェニルマレイミド、アクリロニトリル等が挙げられる。 Examples of other monomers that can be copolymerized with the styrenic monomer include (meth)acrylic acid ester, (meth)acrylic acid, maleic anhydride, vinylnaphthalene, bromostyrene, phenylmaleimide, acrylonitrile, etc. It will be done.
　ゴム変性ポリスチレン系樹脂（耐衝撃性ポリスチレン系樹脂）としては、例えば、ポリブタジエングラフトスチレン重合体（ＨＩＰＳ樹脂）、ポリブタジエングラフトスチレン－メタクリル酸共重合体（ＨＩＳＭＡＡ樹脂）、ポリブタジエングラフトスチレン－アクリロニトリル共重合体（ＡＢＳ樹脂）等が挙げられる。中でも、透明樹脂フィルムの表面硬度、表面の外観、曲げ耐性及び耐カール性等を高める観点から、ＨＩＰＳ樹脂が好ましい。 Examples of rubber-modified polystyrene resins (impact-resistant polystyrene resins) include polybutadiene-grafted styrene polymers (HIPS resins), polybutadiene-grafted styrene-methacrylic acid copolymers (HISMAA resins), and polybutadiene-grafted styrene-acrylonitrile copolymers. (ABS resin), etc. Among these, HIPS resin is preferred from the viewpoint of improving the surface hardness, surface appearance, bending resistance, curl resistance, etc. of the transparent resin film.
　１種以上のスチレン系単量体と１種以上の他の単量体との共重合体としては、例えば、スチレン－メチルメタクリレート共重合体（ＭＳ樹脂）、スチレン－メタクリル酸共重合体（ＳＭＡＡ樹脂）、スチレン－アクリル酸共重合体（ＳＡＡ樹脂）、スチレン－アクリロニトリル共重合体（ＡＳ樹脂）等が挙げられる。 Copolymers of one or more styrene monomers and one or more other monomers include, for example, styrene-methyl methacrylate copolymer (MS resin), styrene-methacrylic acid copolymer (SMAA resin), styrene-acrylic acid copolymer (SAA resin), styrene-acrylonitrile copolymer (AS resin), and the like.
　透明樹脂フィルムの表面硬度、表面の外観、曲げ耐性及び耐カール性等を高める観点から、第１樹脂のメルトフローレートＭ１は、好ましくは０．５ｇ／１０分以上１０ｇ／１０分以下、より好ましくは０．８ｇ／１０分以上８．０ｇ／１０分以下、さらに好ましくは１．０ｇ／１０分以上５．０ｇ／１０分以下、なおさらに好ましくは２．０ｇ／１０分以上５．０ｇ／１０分以下、特に好ましくは２．５ｇ／１０分以上５．０ｇ／１０分以下である。第１樹脂等の樹脂のメルトフローレートは、後述する［実施例］の項の記載に従って測定される。 From the viewpoint of improving the surface hardness, surface appearance, bending resistance, curl resistance, etc. of the transparent resin film, the melt flow rate M1 of the first resin is preferably 0.5 g/10 minutes or more and 10 g/10 minutes or less, and more Preferably from 0.8 g/10 minutes to 8.0 g/10 minutes, more preferably from 1.0 g/10 minutes to 5.0 g/10 minutes, even more preferably from 2.0 g/10 minutes to 5.0 g/10 minutes. It is 10 minutes or less, particularly preferably 2.5 g/10 minutes or more and 5.0 g/10 minutes or less. The melt flow rate of the resin such as the first resin is measured according to the description in the [Example] section below.
　第１樹脂層１０における第１樹脂の含有率は、第１樹脂層１０の総量に対して、例えば５０質量％以上であり、好ましくは６０質量％以上、より好ましくは７０質量％以上、さらに好ましくは８０質量％以上、なおさらに好ましくは８５質量％以上、特に好ましくは９０質量％以上であり、例えば９９．９質量％以下であり、好ましくは９９．５質量％以下、より好ましくは９９．０質量％以下である。第１樹脂層１０における第１樹脂の含有率が上記範囲内であると、透明樹脂フィルムの表面硬度、表面の外観、曲げ耐性及び耐カール性等を高めやすい。 The content of the first resin in the first resin layer 10 is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably is 80% by mass or more, still more preferably 85% by mass or more, particularly preferably 90% by mass or more, for example 99.9% by mass or less, preferably 99.5% by mass or less, more preferably 99.0% by mass or less. % by mass or less. When the content of the first resin in the first resin layer 10 is within the above range, it is easy to improve the surface hardness, surface appearance, bending resistance, curl resistance, etc. of the transparent resin film.
　（２－３）第１樹脂層に含まれ得る他の成分
　第１樹脂層１０は、無機粒子１５及び第１樹脂以外の他の成分を含むことができる。他の成分としては、例えば、紫外線吸収剤、酸化防止剤、滑剤、可塑剤、離型剤、着色防止剤、難燃剤、核剤、帯電防止剤等の添加剤が挙げられる。第１樹脂層１０は、２種以上の添加剤を含有してもよい。 (2-3) Other components that may be included in the first resin layer The first resin layer 10 may contain other components other than the inorganic particles 15 and the first resin. Examples of other components include additives such as ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, color inhibitors, flame retardants, nucleating agents, and antistatic agents. The first resin layer 10 may contain two or more types of additives.
　酸化防止剤としては、工業的に一般に使用される酸化防止剤であれば特に限定はなく、フェノール系酸化防止剤、リン系酸化防止剤、リン／フェノール複合型酸化防止剤及び硫黄系酸化防止剤等を用いることができる。２種以上の酸化防止剤を用いてもよい。 Antioxidants are not particularly limited as long as they are commonly used industrially, and include phenolic antioxidants, phosphorus antioxidants, phosphorus/phenol complex antioxidants, and sulfur antioxidants. etc. can be used. Two or more kinds of antioxidants may be used.
　リン／フェノール複合型酸化防止剤は、例えば、分子中にリン原子とフェノール構造とをそれぞれ１以上有する化合物である。中でも、透明樹脂フィルムの発光強度の観点から、酸化防止剤は、リン／フェノール複合型酸化防止剤を含むことが好ましい。 A phosphorus/phenol composite antioxidant is, for example, a compound that has one or more phosphorus atoms and one or more phenol structures in its molecule. Among these, from the viewpoint of the luminescence intensity of the transparent resin film, it is preferable that the antioxidant includes a phosphorus/phenol composite type antioxidant.
　フェノール系酸化防止剤としては、例えば、イルガノックス（登録商標）１０１０（Ｉｒｇａｎｏｘ　１０１０：ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、ＢＡＳＦ（株）製）、同１０７６（Ｉｒｇａｎｏｘ　１０７６：オクタデシル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、ＢＡＳＦ（株）製）、同１３３０（Ｉｒｇａｎｏｘ　１３３０：３，３’，３’’，５，５’，５’’－ヘキサ－ｔｅｒｔ－ブチル－ａ，ａ’，ａ’’－（メシチレン－２，４，６－トリイル）トリ－ｐ－クレゾール、ＢＡＳＦ（株）製）、同３１１４（Ｉｒｇａｎｏｘ　３１１４：１，３，５－トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン、ＢＡＳＦ（株）製）、同３７９０（Ｉｒｇａｎｏｘ　３７９０：１，３，５－トリス（（４－ｔｅｒｔ－ブチル－３－ヒドロキシ－２，６－キシリル）メチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン、ＢＡＳＦ（株）製）、同１０３５（Ｉｒｇａｎｏｘ　１０３５：チオジエチレンビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、ＢＡＳＦ（株）製）、同１１３５（Ｉｒｇａｎｏｘ　１１３５：ベンゼンプロパン酸の３，５－ビス（１，１－ジメチルエチル）－４－ヒドロキシ－Ｃ７－Ｃ９側鎖アルキルエステル、ＢＡＳＦ（株）製）、同１５２０Ｌ（Ｉｒｇａｎｏｘ　１５２０Ｌ：４，６－ビス（オクチルチオメチル）－ｏ－クレゾール、ＢＡＳＦ（株）製）、同３１２５（Ｉｒｇａｎｏｘ　３１２５、ＢＡＳＦ（株）製）、同５６５（Ｉｒｇａｎｏｘ　５６５：２，４－ビス（ｎ－オクチルチオ）－６－（４－ヒドロキシ－３’、５’－ジ－ｔｅｒｔ－ブチルアニリノ）－１，３，５－トリアジン、ＢＡＳＦ（株）製）、アデカスタブ（登録商標）ＡＯ－８０（アデカスタブ　ＡＯ－８０：３，９－ビス（２－（３－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ）－１，１－ジメチルエチル）－２，４，８，１０－テトラオキサスピロ（５，５）ウンデカン、（株）ＡＤＥＫＡ製）、スミライザー（登録商標）ＢＨＴ、同ＧＡ－８０、同ＧＳ（以上、住友化学（株）製）、サイアノックス（登録商標）１７９０（Ｃｙａｎｏｘ　１７９０、（株）サイテック製）、ビタミンＥ（エーザイ（株）製）等が挙げられる。 Examples of the phenolic antioxidant include Irganox (registered trademark) 1010 (Irganox 1010: pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Corporation) ), 1076 (Irganox 1076: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, manufactured by BASF Corporation), 1330 (Irganox 1330: 3,3',3) '',5,5',5''-hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol, manufactured by BASF Corporation) , 3114 (Irganox 3114: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H )-trione, manufactured by BASF Corporation), 3790 (Irganox 3790: 1,3,5-tris((4-tert-butyl-3-hydroxy-2,6-xylyl)methyl)-1,3,5 -triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Corporation), 1035 (Irganox 1035: Thiodiethylenebis[3-(3,5-di-tert-butyl-4- 1135 (Irganox 1135: 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 side chain alkyl ester of benzenepropanoic acid, BASF) Co., Ltd.), Irganox 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl)-o-cresol, BASF Co., Ltd.), Irganox 3125 (Irganox 3125, BASF Co., Ltd.), Irganox 565 ( Irganox 565: 2,4-bis(n-octylthio)-6-(4-hydroxy-3',5'-di-tert-butylanilino)-1,3,5-triazine (manufactured by BASF Corporation), Adekastab (Registered Trademark) AO-80 (ADEKA STAB AO-80: 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl )-2,4,8,10-tetraoxaspiro(5,5)undecane, manufactured by ADEKA Co., Ltd.), Sumilizer (registered trademark) BHT, GA-80, GS (all manufactured by Sumitomo Chemical Co., Ltd.) ), Cyanox (registered trademark) 1790 (Cyanox 1790, manufactured by Cytec Co., Ltd.), vitamin E (manufactured by Eisai Co., Ltd.), and the like.
　フェノール系酸化防止剤としては、フェノール性ヒドロキシ基の少なくとも一方のオルト位に嵩高い有機基が結合したヒンダードフェノール構造を有する酸化防止剤が好ましい。嵩高い有機基としては、２級又は３級アルキル基が好ましく、具体的には、イソプロピル基、ｓ－ブチル基、ｔ－ブチル基、ｓ－アミル基、ｔ－アミル基等が挙げられる。中でも、３級アルキル基が好ましく、ｔ－ブチル基又はｔ－アミル基が特に好ましい。 As the phenolic antioxidant, an antioxidant having a hindered phenol structure in which a bulky organic group is bonded to at least one ortho position of a phenolic hydroxy group is preferable. The bulky organic group is preferably a secondary or tertiary alkyl group, and specific examples include isopropyl group, s-butyl group, t-butyl group, s-amyl group, and t-amyl group. Among these, a tertiary alkyl group is preferred, and a t-butyl group or a t-amyl group is particularly preferred.
　リン系酸化防止剤としては、例えば、イルガフォス（登録商標）１６８（Ｉｒｇａｆｏｓ　１６８：トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）フォスファイト、ＢＡＳＦ（株）製）、同１２（Ｉｒｇａｆｏｓ　１２：トリス［２－［［２，４，８，１０－テトラ－ｔｅｒｔ－ブチルジベンゾ［ｄ、ｆ］［１，３，２］ジオキサフォスフィン－６－イル］オキシ］エチル］アミン、ＢＡＳＦ（株）製）、同３８（Ｉｒｇａｆｏｓ　３８：ビス（２，４－ビス（１，１－ジメチルエチル）－６－メチルフェニル）エチルエステル亜りん酸、ＢＡＳＦ（株）製）、アデカスタブ（登録商標）３２９Ｋ、同ＰＥＰ３６、同ＰＥＰ－８（以上、（株）ＡＤＥＫＡ製）、Ｓａｎｄｓｔａｂ　Ｐ－ＥＰＱ（クラリアント社製）、Ｗｅｓｔｏｎ（登録商標）６１８、同６１９Ｇ（以上、ＧＥ社製）、Ｕｌｔｒａｎｏｘ６２６（ＧＥ社製）等が挙げられる。 Examples of the phosphorus antioxidant include Irgafos (registered trademark) 168 (Irgafos 168: tris(2,4-di-tert-butylphenyl) phosphite, manufactured by BASF Corporation) and Irgafos 12 (Irgafos 12: tris). [2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphine-6-yl]oxy]ethyl]amine, BASF Corporation (manufactured by BASF Corporation), Irgafos 38 (Irgafos 38: bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl ester phosphorous acid, manufactured by BASF Corporation), Adekastab (registered trademark) 329K, PEP36, PEP-8 (manufactured by ADEKA), Sandstab P-EPQ (manufactured by Clariant), Weston (registered trademark) 618, 619G (manufactured by GE), Ultranox626 (manufactured by GE) etc.
　リン／フェノール複合型酸化防止剤としては、例えば、スミライザー（登録商標）ＧＰ（６－［３－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロポキシ］－２，４，８，１０－テトラ－ｔｅｒｔ－ブチルジベンズ［ｄ，ｆ］［１．３．２］ジオキサホスフェピン）（住友化学（株）製）等が挙げられる。 Examples of the phosphorus/phenol complex antioxidant include Sumilizer (registered trademark) GP (6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8, Examples include 10-tetra-tert-butyldibenz[d,f][1.3.2]dioxaphosphepine (manufactured by Sumitomo Chemical Co., Ltd.).
　硫黄系酸化防止剤としては、例えば、チオジプロピオン酸ジラウリル、ジミリスチル又はジステアリール等のジアルキルチオジプロピオネート化合物及びテトラキス［メチレン（３－ドデシルチオ）プロピオネート］メタン等のポリオールのβ－アルキルメルカプトプロピオン酸エステル化合物等が挙げられる。 Examples of sulfur-based antioxidants include dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl or distearyl thiodipropionate, and β-alkylmercaptopropionate esters of polyols such as tetrakis[methylene(3-dodecylthio)propionate]methane. Examples include compounds.
　第１樹脂層１０が酸化防止剤を含む場合、第１樹脂層１０における酸化防止剤の含有率は、第１樹脂層１０の総量に対して、例えば０．００１質量％以上１０質量％以下であり、透明樹脂フィルムの発光強度の観点から、好ましくは０．０１質量％以上５質量％以下、より好ましくは０．０５質量％以上２質量％以下、さらに好ましくは０．１質量％以上１質量％以下である。 When the first resin layer 10 contains an antioxidant, the content of the antioxidant in the first resin layer 10 is, for example, 0.001% by mass or more and 10% by mass or less with respect to the total amount of the first resin layer 10. From the viewpoint of the luminescence intensity of the transparent resin film, preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.05% by mass or more and 2% by mass or less, even more preferably 0.1% by mass or more and 1% by mass. % or less.
　紫外線吸収剤の例としては、２，２’－メチレンビス〔４－（１，１，３，３－テトラメチルブチル）－６－（２Ｈ－ベンゾトリアゾール－２－イル）フェノール〕、２－（５
－メチル－２－ヒドロキシフェニル）－２Ｈ－ベンゾトリアゾール、２－〔２－ヒドロキシ－３，５－ビス（α，α－ジメチルベンジル）フェニル〕－２Ｈ－ベンゾトリアゾール、２－（３，５－ジ－ｔｅｒｔ－ブチル－２－ヒドロキシフェニル）－２Ｈ－ベンゾトリアゾール、２－（３－ｔｅｒｔ－ブチル－５－メチル－２－ヒドロキシフェニル）－５－クロロ－２Ｈ－ベンゾトリアゾール、２－（３，５－ジ－ｔｅｒｔ－ブチル－２－ヒドロキシフェニル）－５－クロロ－２Ｈ－ベンゾトリアゾール、２－（３，５－ジ－ｔｅｒｔ－アミル－２－ヒドロキシフェニル）－２Ｈ－ベンゾトリアゾール、２－（２’－ヒドロキシ－５’－ｔｅｒｔ－オクチルフェニル）－２Ｈ－ベンゾトリアゾール等のベンゾトリアゾール系紫外線吸収剤；２－ヒドロキシ－４－メトキシベンゾフェノン、２－ヒドロキシ－４－オクチルオキシベンゾフェノン、２，４－ジヒドロキシベンゾフェノン、２－ヒドロキシ－４－メトキシ－４’－クロロベンゾフェノン、２，２’－ジヒドロキシ－４－メトキシベンゾフェノン、２，２’－ジヒドロキシ－４，４’－ジメトキシベンゾフェノン等の２－ヒドロキシベンゾフェノン系紫外線吸収剤；ｐ－ｔｅｒｔ－ブチルフェニルサリチル酸エステル、ｐ－オクチルフェニルサリチル酸エステル等のサリチル酸フェニルエステル系紫外線吸収剤；２，４－ジフェニル－６－（２－ヒドロキシ－４－メトキシフェニル）－１，３，５－トリアジン、２，４－ジフェニル－６－（２－ヒドロキシ－４－エトキシフェニル）－１，３，５－トリアジン、２，４－ジフェニル－（２－ヒドロキシ－４－プロポキシフェニル）－１，３，５－トリアジン、２，４－ジフェニル－（２－ヒドロキシ－４－ブトキシフェニル）－１，３，５－トリアジン、２，４－ジフェニル－６－（２－ヒドロキシ－４－ブトキシフェニル）－１，３，５－トリアジン、２，４－ジフェニル－６－（２－ヒドロキシ－４－ヘキシルオキシフェニル）－１，３，５－トリアジン、２，４－ジフェニル－６－（２－ヒドロキシ－４－オクチルオキシフェニル）－１，３，５－トリアジン、２，４－ジフェニル－６－（２－ヒドロキシ－４－ドデシルオキシフェニル）－１，３，５－トリアジン、２，４－ジフェニル－６－（２－ヒドロキシ－４－ベンジルオキシフェニル）－１，３，５－トリアジン、２－（２－ヒドロキシ－４－［１－オクチルオキシカルボニルエトキシ］フェニル）－４，６－ビス（４－フェニルフェニル）－１，３，５－トリアジン、４－ビス［２－ヒドロキシ－４－ブトキシフェニル］－６－（２，４－ジブトキシフェニル）－１，３，５－トリアジン、２－［４－［（２－ヒドロキシ－３－（２’－エチル）ヘキシルオキシ］－２－ヒドロキシフェニル］－４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン、２－（４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン－２－イル）－５－ヒドロキシフェニル、２－［４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン－２－イル］－５－（オクチルオキシ）フェノール、２－［２，６－ジ（２，４－キシリル）－１，３，５－トリアジン－２－イル］－５－オクチルオキシフェノール、２－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－５－［２－（２－エチルヘキサノイル）エトキシ］フェノール、２，４，６－トリス（２－ヒドロキシ－４－ヘキシルオキシ－３－メトキシフェニル）－１，３，５トリアジン等のトリアジン系紫外線吸収剤などが挙げられ、必要に応じてそれらの２種以上を用いてもよい。 Examples of ultraviolet absorbers include 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(5
-Methyl-2-hydroxyphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-dimethylbenzyl)phenyl -tert-butyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3,5 -di-tert-butyl-2-hydroxyphenyl)-5-chloro-2H-benzotriazole, 2-(3,5-di-tert-amyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2 Benzotriazole UV absorbers such as '-hydroxy-5'-tert-octylphenyl)-2H-benzotriazole; 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2,4-dihydroxy 2-hydroxybenzophenone ultraviolet rays such as benzophenone, 2-hydroxy-4-methoxy-4'-chlorobenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, etc. Absorbent: Salicylic acid phenyl ester type UV absorber such as p-tert-butylphenyl salicylic acid ester, p-octylphenyl salicylic acid ester; 2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3 ,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-ethoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-propoxyphenyl)-1 , 3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy- 4-octyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-dodecyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6 -(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenyl) phenyl)-1,3,5-triazine, 4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-[4- [(2-hydroxy-3-(2'-ethyl)hexyloxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(4 ,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hydroxyphenyl, 2-[4,6-bis(2,4-dimethylphenyl)-1, 3,5-triazin-2-yl]-5-(octyloxy)phenol, 2-[2,6-di(2,4-xylyl)-1,3,5-triazin-2-yl]-5- Octyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyl)ethoxy]phenol, 2,4,6-tris( Examples include triazine-based ultraviolet absorbers such as 2-hydroxy-4-hexyloxy-3-methoxyphenyl)-1,3,5-triazine, and two or more of these may be used if necessary.
　紫外線吸収剤としては、市販品を使用してもよく、例えば、トリアジン系紫外線吸収剤として、ケミプロ化成株式会社製のＫｅｍｉｓｏｒｂ　１０２、株式会社ＡＤＥＫＡ製のアデカスタブ　ＬＡ４６、アデカスタブ　ＬＡＦ７０、ＢＡＳＦ社製のＴＩＮＵＶＩＮ　４６０、ＴＩＮＵＶＩＮ　４０５、ＴＩＮＵＶＩＮ　４００及びＴＩＮＵＶＩＮ　４７７、サンケミカル株式会社製のＣＹＡＳＯＲＢ　ＵＶ－１１６４（以上、いずれも商品名）等がある。ベンゾトリアゾール系紫外線吸収剤としては、株式会社ＡＤＥＫＡ製のアデカスタブ　ＬＡ３１及びアデカスタブ　ＬＡ３６、住化ケムテックス株式会社製のスミソーブ　２００、スミソーブ　２５０、スミソーブ　３００、スミソーブ　３４０及びスミソーブ　３５０、ケミプロ化成株式会社製のＫｅｍｉｓｏｒｂ　７４、Ｋｅｍｉｓｏｒｂ　７９及びＫｅｍｉｓｏｒｂ　２７９、ＢＡＳＦ社製のＴＩＮＵＶＩＮ　９９－２、ＴＩＮＵＶＩＮ　３６０、ＴＩＮＵＶＩＮ　９００及びＴＩＮＵＶＩＮ　９２８、城北化学工業株式会社製のＪＦ－７７、ＪＦ－７９、ＪＦ－８０、ＪＦ－８３、ＪＦ－８３２、ＪＡＳＴ－５００、ＪＦ－９０Ｇ、ＪＦ－９５（以上、いずれも商品名）等が挙げられる。 As the ultraviolet absorber, commercially available products may be used. For example, as a triazine-based ultraviolet absorber, Kemisorb 102 manufactured by ChemiPro Kasei Co., Ltd., ADEKA STAB LA46, ADEKA STAB LAF70, manufactured by BASF Corporation, and TINUVIN 460 manufactured by BASF Corporation. , TINUVIN 405, TINUVIN 400 and TINUVIN 477, and CYASORB UV-1164 manufactured by Sun Chemical Co., Ltd. (all of the above are product names). Examples of benzotriazole ultraviolet absorbers include ADEKA STAB LA31 and ADEKA STAB LA36 manufactured by ADEKA Co., Ltd., SUMISORB 200, SUMISORB 250, SUMISORB 300, SUMISORB 340 and SUMISORB 350 manufactured by Sumika Chemtex Co., Ltd., and Kemisorb manufactured by ChemiPro Kasei Co., Ltd. 74 , Kemisorb 79 and Kemisorb 279, TINUVIN 99-2, TINUVIN 360, TINUVIN 900 and TINUVIN 928 manufactured by BASF, JF-77, JF-79, JF-80, JF manufactured by Johoku Kagaku Kogyo Co., Ltd. -83, JF- 832, JAST-500, JF-90G, JF-95 (all of the above are trade names).
　第１樹脂層１０が紫外線吸収剤を含む場合、第１樹脂層１０における紫外線吸収剤の含有率は、第１樹脂層１０の総量に対して、例えば０．００１質量％以上１０質量％以下であり、透明樹脂フィルムの耐候性向上等の観点から、好ましくは０．０１質量％以上５質量％以下、より好ましくは０．０５質量％以上２質量％以下、さらに好ましくは０．１質量％以上１質量％以下である。 When the first resin layer 10 contains an ultraviolet absorber, the content of the ultraviolet absorber in the first resin layer 10 is, for example, 0.001% by mass or more and 10% by mass or less with respect to the total amount of the first resin layer 10. Yes, from the viewpoint of improving the weather resistance of the transparent resin film, preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.05% by mass or more and 2% by mass or less, even more preferably 0.1% by mass or more. It is 1% by mass or less.
　（２－４）第１樹脂層の平均厚み
　透明樹脂フィルムの表面硬度、表面の外観、曲げ耐性及び耐カール性等を高める観点から、第１樹脂層１０の平均厚みＴ１ＡＶは、好ましくは５０μｍ以上５００μｍ以下、より好ましくは７０μｍ以上４００μｍ以下、さらに好ましくは８０μｍ以上３５０μｍ以下、なおさらに好ましくは１００μｍ以上３００μｍ以下、特に好ましくは１５０μｍ以上２５０μｍ以下である。第１樹脂層の平均厚みＴ１ＡＶは、３つの測定点で測定される第１樹脂層の厚みＴ１の平均値であり、測定方法の詳細は、［実施例］の項で詳述する。第１樹脂層の厚みＴ１もまた、上記範囲内であることが好ましい。 (2-4) Average thickness of the first resin layer From the viewpoint of improving the surface hardness, surface appearance, bending resistance, curl resistance, etc. of the transparent resin film, the average thickness T 1AV of the first resin layer 10 is preferably 50 μm. 500 μm or less, more preferably 70 μm or more and 400 μm or less, even more preferably 80 μm or more and 350 μm or less, even more preferably 100 μm or more and 300 μm or less, particularly preferably 150 μm or more and 250 μm or less. The average thickness T 1AV of the first resin layer is the average value of the thickness T 1 of the first resin layer measured at three measurement points, and the details of the measurement method will be described in detail in the [Example] section. The thickness T 1 of the first resin layer is also preferably within the above range.
　（３）第２樹脂層及び第３樹脂層
　第２樹脂層２０は、第１樹脂層１０の第１表面上に配置される樹脂層である。第２樹脂層２０に含まれる樹脂は第２樹脂を含み、好ましくは、第２樹脂層２０に含まれる樹脂は第２樹脂からなる。 (3) Second resin layer and third resin layer The second resin layer 20 is a resin layer disposed on the first surface of the first resin layer 10. The resin contained in the second resin layer 20 includes a second resin, and preferably the resin contained in the second resin layer 20 is made of the second resin.
　第３樹脂層３０は、第１樹脂層１０の第１表面と対向する第２表面上に配置される樹脂層である。第３樹脂層３０に含まれる樹脂は第３樹脂を含み、好ましくは、第３樹脂層３０に含まれる樹脂は第３樹脂からなる。 The third resin layer 30 is a resin layer disposed on the second surface of the first resin layer 10 that faces the first surface. The resin contained in the third resin layer 30 includes a third resin, and preferably, the resin contained in the third resin layer 30 is made of the third resin.
　好ましくは、第１樹脂層１０は、光散乱剤及び発光性の半導体粒子から選択される無機粒子１５を含有し、第２樹脂層２０及び第３樹脂層３０は、光散乱剤及び半導体粒子を含有しない。これにより、透明樹脂フィルムにおいて、無機粒子１５に基づく光学特性と機械的強度とを両立させやすくなる。また、第１樹脂層１０に光散乱剤及び半導体粒子の両方を含有させることにより、半導体粒子の近傍に光散乱剤を存在させることができるため、透明樹脂フィルムの発光強度向上に有利となり得る。 Preferably, the first resin layer 10 contains a light scattering agent and inorganic particles 15 selected from luminescent semiconductor particles, and the second resin layer 20 and the third resin layer 30 contain a light scattering agent and semiconductor particles. Contains no. This makes it easier to achieve both optical properties based on the inorganic particles 15 and mechanical strength in the transparent resin film. Furthermore, by including both the light scattering agent and the semiconductor particles in the first resin layer 10, the light scattering agent can be present near the semiconductor particles, which may be advantageous in improving the luminescence intensity of the transparent resin film.
　第２樹脂層２０、第３樹脂層３０はそれぞれ、無機粒子を含有し得る。ただし、第２樹脂層２０及び第３樹脂層３０は、発光性の半導体粒子を含有しないことが好ましく、発光性の半導体粒子及び光散乱剤を含有しないことがより好ましい。 The second resin layer 20 and the third resin layer 30 may each contain inorganic particles. However, the second resin layer 20 and the third resin layer 30 preferably do not contain luminescent semiconductor particles, and more preferably do not contain luminescent semiconductor particles and light scattering agents.
　（３－１）アンチブロッキング剤
　第２樹脂層２０及び第３樹脂層３０は、好ましくは、少なくともいずれか一方の樹脂層がアンチブロッキング剤を含有し、より好ましくは、両方の樹脂層がアンチブロッキング剤を含有する。これにより、透明樹脂フィルムをロール状態にしたときや枚葉状態の透明樹脂フィルムを積層させたときのフィルムの密着（ブロッキング）を抑制することができる。また、いずれか一方又は両方の樹脂層にアンチブロッキング剤を含有させることにより、透明樹脂フィルムの表面硬度を高め得る。第２樹脂層２０、第３樹脂層３０はそれぞれ、２種以上のアンチブロッキング剤を含有してもよい。なお、第１樹脂層１０は、アンチブロッキング剤を含有していてもよいが、透明樹脂フィルムの発光強度を高めやすいことから、アンチブロッキング剤を含有しないことが好ましい。 (3-1) Anti-blocking agent Preferably, at least one of the second resin layer 20 and the third resin layer 30 contains an anti-blocking agent, and more preferably, both resin layers contain an anti-blocking agent. Contains an agent. Thereby, it is possible to suppress adhesion (blocking) of the films when the transparent resin films are made into a roll or when the transparent resin films in the sheet state are laminated. Furthermore, by containing an anti-blocking agent in one or both resin layers, the surface hardness of the transparent resin film can be increased. The second resin layer 20 and the third resin layer 30 may each contain two or more types of anti-blocking agents. Although the first resin layer 10 may contain an anti-blocking agent, it is preferable that the first resin layer 10 does not contain an anti-blocking agent since this tends to increase the luminescence intensity of the transparent resin film.
　アンチブロッキング剤を第２樹脂層２０及び／又は第３樹脂層３０に含有させ、第１樹脂層１０には含有させないことにより、透明樹脂フィルムの全光線透過率を高めやすくなり、光学特性の観点から有利である。 By containing the anti-blocking agent in the second resin layer 20 and/or the third resin layer 30, but not in the first resin layer 10, it becomes easier to increase the total light transmittance of the transparent resin film, which improves the optical properties. It is advantageous from
　アンチブロッキング剤としては、例えば、シリカ、アルミナ、炭酸カルシウム、炭酸マグネシウム、硫酸カルシウム、硫酸バリウム、カオリン、これらの疎水処理物等からなる無機系の粒子；（メタ）アクリル樹脂、ウレタン樹脂、フェノール樹脂、シリコン樹脂、フッ素樹脂、ポリアミド、ポリプロピレン等のポリオレフィン、ポリカーボネート等からなる樹脂粒子が挙げられる。樹脂粒子の好ましい一例は、（メタ）アクリル樹脂粒子である。 Examples of anti-blocking agents include inorganic particles made of silica, alumina, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, kaolin, hydrophobically treated products of these, etc.; (meth)acrylic resin, urethane resin, phenol resin. , silicone resin, fluororesin, polyamide, polyolefin such as polypropylene, polycarbonate, and the like. A preferable example of the resin particles is (meth)acrylic resin particles.
　アンチブロッキング剤は、好ましくは樹脂粒子である。アンチブロッキング剤が樹脂粒子であると、透明樹脂フィルムの表面に存在するアンチブロッキング剤により、透明樹脂フィルムの表面硬度だけでなく、耐衝撃性を高めることができる。さらには、透明樹脂フィルムの内部、好ましくは第１樹脂層から発せられる光の散乱を抑制できるとともに、例えば無機系の粒子を含有させた場合に比して透明樹脂フィルムの透明性を高めることができるため、透明樹脂フィルムの出射光強度の低下を抑制することができる。 The anti-blocking agent is preferably resin particles. When the anti-blocking agent is a resin particle, the anti-blocking agent present on the surface of the transparent resin film can improve not only the surface hardness of the transparent resin film but also the impact resistance. Furthermore, scattering of light emitted from the inside of the transparent resin film, preferably from the first resin layer, can be suppressed, and the transparency of the transparent resin film can be increased compared to the case where, for example, inorganic particles are included. Therefore, a decrease in the intensity of light emitted from the transparent resin film can be suppressed.
　アンチブロッキング剤は、それが分散される第２樹脂又は第３樹脂との屈折率差が小さい粒子であることが好ましい。屈折率差を小さくすることにより、アンチブロッキング剤により生じる、透明樹脂フィルム内部から発せられる光の散乱を抑制できるため、透明樹脂フィルムの出射光強度を向上させることができる。上記屈折率差を小さくする観点から、アンチブロッキング剤は、好ましくは樹脂粒子であり、より好ましくは（メタ）アクリル樹脂粒子である。 The anti-blocking agent is preferably a particle that has a small refractive index difference with the second resin or third resin in which it is dispersed. By reducing the refractive index difference, it is possible to suppress the scattering of light emitted from inside the transparent resin film caused by the anti-blocking agent, and therefore it is possible to improve the intensity of light emitted from the transparent resin film. From the viewpoint of reducing the refractive index difference, the anti-blocking agent is preferably resin particles, more preferably (meth)acrylic resin particles.
　アンチブロッキング剤の平均粒径は、透明樹脂フィルムの表面硬度、耐衝撃性、曲げ耐性及び耐カール性を考慮して、好ましくは１μｍ以上４５μｍ以下、より好ましくは２μｍ以上３０μｍ以下、さらに好ましくは３μｍ以上１５μｍ以下、なおさらに好ましくは４μｍ以上１０μｍ以下である。 The average particle size of the anti-blocking agent is preferably 1 μm or more and 45 μm or less, more preferably 2 μm or more and 30 μm or less, and even more preferably 3 μm, considering the surface hardness, impact resistance, bending resistance, and curl resistance of the transparent resin film. The thickness is preferably 4 μm or more and 10 μm or less, and more preferably 4 μm or more and 10 μm or less.
　第２樹脂層２０及び／又は第３樹脂層３０がアンチブロッキング剤を含む場合、該樹脂層におけるアンチブロッキング剤の含有率は、該樹脂層の総量に対して、例えば０．０１質量％以上５０質量％以下であり、好ましくは０．１質量％以上３０質量％以下、より好ましくは０．５質量％以上２０質量％以下、さらに好ましくは１．０質量％以上１５質量％以下、なおさらに好ましくは３．０質量％以上１２質量％以下、特に好ましくは５．０質量％以上１２質量％以下である。該樹脂層におけるアンチブロッキング剤の含有率が上記範囲であると、透明樹脂フィルムをロール状態にしたときや枚葉状態の透明樹脂フィルムを積層させたときのフィルムの密着（ブロッキング）を抑制することができ、また、透明樹脂フィルムの発光強度を高めやすい。さらに、該樹脂層におけるアンチブロッキング剤の含有率が上記範囲であると、透明樹脂フィルムの耐衝撃性を高め得る。 When the second resin layer 20 and/or the third resin layer 30 contains an anti-blocking agent, the content of the anti-blocking agent in the resin layer is, for example, 0.01% by mass or more and 50% by mass or more with respect to the total amount of the resin layer. mass% or less, preferably 0.1 mass% or more and 30 mass% or less, more preferably 0.5 mass% or more and 20 mass% or less, still more preferably 1.0 mass% or more and 15 mass% or less, even more preferably is 3.0% by mass or more and 12% by mass or less, particularly preferably 5.0% by mass or more and 12% by mass or less. When the content of the anti-blocking agent in the resin layer is within the above range, adhesion (blocking) of the film can be suppressed when the transparent resin film is made into a roll or when the transparent resin films in the sheet state are laminated. In addition, it is easy to increase the luminous intensity of the transparent resin film. Furthermore, when the content of the anti-blocking agent in the resin layer is within the above range, the impact resistance of the transparent resin film can be improved.
　（３－２）第２樹脂及び第３樹脂
　第２樹脂及び第３樹脂は、好ましくは、それぞれ熱可塑性樹脂である。第２樹脂及び第３樹脂はそれぞれ、２種以上の熱可塑性樹脂を含んでいてもよい。熱可塑性樹脂の例については上記（２－２）での記載が引用される。
　第２樹脂層２０に含まれる樹脂は、１種の第２樹脂からなっていてもよいし、２種以上の第２樹脂からなっていてもよいが、好ましくは、１種の第２樹脂からなる。第３樹脂層３０に含まれる樹脂は、１種の第３樹脂からなっていてもよいし、２種以上の第３樹脂からなっていてもよいが、好ましくは、１種の第３樹脂からなる。 (3-2) Second resin and third resin The second resin and the third resin are each preferably a thermoplastic resin. The second resin and the third resin may each contain two or more types of thermoplastic resins. Regarding examples of thermoplastic resins, the description in (2-2) above is cited.
The resin contained in the second resin layer 20 may be made of one type of second resin, or may be made of two or more types of second resin, but is preferably made of one type of second resin. Become. The resin contained in the third resin layer 30 may be made of one type of third resin, or may be made of two or more types of third resin, but is preferably made of one type of third resin. Become.
　第１樹脂層１０が半導体粒子を含む場合、第２樹脂及び第３樹脂はそれぞれ、透明樹脂フィルムの成形時に、半導体粒子の光学特性等に悪影響が与えない程度の温度で溶融可能な熱可塑性樹脂であることが好ましい。 When the first resin layer 10 contains semiconductor particles, the second resin and the third resin are respectively thermoplastic resins that can be melted at a temperature that does not adversely affect the optical properties of the semiconductor particles during molding of the transparent resin film. It is preferable that
　第２樹脂及び第３樹脂はそれぞれ、透明樹脂フィルムの表面硬度、表面の外観、曲げ耐性及び耐カール性等を高める観点から、好ましくは、ポリスチレン系樹脂及び（メタ）アクリル系樹脂から選択される１種以上の熱可塑性樹脂であり、より好ましくはポリスチレン系樹脂である。第２樹脂及び第３樹脂はそれぞれ、１種又は２種以上のポリスチレン系樹脂を含むことができる。中でも、透明樹脂フィルムの表面硬度、表面の外観、曲げ耐性及び耐カール性等を高める観点から、第２樹脂及び第３樹脂はそれぞれ、好ましくは、ＨＩＰＳ樹脂である。 The second resin and the third resin are preferably selected from polystyrene resins and (meth)acrylic resins from the viewpoint of improving the surface hardness, surface appearance, bending resistance, curl resistance, etc. of the transparent resin film, respectively. One or more thermoplastic resins, more preferably polystyrene resins. The second resin and the third resin can each contain one or more polystyrene resins. Among these, each of the second resin and the third resin is preferably a HIPS resin from the viewpoint of improving the surface hardness, surface appearance, bending resistance, curl resistance, etc. of the transparent resin film.
　第１樹脂と第２樹脂とは同じであってもよいし、異なっていてもよい。第１樹脂と第３樹脂とは同じであってもよいし、異なっていてもよい。第２樹脂と第３樹脂とは同じであってもよいし、異なっていてもよい。第１樹脂、第２樹脂及び第３樹脂は、好ましくは、いずれも熱可塑性樹脂であり、より好ましくは、同一の熱可塑性樹脂である。 The first resin and the second resin may be the same or different. The first resin and the third resin may be the same or different. The second resin and the third resin may be the same or different. The first resin, the second resin, and the third resin are preferably all thermoplastic resins, more preferably the same thermoplastic resin.
　１つの好ましい実施形態において、透明樹脂フィルムは第１樹脂層１０、第２樹脂層２０及び第３樹脂層３０を有し、第１樹脂、第２樹脂及び第３樹脂はＨＩＰＳ樹脂である。 In one preferred embodiment, the transparent resin film has a first resin layer 10, a second resin layer 20, and a third resin layer 30, and the first resin, second resin, and third resin are HIPS resins.
　透明樹脂フィルムの表面硬度、表面の外観、曲げ耐性及び耐カール性等を高める観点から、第２樹脂のメルトフローレートＭ２、第３樹脂のメルトフローレートＭ３はそれぞれ、好ましくは０．５ｇ／１０分以上１０ｇ／１０分以下、より好ましくは０．８ｇ／１０分以上８．０ｇ／１０分以下、さらに好ましくは１．０ｇ／１０分以上５．０ｇ／１０分以下、なおさらに好ましくは２．０ｇ／１０分以上５．０ｇ／１０分以下、特に好ましくは２．５ｇ／１０分以上５．０ｇ／１０分以下である。 From the viewpoint of improving the surface hardness, surface appearance, bending resistance, curl resistance, etc. of the transparent resin film, the melt flow rate M 2 of the second resin and the melt flow rate M 3 of the third resin are each preferably 0.5 g. /10 minutes or more and 10 g/10 minutes or less, more preferably 0.8 g/10 minutes or more and 8.0 g/10 minutes or less, even more preferably 1.0 g/10 minutes or more and 5.0 g/10 minutes or less, even more preferably It is 2.0 g/10 minutes or more and 5.0 g/10 minutes or less, particularly preferably 2.5 g/10 minutes or more and 5.0 g/10 minutes or less.
　第２樹脂のメルトフローレートＭ２に対する第３樹脂のメルトフローレートＭ３の比Ｍ３／Ｍ２は、好ましくは０．５以上２以下、より好ましくは０．７以上１．５以下、さらに好ましくは０．９以上１．２以下、特に好ましくは１である。 The ratio M 3 /M 2 of the melt flow rate M 3 of the third resin to the melt flow rate M 2 of the second resin is preferably 0.5 or more and 2 or less, more preferably 0.7 or more and 1.5 or less, and It is preferably 0.9 or more and 1.2 or less, particularly preferably 1.
　第２樹脂層２０における第２樹脂の含有率、第３樹脂層３０における第３樹脂の含有率はそれぞれ、該樹脂層の総量に対して、例えば５０質量％以上であり、好ましくは６０質量％以上、より好ましくは７０質量％以上、さらに好ましくは８０質量％、なおさらに好ましくは８５質量％以上、特に好ましくは９０質量％以上であり、例えば９９．９質量％以下であり、好ましくは９９．５質量％以下、より好ましくは９９．０質量％以下、さらに好ましくは９８．０％以下、なおさらに好ましくは９６．０％以下である。第２樹脂層２０における第２樹脂の含有率及び第３樹脂層３０における第３樹脂の含有率が上記範囲内であると、透明樹脂フィルムの表面硬度、表面の外観、曲げ耐性及び耐カール性等を高めやすい。 The content rate of the second resin in the second resin layer 20 and the content rate of the third resin in the third resin layer 30 are each, for example, 50% by mass or more, preferably 60% by mass, based on the total amount of the resin layer. The above content is more preferably 70% by mass or more, still more preferably 80% by mass, even more preferably 85% by mass or more, particularly preferably 90% by mass or more, and, for example, 99.9% by mass or less, preferably 99. It is 5% by mass or less, more preferably 99.0% by mass or less, even more preferably 98.0% or less, even more preferably 96.0% or less. When the content of the second resin in the second resin layer 20 and the content of the third resin in the third resin layer 30 are within the above ranges, the surface hardness, surface appearance, bending resistance, and curl resistance of the transparent resin film are etc. is easy to increase.
　第２樹脂層２０及び第３樹脂層３０は、アンチブロッキング剤及び第２樹脂又は第３樹脂以外の他の成分を含むことができる。他の成分の例は、上記（２－３）に記載の添加剤の例と同様である。 The second resin layer 20 and the third resin layer 30 can contain components other than the anti-blocking agent and the second resin or third resin. Examples of other components are the same as the additives described in (2-3) above.
　（３－３）第２樹脂層及び第３樹脂層の平均厚み
　透明樹脂フィルムの表面硬度、表面の外観、曲げ耐性及び耐カール性等を高める観点から、第２樹脂層２０の平均厚みＴ２ＡＶ、第３樹脂層３０の平均厚みＴ３ＡＶはそれぞれ、好ましくは５μｍ以上、より好ましくは１０μｍ以上、さらに好ましくは１５μｍ以上、なおさらに好ましくは２０μｍ以上であり、好ましくは２００μｍ以下、より好ましくは１５０μｍ以下、さらに好ましくは１００μｍ以下、なおさらに好ましくは５０μｍ以下、特に好ましくは４５μｍ以下である。第２樹脂層の平均厚みＴ２ＡＶ、第３樹脂層の平均厚みＴ３ＡＶはそれぞれ、３つの測定点で測定される第２樹脂層の厚みＴ２の平均値、第３樹脂層の厚みＴ２の平均値であり、測定方法の詳細は、［実施例］の項で詳述する。第２樹脂層の厚みＴ２、第３樹脂層の厚みＴ３もそれぞれ、上記範囲内であることが好ましい。 (3-3) Average thickness of second resin layer and third resin layer From the viewpoint of improving the surface hardness, surface appearance, bending resistance, curl resistance, etc. of the transparent resin film, the average thickness of the second resin layer 20 is T 2AV , the average thickness T 3AV of the third resin layer 30 is preferably 5 μm or more, more preferably 10 μm or more, even more preferably 15 μm or more, even more preferably 20 μm or more, and preferably 200 μm or less, more preferably 150 μm or less. , more preferably 100 μm or less, even more preferably 50 μm or less, particularly preferably 45 μm or less. The average thickness T 2AV of the second resin layer and the average thickness T 3AV of the third resin layer are the average value of the thickness T 2 of the second resin layer measured at three measurement points, and the thickness T 2 of the third resin layer, respectively. The details of the measurement method are described in the [Example] section. It is also preferable that the thickness T 2 of the second resin layer and the thickness T 3 of the third resin layer are each within the above ranges.
　（４）厚み比及びその標準偏差
　透明樹脂フィルムにおいて、透明樹脂フィルムの厚み（総厚み）Ｔ［μｍ］に対する第２樹脂層の厚みＴ２［μｍ］の比Ｔ２／Ｔの標準偏差は０．０１５以下であり、透明樹脂フィルムの厚みＴ［μｍ］に対する第３樹脂層の厚みＴ３［μｍ］の比Ｔ３／Ｔの標準偏差は０．０１５以下である。Ｔ２／Ｔの標準偏差及びＴ３／Ｔの標準偏差が該範囲内であることにより、透明樹脂フィルム両面の表面硬度のバラツキを小さくすることができ、これにより、該両面の耐擦傷性を優れたものとすることができる。上記表面硬度は、ＪＩＳ
　Ｋ　５６００－５－４：１９９９に規定される鉛筆硬度試験に従って測定される鉛筆硬度であってよい。 (4) Thickness ratio and its standard deviation In a transparent resin film, the standard deviation of the ratio T 2 /T of the thickness T 2 [μm] of the second resin layer to the thickness (total thickness) T [μm] of the transparent resin film is 0 The standard deviation of the ratio T 3 /T of the thickness T 3 [μm] of the third resin layer to the thickness T [μm] of the transparent resin film is 0.015 or less. By setting the standard deviation of T 2 /T and the standard deviation of T 3 /T within the range, it is possible to reduce the variation in surface hardness on both sides of the transparent resin film, thereby improving the scratch resistance of both sides. It can be made excellent. The above surface hardness is JIS
It may be the pencil hardness measured according to the pencil hardness test specified in K 5600-5-4:1999.
　Ｔ２／Ｔの標準偏差及びＴ３／Ｔの標準偏差は、透明樹脂フィルム両面の表面硬度のバラツキを小さくする観点から、それぞれ、好ましくは０．０１４５以下、より好ましくは０．０１２以下、さらに好ましくは０．０１０以下、なおさらに好ましくは０．００８以下、特に好ましくは０．００５以下である。Ｔ２／Ｔの標準偏差及びＴ３／Ｔの標準偏差は、それぞれ、例えば０．０００５以上であり、０．００１以上であってもよい。 The standard deviation of T 2 /T and the standard deviation of T 3 /T are each preferably 0.0145 or less, more preferably 0.012 or less, and It is preferably 0.010 or less, even more preferably 0.008 or less, particularly preferably 0.005 or less. The standard deviation of T 2 /T and the standard deviation of T 3 /T are each, for example, 0.0005 or more, and may be 0.001 or more.
　透明樹脂フィルムの厚みＴ、各樹脂層の厚みＴ１、Ｔ２及びＴ３、並びに、上記標準偏差は、後述する［実施例］の項の記載に従って測定することができる。透明樹脂フィルムの厚みＴ、各樹脂層の厚みＴ１、Ｔ２及びＴ３を測定する際の透明樹脂フィルム面内における測定点は、通常同じである。 The thickness T of the transparent resin film, the thicknesses T 1 , T 2 and T 3 of each resin layer, and the above standard deviation can be measured according to the description in the [Example] section below. The measurement points within the plane of the transparent resin film when measuring the thickness T of the transparent resin film and the thicknesses T 1 , T 2 and T 3 of each resin layer are usually the same.
　透明樹脂フィルム両面の表面硬度のバラツキを小さくする観点から、Ｔ２／Ｔの標準偏差とＴ３／Ｔの標準偏差との和は、０．０２０以下であることが好ましく、該和は、より好ましくは０．０１８以下、さらに好ましくは０．０１５以下、なおさらに好ましくは０．０１０以下、特に好ましくは０．００８以下である。該和は、例えば０．００１以上であり、０．００２以上であってもよい。 From the viewpoint of reducing the variation in surface hardness on both sides of the transparent resin film, the sum of the standard deviation of T 2 /T and the standard deviation of T 3 /T is preferably 0.020 or less, and the sum is more It is preferably 0.018 or less, more preferably 0.015 or less, even more preferably 0.010 or less, particularly preferably 0.008 or less. The sum is, for example, 0.001 or more, and may be 0.002 or more.
　透明樹脂フィルムの平均厚みＴＡＶは、該フィルムの取扱性及び該フィルムを適用した表示装置の薄型化の観点から、好ましくは５５μｍ以上９００μｍ以下、より好ましくは７５μｍ以上７００μｍ以下、さらに好ましくは９５μｍ以上５５０μｍ以下、なおさらに好ましくは１２０μｍ以上４００μｍ以下、特に好ましくは１５０μｍ以上３００μｍ以下である。透明樹脂フィルムの平均厚みＴＡＶは、３つの測定点で測定される透明樹脂フィルムの厚みＴの平均値であり、測定方法の詳細は、［実施例］の項で詳述する。透明樹脂フィルムの厚みＴもまた、上記範囲内であることが好ましい。 The average thickness T AV of the transparent resin film is preferably 55 μm or more and 900 μm or less, more preferably 75 μm or more and 700 μm or less, and even more preferably 95 μm or more, from the viewpoint of handling the film and making the display device to which the film is applied thinner. It is 550 μm or less, still more preferably 120 μm or more and 400 μm or less, particularly preferably 150 μm or more and 300 μm or less. The average thickness T AV of the transparent resin film is the average value of the thickness T of the transparent resin film measured at three measurement points, and the details of the measurement method will be described in detail in the [Example] section. The thickness T of the transparent resin film is also preferably within the above range.
　透明樹脂フィルムにおいて、無機粒子１５に基づく光学特性と機械的強度とを両立させやすくなることから、また、透明樹脂フィルム両面の表面硬度、表面の外観、曲げ耐性及び耐カール性等を高める観点から、第２樹脂層の平均厚みＴ２ＡＶ［μｍ］に対する第１樹脂層の平均厚みＴ１ＡＶ［μｍ］の比Ｔ１ＡＶ／Ｔ２ＡＶ、及び、第３樹脂層の平均厚みＴ３ＡＶ［μｍ］に対する第１樹脂層の平均厚みＴ１ＡＶ［μｍ］の比Ｔ１ＡＶ／Ｔ３ＡＶはいずれも、好ましくは３０以下、より好ましくは２０以下、さらに好ましくは１５以下、なおさらに好ましくは１２以下、特に好ましくは１０以下、最も好ましくは７．０以下であり、好ましくは０．５以上、より好ましくは１．０以上、さらに好ましくは２．０以上、なおさらに好ましくは３．０以上である。 In the transparent resin film, it becomes easier to achieve both optical properties and mechanical strength based on the inorganic particles 15, and from the viewpoint of improving the surface hardness, surface appearance, bending resistance, curl resistance, etc. on both sides of the transparent resin film. , the ratio T 1AV / T 2AV of the average thickness T 1AV [μm] of the first resin layer to the average thickness T 2AV [μm] of the second resin layer, and the ratio T 1AV /T 2AV of the average thickness T 3AV [μm] of the third resin layer The ratio T 1AV /T 3AV of the average thickness T 1AV [μm] of one resin layer is preferably 30 or less, more preferably 20 or less, even more preferably 15 or less, even more preferably 12 or less, particularly preferably 10 Below, it is most preferably 7.0 or less, preferably 0.5 or more, more preferably 1.0 or more, still more preferably 2.0 or more, and even more preferably 3.0 or more.
　第２樹脂層２０の平均厚みＴ２ＡＶに対する第３樹脂層３０の平均厚みＴ３ＡＶの比Ｔ３ＡＶ／Ｔ２ＡＶは、好ましくは０．５以上２以下、より好ましくは０．７以上１．５以下、さらに好ましくは０．８以上１．２以下である。 The ratio T 3AV /T 2AV of the average thickness T 3AV of the third resin layer 30 to the average thickness T 2AV of the second resin layer 20 is preferably 0.5 or more and 2 or less, more preferably 0.7 or more and 1.5 or less. , more preferably 0.8 or more and 1.2 or less.
　（５）厚み比とメルトフローレート比との積
　第２樹脂層２０の平均厚みＴ２ＡＶ［μｍ］に対する第１樹脂層１０の平均厚みＴ１ＡＶ［μｍ］の比Ｔ１ＡＶ／Ｔ２ＡＶをＡとし、第２樹脂のメルトフローレートＭ２［ｇ／１０分］に対する第１樹脂のメルトフローレートＭ１［ｇ／１０分］の比Ｍ１／Ｍ２をＢとするとき、透明樹脂フィルムは、式（ｉ）：
　Ａ×Ｂ≦１８　　　　（ｉ）
を満たすことが好ましい。
　式（ｉ）を満たすことは、透明樹脂フィルムの表面硬度、表面の外観、曲げ耐性及び耐カール性等を向上させるうえで有利である。また、第１樹脂層１０が発光性半導体微粒子を含有する場合、フローマークが低減されることで、透明樹脂フィルムからの発光の面内均一性が向上しやすい。 (5) Product of thickness ratio and melt flow rate ratio Ratio of average thickness T 1AV [μm] of first resin layer 10 to average thickness T 2AV [μm] of second resin layer 20 Let A be T 1AV /T 2AV , where B is the ratio M 1 /M 2 of the melt flow rate M 1 [g/10 minutes] of the first resin to the melt flow rate M 2 [g/10 minutes] of the second resin, the transparent resin film is Formula (i):
A×B≦18 (i)
It is preferable to satisfy the following.
Satisfying the formula (i) is advantageous in improving the surface hardness, surface appearance, bending resistance, curl resistance, etc. of the transparent resin film. Moreover, when the first resin layer 10 contains luminescent semiconductor fine particles, flow marks are reduced, and the in-plane uniformity of light emission from the transparent resin film is likely to be improved.
　メルトフローレートＭ１とメルトフローレートＭ２とは同一条件下で測定されるメルトフローレートであり、具体的には、ＪＩＳ　Ｋ　７２１０に準拠し、２００℃、荷重５ｋｇの条件下で測定されるメルトフローレート［ｇ／１０分］である。 Melt flow rate M1 and melt flow rate M2 are melt flow rates measured under the same conditions, specifically, in accordance with JIS K 7210, at 200 ° C. and under a load of 5 kg. Melt flow rate [g/10 minutes].
　Ａ×Ｂの値は、透明樹脂フィルムの表面硬度、表面の外観、曲げ耐性及び耐カール性等を高める観点から、より好ましくは１５以下、さらに好ましくは１２以下、なおさらに好ましくは１０以下、特に好ましくは８以下、最も好ましくは６以下である。Ａ×Ｂの値は、透明樹脂フィルムの表面硬度、表面の外観、曲げ耐性、耐カール性及び発光特性を高めやすいことから、好ましくは１以上であり、２以上、３以上又は４以上であってもよい。 From the viewpoint of improving the surface hardness, surface appearance, bending resistance, curl resistance, etc. of the transparent resin film, the value of A×B is more preferably 15 or less, still more preferably 12 or less, still more preferably 10 or less, especially Preferably it is 8 or less, most preferably 6 or less. The value of A×B is preferably 1 or more, 2 or more, 3 or more, or 4 or more, since it is easy to improve the surface hardness, surface appearance, bending resistance, curl resistance, and luminescent properties of the transparent resin film. It's okay.
　Ｂの値は、透明樹脂フィルムにおいて、無機粒子１５に基づく光学特性と機械的強度とを両立させやすくなることから、また、透明樹脂フィルムの表面硬度、表面の外観、曲げ耐性及び耐カール性等を高める観点から、好ましくは１０以下、より好ましくは５以下、さらに好ましくは３以下、なおさらに好ましくは２以下、特に好ましくは１．５以下、特により好ましくは１．２以下、最も好ましくは１．０であり、好ましくは０．５以上、より好ましくは０．７以上、さらに好ましくは０．９以上、なおさらに好ましくは０．９５以上である。さらに、Ｂの値を上記範囲内にすることにより、第１樹脂層１０と第２樹脂層２０との密着性を高めることができる。 The value of B is determined because it becomes easier to achieve both optical properties based on the inorganic particles 15 and mechanical strength in the transparent resin film, and also depends on the surface hardness, surface appearance, bending resistance, curl resistance, etc. of the transparent resin film. From the viewpoint of increasing the .0, preferably 0.5 or more, more preferably 0.7 or more, even more preferably 0.9 or more, even more preferably 0.95 or more. Furthermore, by setting the value of B within the above range, the adhesion between the first resin layer 10 and the second resin layer 20 can be improved.
　また、第３樹脂層３０の平均厚みＴ３ＡＶ［μｍ］に対する第１樹脂層１０の平均厚みＴ１ＡＶ［μｍ］の比Ｔ１ＡＶ／Ｔ３ＡＶをＡ’とし、第３樹脂のメルトフローレートＭ３［ｇ／１０分］に対する第１樹脂のメルトフローレートＭ１［ｇ／１０分］の比Ｍ１／Ｍ３をＢ’とするとき、透明樹脂フィルムは、式（ｉｉ）：
　Ａ’×Ｂ’≦１８　　　　（ｉｉ）
を満たすことが好ましい。
　式（ｉｉ）を満たすことは、透明樹脂フィルムの表面硬度、表面の外観、曲げ耐性及び耐カール性を向上させるうえでさらに有利である。 Further, the ratio T 1AV /T 3AV of the average thickness T 1AV [μm] of the first resin layer 10 to the average thickness T 3AV [μm] of the third resin layer 30 is defined as A', and the melt flow rate M 3 of the third resin is When the ratio M 1 /M 3 of the melt flow rate M 1 [g/10 min] of the first resin to [g/10 min] is B', the transparent resin film has the formula (ii):
A'×B'≦18 (ii)
It is preferable to satisfy the following.
Satisfying formula (ii) is further advantageous in improving the surface hardness, surface appearance, bending resistance, and curl resistance of the transparent resin film.
　メルトフローレートＭ１とメルトフローレートＭ３とは同一条件下で測定されるメルトフローレートであり、具体的には、ＪＩＳ　Ｋ　７２１０に準拠し、２００℃、荷重５ｋｇの条件下で測定されるメルトフローレート［ｇ／１０分］である。 Melt flow rate M1 and melt flow rate M3 are melt flow rates measured under the same conditions, specifically, in accordance with JIS K 7210, at 200 ° C. and under a load of 5 kg. Melt flow rate [g/10 minutes].
　Ａ’×Ｂ’の値は、透明樹脂フィルムの表面硬度、表面の外観、曲げ耐性及び耐カール性等を高める観点から、より好ましくは１５以下、さらに好ましくは１２以下、なおさらに好ましくは１０以下、特に好ましくは８以下、最も好ましくは６以下である。Ａ’×Ｂ’の値は、透明樹脂フィルムの表面硬度、表面の外観、曲げ耐性、耐カール性及び発光特性を高めやすいことから、好ましくは１以上であり、２以上、３以上又は４以上であってもよい。 From the viewpoint of improving the surface hardness, surface appearance, bending resistance, curl resistance, etc. of the transparent resin film, the value of A'×B' is more preferably 15 or less, still more preferably 12 or less, and even more preferably 10 or less. , particularly preferably 8 or less, most preferably 6 or less. The value of A'×B' is preferably 1 or more, 2 or more, 3 or more, or 4 or more because it is easy to improve the surface hardness, surface appearance, bending resistance, curl resistance, and luminescent properties of the transparent resin film. It may be.
　Ｂ’の値は、透明樹脂フィルムにおいて、無機粒子１５に基づく光学特性と機械的強度とを両立させやすくなることから、また、透明樹脂フィルムの表面硬度、表面の外観、曲げ耐性及び耐カール性等を高める観点から、好ましくは１０以下、より好ましくは５以下、さらに好ましくは３以下、なおさらに好ましくは２以下、特に好ましくは１．５以下、特により好ましくは１．２以下、最も好ましくは１．０であり、好ましくは０．５以上、より好ましくは０．７以上、さらに好ましくは０．９以上、なおさらに好ましくは０．９５以上である。さらに、Ｂ’の値を上記範囲内にすることにより、第１樹脂層１０と第３樹脂層３０との密着性を高めることができる。 The value of B' is determined because it becomes easier to achieve both optical properties based on the inorganic particles 15 and mechanical strength in the transparent resin film. From the viewpoint of increasing the 1.0, preferably 0.5 or more, more preferably 0.7 or more, even more preferably 0.9 or more, even more preferably 0.95 or more. Furthermore, by setting the value of B' within the above range, the adhesion between the first resin layer 10 and the third resin layer 30 can be improved.
　１つの実施形態において透明樹脂フィルムは、第２樹脂層２０と第１樹脂層１０と第３樹脂層３０とをこの順に含み、好ましくは下記のいずれかを満たし、より好ましくは下記の２以上を満たし、さらに好ましくは下記のすべてを満たす。
　〔ａ〕比Ｔ３／Ｔ２が０．８以上１．２以下である。
　〔ｂ〕比Ｍ３／Ｍ２が０．９以上１．２以下、好ましくは１である。
　〔ｃ〕第１樹脂と、第２樹脂又は第３樹脂とが同一である。
　〔ｄ〕第２樹脂と第３樹脂とが同一である。
　〔ｅ〕第２樹脂層と第３樹脂層とが、それらを構成する材料組成において同一である。
　〔ｆ〕ＡとＡ’とがいずれも、３０以下、好ましくは２０以下、より好ましくは１５以下、さらに好ましくは１２以下、なおさらに好ましくは１０以下である。
　〔ｇ〕ＢとＢ’とが同一である。
　〔ｈ〕Ａ×ＢとＡ’×Ｂ’とがいずれも、１８以下、好ましくは１５以下、より好ましくは１２以下、さらに好ましくは１０以下である。
　上記〔ｇ〕において「同一である」とは、一方の値が他方の値の±５％の範囲内である場合を含む。 In one embodiment, the transparent resin film includes a second resin layer 20, a first resin layer 10, and a third resin layer 30 in this order, and preferably satisfies any of the following, more preferably satisfies two or more of the following. and more preferably all of the following.
[a] The ratio T 3 /T 2 is 0.8 or more and 1.2 or less.
[b] The ratio M 3 /M 2 is 0.9 or more and 1.2 or less, preferably 1.
[c] The first resin and the second or third resin are the same.
[d] The second resin and the third resin are the same.
[e] The second resin layer and the third resin layer have the same material composition.
[f] Both A and A' are 30 or less, preferably 20 or less, more preferably 15 or less, still more preferably 12 or less, even more preferably 10 or less.
[g] B and B' are the same.
[h] Both A×B and A′×B′ are 18 or less, preferably 15 or less, more preferably 12 or less, still more preferably 10 or less.
In [g] above, "being the same" includes the case where one value is within the range of ±5% of the other value.
　（６）透明樹脂フィルムの優位性
　透明樹脂フィルムは、その両面の表面硬度のバラツキが小さい。また、透明樹脂フィルムは、その両面の表面硬度が高いものであり得る。透明樹脂フィルムの第２樹脂層における第１樹脂層とは反対側の表面、及び、第３樹脂層における第１樹脂層とは反対側の表面の鉛筆硬度は、それぞれ、好ましくはＨＢ以上である。鉛筆硬度は、後述する［実施例］の項に記載の方法に従って測定することができる。 (6) Advantages of transparent resin film A transparent resin film has small variations in surface hardness on both sides. Further, the transparent resin film may have high surface hardness on both sides. The pencil hardness of the surface of the second resin layer of the transparent resin film opposite to the first resin layer and the surface of the third resin layer opposite to the first resin layer are preferably HB or higher. . Pencil hardness can be measured according to the method described in the [Examples] section below.
　透明樹脂フィルムは、表面の外観及び耐カール性が良好なものであり得る。表面の外観が良好な透明樹脂フィルムは、フィルム成形時にフィルム表面に形成され得るフローマーク（斑点模様等）が低減されているか、又はこれを有しない。耐カール性が良好な透明樹脂フィルムは、ロール（巻回物）状態にしても巻癖が付きにくい。さらには、第１樹脂層が発光性半導体微粒子を含有する場合、フローマークが低減されることで、透明樹脂フィルムからの発光の面内均一性が向上しやすい。 The transparent resin film may have good surface appearance and curl resistance. A transparent resin film with a good surface appearance has reduced or no flow marks (spotted patterns, etc.) that may be formed on the film surface during film molding. A transparent resin film with good curl resistance is resistant to curling even when rolled. Furthermore, when the first resin layer contains luminescent semiconductor fine particles, flow marks are reduced, and the in-plane uniformity of light emission from the transparent resin film is likely to be improved.
　透明樹脂フィルムの表面の外観は、目視で確認することができる。透明樹脂フィルムの耐カール性は、後述する［実施例］の項に記載の方法によって測定される距離［ｍｍ］によって評価することができる。該距離は、好ましくは１５ｍｍ以下、より好ましくは１２ｍｍ以下、さらに好ましくは１０ｍｍ以下である。 The appearance of the surface of the transparent resin film can be visually confirmed. The curl resistance of the transparent resin film can be evaluated by the distance [mm] measured by the method described in the [Examples] section below. The distance is preferably 15 mm or less, more preferably 12 mm or less, even more preferably 10 mm or less.
　透明樹脂フィルムは、曲げ耐性が良好なものであり得る。曲げ耐性が良好な透明樹脂フィルムは、曲率半径４ｍｍでフィルムを折り曲げても、少なくとも一方向に折り曲げたときにワレを生じにくい。 The transparent resin film may have good bending resistance. A transparent resin film with good bending resistance is unlikely to crack when folded in at least one direction, even if the film is folded with a radius of curvature of 4 mm.
　＜透明樹脂フィルムの製造方法＞
　透明樹脂フィルムは、特に制限されるものではないが、押出成形によって製造されることが好ましく、共押出成形によって製造されることがより好ましい。この場合、透明樹脂フィルムは押出成形品であり、好ましくは共押出成形品である。透明樹脂フィルムを押出成形により製造する場合、各層の厚みを均一にしやすい観点から、第１樹脂、第２樹脂及び第３樹脂にそれぞれＨＩＰＳ樹脂を用いることが好ましい。 <Method for manufacturing transparent resin film>
Although the transparent resin film is not particularly limited, it is preferably manufactured by extrusion molding, and more preferably manufactured by coextrusion molding. In this case, the transparent resin film is an extrusion molded product, preferably a coextrusion molded product. When manufacturing a transparent resin film by extrusion molding, it is preferable to use HIPS resin as each of the first resin, second resin, and third resin from the viewpoint of easily making the thickness of each layer uniform.
　共押出成形による透明樹脂フィルムの製造方法は、例えば、以下の工程を含む製造方法であることができる。
　第１樹脂層用の第１樹脂組成物を調製する工程（Ｘ）、
　第２樹脂層用の第２樹脂組成物を調製する工程（Ｙ－１）、
　第３樹脂層用の第３樹脂組成物を調製する工程（Ｙ－２）、
　第１樹脂組成物、第２樹脂組成物及び第３樹脂組成物を用い、共押出成形により透明樹脂フィルムを製造する工程（Ｚ）。 A method for manufacturing a transparent resin film by coextrusion molding may include, for example, the following steps.
Step (X) of preparing a first resin composition for the first resin layer;
Step (Y-1) of preparing a second resin composition for the second resin layer;
Step (Y-2) of preparing a third resin composition for the third resin layer;
Step (Z) of manufacturing a transparent resin film by coextrusion molding using the first resin composition, the second resin composition, and the third resin composition.
　第２樹脂組成物と第３樹脂組成物とが同一組成である場合には、工程（Ｙ－１）と別に工程（Ｙ－２）を設ける必要はなく、第３樹脂組成物として第２樹脂組成物を用いればよい。 When the second resin composition and the third resin composition have the same composition, there is no need to provide a step (Y-2) separately from the step (Y-1), and the second resin composition is used as the third resin composition. A composition may be used.
　工程（Ｘ）は、所望の含有率で無機粒子、第１樹脂及び任意で含有される添加剤等を含有する第１樹脂組成物を、好ましくは加熱溶融混練を経て、調製する工程である。工程（Ｘ）は、複数の工程からなっていてもよい。例えば、工程（Ｘ）は、無機粒子である光散乱剤と第１樹脂とを加熱溶融混練してこれらを含むマスターバッチ（ＭＢ）を調製する工程；無機粒子である半導体粒子と第１樹脂とを加熱溶融混練してこれらを含むＭＢを調製する工程；及び、各ＭＢと第１樹脂とを加熱溶融混練してこれらを含む第１樹脂組成物を調製する工程を含むことができる。ＭＢが複数ある場合、添加剤は、複数のＭＢのいずれか又はすべてに含有させることができる。各ＭＢは、ペレットの形態で調製されてよい。ＭＢを用いる方法によれば、無機粒子や添加剤の濃度が均一な第１樹脂組成物を調製しやすい。 Step (X) is a step of preparing a first resin composition containing inorganic particles, a first resin, optional additives, etc. at a desired content, preferably through heating and melt-kneading. Step (X) may consist of a plurality of steps. For example, step (X) is a step of preparing a masterbatch (MB) containing a light scattering agent, which is an inorganic particle, and a first resin by heating and melt-kneading them; The method may include a step of heating and melt-kneading each MB and a first resin to prepare an MB containing them; and a step of heating and melt-kneading each MB and a first resin to prepare a first resin composition containing them. When there are multiple MBs, the additive can be contained in any or all of the multiple MBs. Each MB may be prepared in pellet form. According to the method using MB, it is easy to prepare a first resin composition with uniform concentrations of inorganic particles and additives.
　加熱溶融混練による第１樹脂組成物の調製及び各ＭＢの調製は、所定成分を二軸押出機等の押出機に投入し、加熱溶融混練する方法によって実施できる。加熱溶融混練時の温度は、例えば１５０℃以上、好ましくは１８０℃以上、より好ましくは２００℃以上であり、例えば３５０℃以下、好ましくは３２０℃以下、より好ましくは３００℃以下、さらに好ましくは２８０℃以下、特に好ましくは２６０℃以下である。 Preparation of the first resin composition and preparation of each MB by heating and melt-kneading can be carried out by a method in which predetermined components are put into an extruder such as a twin-screw extruder and then heated and melt-kneaded. The temperature during heating and melt-kneading is, for example, 150°C or higher, preferably 180°C or higher, more preferably 200°C or higher, and, for example, 350°C or lower, preferably 320°C or lower, more preferably 300°C or lower, and still more preferably 280°C or lower. The temperature is preferably 260°C or lower, particularly preferably 260°C or lower.
　第１樹脂組成物の調製及びＭＢの調製において、所定成分の混合物に溶剤や水分が含まれる場合には、加熱溶融混練しながら又は加熱溶融混練後に、これらを除去するための脱揮処理を行うことができる。所定成分の混合物に溶剤が含まれる場合とは、例えば、半導体粒子を、これを分散媒に分散させた分散液の形態で投入する場合である。 In the preparation of the first resin composition and the preparation of MB, if the mixture of predetermined components contains a solvent or water, a devolatilization treatment is performed to remove these during or after heating and melting and kneading. be able to. The case where a solvent is included in the mixture of predetermined components is, for example, the case where semiconductor particles are introduced in the form of a dispersion liquid in which semiconductor particles are dispersed in a dispersion medium.
　工程（Ｙ－１）及び工程（Ｙ－２）における第２樹脂組成物及び第３樹脂組成物についても、第１樹脂組成物と同様にして調製することができる。例えば、工程（Ｙ－１）は、アンチブロッキング剤と第２樹脂とを溶融混練してこれらを含むＭＢを調製する工程；及び、ＭＢと第２樹脂とを溶融混練してこれらを含む第２樹脂組成物を調製する工程を含むことができる。添加剤は、ＭＢに含有させることができる。 The second resin composition and third resin composition in step (Y-1) and step (Y-2) can also be prepared in the same manner as the first resin composition. For example, step (Y-1) is a step of melt-kneading an anti-blocking agent and a second resin to prepare a MB containing them; and a step of melt-kneading an MB and a second resin to prepare a second resin containing them. The method may include a step of preparing a resin composition. Additives can be included in the MB.
　工程（Ｚ）における共押出成形は、従来公知の方法で行ってよい。例えば、工程（Ｘ）において第１押出機内で調製された溶融状態の第１樹脂組成物と、工程（Ｙ－１）及び工程（Ｙ－２）において第１押出機とは異なる第２押出機内で調製された溶融状態の第２樹脂組成物（及び第３樹脂組成物）とを、３層構成のフィードブロックに供給し、さらにＴ－ダイから共押出することにより、第１樹脂層、第２樹脂層及び第３樹脂層を有する透明樹脂フィルムを製造することができる。共押出時の各樹脂組成物の温度は、例えば１５０℃以上、好ましくは１８０℃以上、より好ましくは２００℃以上であり、例えば３５０℃以下、好ましくは３２０℃以下、より好ましくは３００℃以下、さらに好ましくは２８０℃以下、特に好ましくは２６０℃以下である。 Coextrusion molding in step (Z) may be performed by a conventionally known method. For example, a first resin composition in a molten state prepared in a first extruder in step (X) and a second extruder different from the first extruder in steps (Y-1) and (Y-2) The second resin composition (and the third resin composition) in a molten state prepared in the above are supplied to a three-layer feedblock, and further coextruded from a T-die to form the first resin layer and the third resin composition. A transparent resin film having two resin layers and a third resin layer can be manufactured. The temperature of each resin composition during coextrusion is, for example, 150°C or higher, preferably 180°C or higher, more preferably 200°C or higher, and, for example, 350°C or lower, preferably 320°C or lower, more preferably 300°C or lower, The temperature is more preferably 280°C or lower, particularly preferably 260°C or lower.
　Ｔ－ダイから押し出された溶融状態の積層物を成形・冷却ロールに通すことによって、長尺物としての透明樹脂フィルムが得られる。共押出成形において、各樹脂組成物の粘度、押出速度及び／又は押出量を制御したり、成形・冷却ロール間の押し付け圧を制御したり、成形・冷却ロールの温度を均一に保持したりすることで、両面の表面硬度のバラツキが小さい透明樹脂フィルムが得られやすい。 A transparent resin film as a long product is obtained by passing the molten laminate extruded from the T-die through a forming/cooling roll. In coextrusion molding, controlling the viscosity, extrusion speed and/or amount of each resin composition, controlling the pressing pressure between the molding and cooling rolls, and maintaining the temperature of the molding and cooling rolls uniformly. This makes it easy to obtain a transparent resin film with small variations in surface hardness on both sides.
　透明樹脂フィルムのＡ（比Ｔ１／Ｔ２）の値及びＡ’（比Ｔ１／Ｔ３）の値は、例えば、フィードブロックへの樹脂組成物の供給速度比（押出量比）を調整することによって制御できる。透明樹脂フィルムが有する各樹脂層の厚みは、例えば、フィードブロックへの樹脂組成物の供給速度、Ｔ－ダイ吐出口の開口幅、成形・冷却ロールにおけるロール間ギャップ（間隔）等を調整することによって制御できる。第２樹脂層と第３樹脂層とが、組成や厚みにおいて異なる場合には、第３樹脂組成物を調製するための第３押出機を別途準備すればよい。 The value of A (ratio T 1 /T 2 ) and the value of A' (ratio T 1 /T 3 ) of the transparent resin film can be adjusted, for example, by adjusting the supply speed ratio (extrusion amount ratio) of the resin composition to the feed block. It can be controlled by The thickness of each resin layer of the transparent resin film can be adjusted, for example, by adjusting the supply rate of the resin composition to the feed block, the opening width of the T-die discharge port, the gap between the rolls in the forming/cooling roll, etc. can be controlled by If the second resin layer and the third resin layer are different in composition or thickness, a third extruder for preparing the third resin composition may be separately prepared.
　透明樹脂フィルムの製造方法は、上記以外の他の工程を有していてもよい。他の工程としては、上記長尺物である透明樹脂フィルムの長手方向端部をトリミングする工程、上記長尺物である透明樹脂フィルムをロール状に巻き取る工程、上記長尺物である透明樹脂フィルムを所定サイズの枚葉フィルムに裁断する工程等が挙げられる。 The method for producing a transparent resin film may include steps other than those described above. The other steps include a step of trimming the longitudinal ends of the long transparent resin film, a step of winding up the long transparent resin film into a roll, and a step of winding the long transparent resin film into a roll. Examples include a step of cutting the film into sheets of predetermined size.
　＜表示装置＞
　本発明に係る表示装置は、上記透明樹脂フィルムを含む。表示装置としては、液晶表示装置、有機ＥＬ表示装置、無機ＥＬ表示装置等が挙げられる。透明樹脂フィルムは、光源（液晶表示装置のバックライト、有機ＥＬ表示装置や無機ＥＬ表示装置のＥＬ表示素子）の上（視認側）に配置することにより、光源からの光を拡散させたり、波長変換を行ったりするフィルム（すなわち、拡散フィルム又は波長変換フィルム）として好適に用いることができる。 <Display device>
A display device according to the present invention includes the transparent resin film described above. Examples of the display device include a liquid crystal display device, an organic EL display device, an inorganic EL display device, and the like. By placing the transparent resin film over the light source (the backlight of a liquid crystal display device, the EL display element of an organic EL display device or an inorganic EL display device) (on the viewing side), it can diffuse the light from the light source and change the wavelength. It can be suitably used as a film that performs conversion (ie, a diffusion film or a wavelength conversion film).
　以下、実施例により本発明をさらに詳細に説明する。例中の「％」及び「部」は、特記のない限り、質量％及び質量部である。 Hereinafter, the present invention will be explained in more detail with reference to Examples. "%" and "parts" in the examples are mass % and parts by mass unless otherwise specified.
　＜測定及び評価＞
　（１）透明樹脂フィルム及び樹脂層の厚みの測定
　製造した透明樹脂フィルムについて、ミクロトームを用いてその断面を露出させた。透明樹脂フィルムの面内において、ランダムに測定点を３点選択し（以下、それぞれ「測定点１～３」という。）、測定点１～３のそれぞれにおいて、第１樹脂層、第２樹脂層及び第３樹脂層の厚みを、レーザー顕微鏡（オリンパス株式会社製「ＬＥＸＴ　ＯＬＳ４０００」）を用いた断面観測により測定した。これにより、第１樹脂層の厚みＴ１、第２樹脂層の厚みＴ２及び第３樹脂層の厚みＴ３について、それぞれ、３つの測定値を得た。 <Measurement and evaluation>
(1) Measurement of thickness of transparent resin film and resin layer The cross section of the manufactured transparent resin film was exposed using a microtome. Three measurement points are randomly selected within the plane of the transparent resin film (hereinafter referred to as "measurement points 1 to 3"), and at each of measurement points 1 to 3, the first resin layer and the second resin layer are selected at random. And the thickness of the third resin layer was measured by cross-sectional observation using a laser microscope ("LEXT OLS4000" manufactured by Olympus Corporation). As a result, three measured values were obtained for each of the thickness T 1 of the first resin layer, the thickness T 2 of the second resin layer, and the thickness T 3 of the third resin layer.
　測定点１～３について得られた第１樹脂層の厚みＴ１の平均値を第１樹脂層の平均厚みＴ１ＡＶとし、測定点１～３について得られた第２樹脂層の厚みＴ２の平均値を第２樹脂層の平均厚みＴ２ＡＶとし、測定点１～３について得られた第３樹脂層の厚みＴ３の平均値を第３樹脂層の平均厚みＴ３ＡＶとした。 The average value of the thickness T 1 of the first resin layer obtained for measurement points 1 to 3 is taken as the average value of the first resin layer thickness T 1AV , and the thickness T 2 of the second resin layer obtained for measurement points 1 to 3 is The average value was taken as the average thickness T 2AV of the second resin layer, and the average value of the thickness T 3 of the third resin layer obtained at measurement points 1 to 3 was taken as the average thickness T 3AV of the third resin layer.
　また、測定点１～３のそれぞれについて第１樹脂層の厚みＴ１、第２樹脂層の厚みＴ２及び第３樹脂層の厚みＴ３の合計を求めることにより、透明樹脂フィルムの厚みＴについて３つの測定値を得た。測定点１～３について得られた透明樹脂フィルムの厚みＴの平均値を透明樹脂フィルムの平均厚みＴＡＶとした。 In addition, the thickness T of the transparent resin film can be determined by calculating the sum of the thickness T 1 of the first resin layer, the thickness T 2 of the second resin layer, and the thickness T 3 of the third resin layer for each of measurement points 1 to 3. Three measurements were taken. The average value of the thickness T of the transparent resin film obtained for measurement points 1 to 3 was defined as the average thickness T AV of the transparent resin film.
　（２）Ｔ２／Ｔの標準偏差及びＴ３／Ｔの標準偏差の算出
　上記（１）で得られた測定点１～３について得られたＴ２、Ｔ３及びＴの値に基づいてＴ２／Ｔの標準偏差、Ｔ３／Ｔの標準偏差及びこれらの和を求めた。 (2) Calculation of standard deviation of T 2 /T and standard deviation of T 3 /T Based on the values of T 2 , T 3 and T obtained for measurement points 1 to 3 obtained in (1) above, T The standard deviation of 2 /T, the standard deviation of T 3 /T, and the sum of these were determined.
　（３）樹脂のメルトフローレートの測定
　ＪＩＳ　Ｋ　７２１０に準拠し、メルトインデクサ（テクノ・セブン社製「Ｌ２１７－Ｅ１４０１１」）を用いて、２００℃、荷重５ｋｇで測定した。用いたＨＩＰＳ樹脂のメルトフローレートは、３．３ｇ／１０分であった。 (3) Measurement of melt flow rate of resin In accordance with JIS K 7210, measurement was performed at 200° C. and a load of 5 kg using a melt indexer (“L217-E14011” manufactured by Techno Seven). The melt flow rate of the HIPS resin used was 3.3 g/10 minutes.
　（４）透明樹脂フィルム表面の鉛筆硬度の測定及びバラツキ評価
　製造した透明樹脂フィルムから、５０ｍｍ×５０ｍｍの試験片を切り出した。第２樹脂層における第１樹脂層とは反対側の表面（第２樹脂層側表面）について、ＨＥＩＤＯＮ社製　トライボギアを用いて、ＪＩＳ　Ｋ　５６００－５－４：１９９９に規定される鉛筆硬度試験に従って鉛筆硬度を測定した。第３樹脂層における第１樹脂層とは反対側の表面（第３樹脂層側表面）についても、同様にして鉛筆硬度を測定した。第２樹脂層側表面及び第３樹脂層側表面のそれぞれについて、上記測定点１～３の位置で鉛筆硬度の測定を行うことにより、鉛筆硬度のバラツキを評価した。なお、鉛筆硬度の測定において、実施例１～３では荷重を７５０ｇとし、実施例４～６及び比較例１では荷重を２５０ｇとした。測定点１～３の位置での鉛筆硬度は同等であることが好ましい。 (4) Measurement of pencil hardness on the surface of transparent resin film and evaluation of variation A test piece of 50 mm x 50 mm was cut out from the produced transparent resin film. The surface of the second resin layer opposite to the first resin layer (second resin layer side surface) was tested according to the pencil hardness test specified in JIS K 5600-5-4:1999 using Tribogear manufactured by HEIDON. Pencil hardness was measured. The pencil hardness of the surface of the third resin layer opposite to the first resin layer (the surface on the third resin layer side) was similarly measured. The variation in pencil hardness was evaluated by measuring the pencil hardness at the measurement points 1 to 3 on each of the second resin layer side surface and the third resin layer side surface. In the measurement of pencil hardness, the load was 750 g in Examples 1 to 3, and 250 g in Examples 4 to 6 and Comparative Example 1. It is preferable that the pencil hardness at measurement points 1 to 3 be the same.
　（５）透明樹脂フィルム表面の外観評価
　透明樹脂フィルムの表面外観を目視観察し、下記基準に従って評価した。
　Ａ：フローマーク（斑点模様等）が認められない。
　Ｂ：フローマークが認められる。 (5) Appearance evaluation of transparent resin film surface The surface appearance of the transparent resin film was visually observed and evaluated according to the following criteria.
A: Flow marks (spotted patterns, etc.) are not observed.
B: Flow marks are observed.
　（６）透明樹脂フィルムの耐カール性の評価
　製造した透明樹脂フィルムから、長手方向がＭＤ方向となるように１５０ｍｍ×１００ｍｍサイズの試験片を切り出した。この試験片を、直径が１６ｍｍである樹脂製の芯棒に巻き付け、端部をテープで固定し、温度２５℃、相対湿度５０％ＲＨの環境下で１分間静置した。次いで、試験片を芯棒から取り外し、カールした試験片の凸面を上にして水平台に置き、水平台の面から試験片凸部の最高点までの距離［ｍｍ］を測定した。 (6) Evaluation of curl resistance of transparent resin film A test piece of 150 mm x 100 mm size was cut out from the manufactured transparent resin film so that the longitudinal direction was in the MD direction. This test piece was wound around a resin core rod having a diameter of 16 mm, the ends were fixed with tape, and the test piece was left standing for 1 minute in an environment of a temperature of 25° C. and a relative humidity of 50% RH. Next, the test piece was removed from the core rod, placed on a horizontal stand with the convex surface of the curled test piece facing up, and the distance [mm] from the surface of the horizontal stand to the highest point of the test piece's convex portion was measured.
　（７）透明樹脂フィルムの曲げ耐性の評価
　製造した透明樹脂フィルムから、幅２０ｍｍ×長さ８０ｍｍの長方形の試験片を切り出した。下記の評価基準に従って、試験片の長辺方向の中心を曲率半径４ｍｍでフィルムを折り曲げたときのワレ及び分断の有無から、曲げ耐性を評価した。ワレとは、折り目に沿って透明樹脂フィルムの一部に、厚み方向全体にわたって裂け目が生じている状態をいい、分断とは、該裂け目が折り目全体に生じた結果、透明樹脂フィルムが２つに分断された状態をいう。
　ＡＡ：一方向に折り曲げた後、逆方向に折り曲げてもワレを生じない。
　　Ａ：一方向に折り曲げたときにはワレを生じないが、続けて逆方向に折り曲げるとワレを生じる。
　　Ｂ：一方向に折り曲げたときに分断が生じる。 (7) Evaluation of bending resistance of transparent resin film A rectangular test piece with a width of 20 mm and a length of 80 mm was cut out from the produced transparent resin film. The bending resistance was evaluated based on the presence or absence of cracks and splits when the film was bent at a radius of curvature of 4 mm at the center in the long side direction of the test piece according to the following evaluation criteria. Cracking refers to a state in which a tear occurs in a part of the transparent resin film along the fold along the entire thickness direction, and splitting refers to a state in which the transparent resin film is split into two as a result of the tear occurring throughout the fold. A state of being divided.
AA: No cracking occurs even after bending in one direction and then bending in the opposite direction.
A: No cracks occur when folded in one direction, but cracks occur when folded in the opposite direction.
B: Parting occurs when folded in one direction.
　＜製造例１：第１樹脂層用のガラスビーズＭＢの調製＞
　ＨＩＰＳ樹脂ペレット、ガラスビーズ（光散乱剤）、酸化防止剤、紫外線吸収剤を、下記の配合比率でタンブラーにてドライブレンドし、二軸押出機を用い成形温度２００～２６０℃で混練した。押出機から得られたストランドをウォーターバスで冷却した後、ペレタイザーで切断することによって、ガラスビーズが樹脂中に分散した第１樹脂層用のガラスビーズＭＢを得た。
　ＨＩＰＳ樹脂ペレット（ＰＳ　Ｊａｐａｎ社製「ＳＸ１００」、メルトフローレート（ＭＦＲ）：３．３ｇ／１０分）　　　　　　　　７６．０質量％
　ガラスビーズ（ユニチカ社製「ＵＢＳ－００１０Ｅ」、メイン粒径：～１０μｍ、密度：２．６ｇ／ｃｍ３）
　　　　　　　　　　　　　　　　　　　　　　２０．０質量％
　酸化防止剤（住友化学株式会社製「スミライザーＧＰ」）
　　　　　　　　　　　　　　　　　　　　　　　２．０質量％
　紫外線吸収剤（城北化学工業株式会社製「ＪＦ－７７」）
　　　　　　　　　　　　　　　　　　　　　　　２．０質量％ <Manufacture example 1: Preparation of glass beads MB for the first resin layer>
HIPS resin pellets, glass beads (light scattering agent), antioxidant, and ultraviolet absorber were dry blended in a tumbler at the following blending ratio, and kneaded at a molding temperature of 200 to 260°C using a twin-screw extruder. The strand obtained from the extruder was cooled in a water bath and then cut with a pelletizer to obtain glass beads MB for the first resin layer in which glass beads were dispersed in the resin.
HIPS resin pellets (“SX100” manufactured by PS Japan, melt flow rate (MFR): 3.3 g/10 minutes) 76.0% by mass
Glass beads (“UBS-0010E” manufactured by Unitika, main particle size: ~10 μm, density: 2.6 g/cm 3 )
20.0% by mass
Antioxidant (“Sumilyzer GP” manufactured by Sumitomo Chemical Co., Ltd.)
2.0% by mass
Ultraviolet absorber (JF-77 manufactured by Johoku Kagaku Kogyo Co., Ltd.)
2.0% by mass
　＜製造例２：第１樹脂層用の酸化チタン粒子ＭＢの調製＞
　ＨＩＰＳ樹脂ペレット、酸化チタン（ＴｉＯ２）粒子（光散乱剤）、酸化防止剤、紫外線吸収剤を、下記の配合比率でタンブラーにてドライブレンドし、二軸押出機を用い成形温度２００～２６０℃で混練した。押出機から得られたストランドをウォーターバスで冷却した後、ペレタイザーで切断することによって、酸化チタン粒子が樹脂中に分散した第１樹脂層用の酸化チタン粒子ＭＢを得た。
　ＨＩＰＳ樹脂ペレット（ＰＳ　Ｊａｐａｎ社製「ＳＸ１００」、メルトフローレート（ＭＦＲ）：３．３ｇ／１０分）　　　　　　　　９１．０質量％
　酸化チタン粒子（体積基準のメディアン径：０．２μｍ、密度：４．２ｇ／ｃｍ３）
　　　　　　　　　　　　　　　　　　　　　　　５．０質量％
　酸化防止剤（住友化学株式会社製「スミライザーＧＰ」）
　　　　　　　　　　　　　　　　　　　　　　　２．０質量％
　紫外線吸収剤（城北化学工業株式会社製「ＪＦ－７７」）
　　　　　　　　　　　　　　　　　　　　　　　２．０質量％ <Production Example 2: Preparation of titanium oxide particles MB for the first resin layer>
HIPS resin pellets, titanium oxide (TiO 2 ) particles (light scattering agent), antioxidant, and ultraviolet absorber were dry blended in a tumbler at the following blending ratio, and molded at a temperature of 200 to 260°C using a twin-screw extruder. It was kneaded with The strand obtained from the extruder was cooled in a water bath and then cut with a pelletizer to obtain titanium oxide particles MB for the first resin layer in which titanium oxide particles were dispersed in the resin.
HIPS resin pellets (“SX100” manufactured by PS Japan, melt flow rate (MFR): 3.3 g/10 minutes) 91.0% by mass
Titanium oxide particles (median diameter based on volume: 0.2 μm, density: 4.2 g/cm 3 )
5.0% by mass
Antioxidant (“Sumilyzer GP” manufactured by Sumitomo Chemical Co., Ltd.)
2.0% by mass
Ultraviolet absorber (JF-77 manufactured by Johoku Kagaku Kogyo Co., Ltd.)
2.0% by mass
　＜製造例３：第２及び第３樹脂層用のＭＢの調製＞
　ＨＩＰＳ樹脂ペレット、アンチブロッキング剤、酸化防止剤、紫外線吸収剤を、下記の配合比率でタンブラーにてドライブレンドし、二軸押出機を用い成形温度２００～２６０℃で混練した。押出機から得られたストランドをウォーターバスで冷却した後、ペレタイザーで切断することによって、第２及び第３樹脂層用のＭＢを得た。
　ＨＩＰＳ樹脂ペレット（ＰＳ　Ｊａｐａｎ社製「ＳＸ１００」、メルトフローレート（ＭＦＲ）：３．３ｇ／１０分）　　　　　　　　７７．０質量％
　アンチブロッキング剤（アイカ工業社製の架橋ＰＭＭＡ粒子「ガンツパール　ＧＭ－０８０６Ｓ」　平均粒径：８μｍ）
　　　　　　　　　　　　　　　　　　　　　　２０．０質量％
　酸化防止剤（住友化学株式会社製「スミライザーＧＰ」）
　　　　　　　　　　　　　　　　　　　　　　　２．０質量％
　紫外線吸収剤（城北化学工業株式会社製「ＪＦ－７７」）
　　　　　　　　　　　　　　　　　　　　　　　１．０質量％ <Production Example 3: Preparation of MB for second and third resin layers>
HIPS resin pellets, an anti-blocking agent, an antioxidant, and an ultraviolet absorber were dry blended in a tumbler at the following blending ratio, and kneaded using a twin-screw extruder at a molding temperature of 200 to 260°C. After cooling the strand obtained from the extruder in a water bath, it was cut with a pelletizer to obtain MB for the second and third resin layers.
HIPS resin pellets (“SX100” manufactured by PS Japan, melt flow rate (MFR): 3.3 g/10 minutes) 77.0% by mass
Anti-blocking agent (crosslinked PMMA particles “Gantz Pearl GM-0806S” manufactured by Aica Kogyo Co., Ltd. Average particle size: 8 μm)
20.0% by mass
Antioxidant (“Sumilyzer GP” manufactured by Sumitomo Chemical Co., Ltd.)
2.0% by mass
Ultraviolet absorber (JF-77 manufactured by Johoku Kagaku Kogyo Co., Ltd.)
1.0% by mass
　＜実施例１＞
　製造例１で調製した第１樹脂層用のガラスビーズＭＢ、製造例２で調製した第１樹脂層用の酸化チタン粒子ＭＢ、及び、ＨＩＰＳ樹脂ペレット（ＭＢの調製に用いたものと同じもの）の所定量を二軸押出機に投入し、２００～２６０℃の温度で加熱溶融混練して、溶融状態の第１樹脂層用の樹脂組成物を得た。該樹脂組成物の組成を下記に示す。
　一方、製造例３で調製した第２及び第３樹脂層用のＭＢ、及び、ＨＩＰＳ樹脂ペレット（ＭＢの調製に用いたものと同じもの）の所定量を別の二軸押出機に投入し、２００～２６０℃の温度で加熱溶融混練して、溶融状態の第２及び第３樹脂層用の樹脂組成物を得た。該樹脂組成物の組成を下記に示す。 <Example 1>
Glass beads MB for the first resin layer prepared in Production Example 1, titanium oxide particles MB for the first resin layer prepared in Production Example 2, and HIPS resin pellets (same as those used for preparing MB) A predetermined amount of the mixture was put into a twin-screw extruder and heated and melted and kneaded at a temperature of 200 to 260°C to obtain a resin composition for the first resin layer in a molten state. The composition of the resin composition is shown below.
On the other hand, predetermined amounts of MB for the second and third resin layers prepared in Production Example 3 and HIPS resin pellets (same as those used for preparing MB) were put into another twin-screw extruder, The mixture was heated and melted and kneaded at a temperature of 200 to 260°C to obtain a resin composition for the second and third resin layers in a molten state. The composition of the resin composition is shown below.
　（第１樹脂層用の樹脂組成物の組成）
　ＨＩＰＳ樹脂　　　　：９４．５７質量％
　ガラスビーズ　　　　：　４．００質量％
　酸化チタン粒子　　　：　０．３５質量％
　酸化防止剤　　　　　：　０．５４質量％
　紫外線吸収剤　　　　：　０．５４質量％ (Composition of resin composition for first resin layer)
HIPS resin: 94.57% by mass
Glass beads: 4.00% by mass
Titanium oxide particles: 0.35% by mass
Antioxidant: 0.54% by mass
Ultraviolet absorber: 0.54% by mass
　（第２及び第３樹脂層用の樹脂組成物の組成）
　ＨＩＰＳ樹脂　　　　：９１．２６質量％
　アンチブロッキング剤：　７．６０質量％
　酸化防止剤　　　　　：　０．７６質量％
　紫外線吸収剤　　　　：　０．３８質量％ (Composition of resin composition for second and third resin layers)
HIPS resin: 91.26% by mass
Anti-blocking agent: 7.60% by mass
Antioxidant: 0.76% by mass
Ultraviolet absorber: 0.38% by mass
　上記で得た溶融状態の第１樹脂層用の樹脂組成物、並びに、第２及び第３樹脂層用の樹脂組成物を３層構成のフィードブロックに送り、さらにＴ－ダイから共押出した。押し出された溶融状態の積層物を３本の成形・冷却ロールに通すことによって、第２樹脂層、第１樹脂層及び第３樹脂層をこの順に有する透明樹脂フィルムを得た。得られた透明樹脂フィルムについて、株式会社村上色彩技術研究所社製のヘイズメーター（ＨＭ－１５０）を用い、ＪＩＳ　Ｋ　７３６１－１：１９９７に準拠して全光線透過率を測定したところ、５６．８％であった。 The molten resin composition for the first resin layer and the resin compositions for the second and third resin layers obtained above were sent to a three-layer feed block, and further coextruded from a T-die. The extruded molten laminate was passed through three forming/cooling rolls to obtain a transparent resin film having a second resin layer, a first resin layer, and a third resin layer in this order. Regarding the obtained transparent resin film, the total light transmittance was measured using a haze meter (HM-150) manufactured by Murakami Color Research Institute Co., Ltd. in accordance with JIS K 7361-1:1997, and it was found to be 56. It was 8%.
　＜実施例２＞
　フィードブロックへの第１樹脂層用の樹脂組成物、並びに、第２及び第３樹脂層用の樹脂組成物の供給速度を調整することにより、透明樹脂フィルム及びこれを構成する樹脂層の厚みを表１に示されるとおりにするとともに、ロール間の押し付け圧の条件を実施例１から変更することにより、透明樹脂フィルムを得た。上記方法による透明樹脂フィルムの全光線透過率は、５６．６％であった。 <Example 2>
By adjusting the feeding rate of the resin composition for the first resin layer and the resin composition for the second and third resin layers to the feed block, the thickness of the transparent resin film and the resin layers constituting it can be adjusted. A transparent resin film was obtained as shown in Table 1 and by changing the conditions of the pressing pressure between the rolls from Example 1. The total light transmittance of the transparent resin film obtained by the above method was 56.6%.
　＜実施例３＞
　フィードブロックへの第１樹脂層用の樹脂組成物、並びに、第２及び第３樹脂層用の樹脂組成物の供給速度を調整することにより、透明樹脂フィルム及びこれを構成する樹脂層の厚みを表１に示されるとおりにするとともに、ロール間の押し付け圧の条件を実施例１から変更することにより、透明樹脂フィルムを得た。上記方法による透明樹脂フィルムの全光線透過率は、５６．６％であった。 <Example 3>
By adjusting the feeding rate of the resin composition for the first resin layer and the resin composition for the second and third resin layers to the feed block, the thickness of the transparent resin film and the resin layers constituting it can be adjusted. A transparent resin film was obtained as shown in Table 1 and by changing the conditions of the pressing pressure between the rolls from Example 1. The total light transmittance of the transparent resin film obtained by the above method was 56.6%.
　＜実施例４＞
　製造例２で調製した第１樹脂層用の酸化チタン粒子ＭＢ、及び、ＨＩＰＳ樹脂ペレット（ＭＢの調製に用いたものと同じもの）の所定量を二軸押出機に投入し、２００～２６０℃の温度で加熱溶融混練して、溶融状態の第１樹脂層用の樹脂組成物を得た。該樹脂組成物の組成を下記に示す。
　一方、製造例３で調製した第２及び第３樹脂層用のＭＢ、及び、ＨＩＰＳ樹脂ペレット（ＭＢの調製に用いたものと同じもの）の所定量を別の二軸押出機に投入し、２００～２６０℃の温度で加熱溶融混練して、溶融状態の第２及び第３樹脂層用の樹脂組成物を得た。該樹脂組成物の組成を下記に示す。 <Example 4>
A predetermined amount of titanium oxide particles MB for the first resin layer prepared in Production Example 2 and HIPS resin pellets (same as those used for preparing MB) were put into a twin screw extruder, and heated at 200 to 260°C. The resin composition was heated, melted and kneaded at a temperature of 1, to obtain a resin composition for the first resin layer in a molten state. The composition of the resin composition is shown below.
On the other hand, predetermined amounts of MB for the second and third resin layers prepared in Production Example 3 and HIPS resin pellets (same as those used for preparing MB) were put into another twin-screw extruder, The mixture was heated and melted and kneaded at a temperature of 200 to 260°C to obtain a resin composition for the second and third resin layers in a molten state. The composition of the resin composition is shown below.
　（第１樹脂層用の樹脂組成物の組成）
　ＨＩＰＳ樹脂　　　　：９９．３７質量％
　酸化チタン粒子　　　：　０．３５質量％
　酸化防止剤　　　　　：　０．１４質量％
　紫外線吸収剤　　　　：　０．１４質量％ (Composition of resin composition for first resin layer)
HIPS resin: 99.37% by mass
Titanium oxide particles: 0.35% by mass
Antioxidant: 0.14% by mass
Ultraviolet absorber: 0.14% by mass
　（第２及び第３樹脂層用の樹脂組成物の組成）
　ＨＩＰＳ樹脂　　　　：９１．２６質量％
　アンチブロッキング剤：　７．６０質量％
　酸化防止剤　　　　　：　０．７６質量％
　紫外線吸収剤　　　　：　０．３８質量％ (Composition of resin composition for second and third resin layers)
HIPS resin: 91.26% by mass
Anti-blocking agent: 7.60% by mass
Antioxidant: 0.76% by mass
Ultraviolet absorber: 0.38% by mass
　上記で得た溶融状態の第１樹脂層用の樹脂組成物、並びに、第２及び第３樹脂層用の樹脂組成物を３層構成のフィードブロックに送り、さらにＴ－ダイから共押出した。押し出された溶融状態の積層物を３本の成形・冷却ロールに通すことによって、第２樹脂層、第１樹脂層及び第３樹脂層をこの順に有する透明樹脂フィルムを得た。上記方法による透明樹脂フィルムの全光線透過率は、５１．９％であった。 The molten resin composition for the first resin layer and the resin compositions for the second and third resin layers obtained above were sent to a three-layer feed block, and further coextruded from a T-die. The extruded molten laminate was passed through three forming/cooling rolls to obtain a transparent resin film having a second resin layer, a first resin layer, and a third resin layer in this order. The total light transmittance of the transparent resin film obtained by the above method was 51.9%.
　＜実施例５＞
　フィードブロックへの第１樹脂層用の樹脂組成物、並びに、第２及び第３樹脂層用の樹脂組成物の供給速度を調整することにより、透明樹脂フィルム及びこれを構成する樹脂層の厚みを表１に示されるとおりにするとともに、ロール間の押し付け圧の条件を実施例４から変更することにより、透明樹脂フィルムを得た。上記方法による透明樹脂フィルムの全光線透過率は、５１．９％であった。 <Example 5>
By adjusting the feeding rate of the resin composition for the first resin layer and the resin composition for the second and third resin layers to the feed block, the thickness of the transparent resin film and the resin layers constituting it can be adjusted. A transparent resin film was obtained as shown in Table 1 and by changing the conditions of the pressing pressure between the rolls from Example 4. The total light transmittance of the transparent resin film obtained by the above method was 51.9%.
　＜実施例６＞
　フィードブロックへの第１樹脂層用の樹脂組成物、並びに、第２及び第３樹脂層用の樹脂組成物の供給速度を調整することにより、透明樹脂フィルム及びこれを構成する樹脂層の厚みを表１に示されるとおりにするとともに、ロール間の押し付け圧の条件を実施例４から変更することにより、透明樹脂フィルムを得た。上記方法による透明樹脂フィルムの全光線透過率は、５１．９％であった。 <Example 6>
By adjusting the feeding rate of the resin composition for the first resin layer and the resin composition for the second and third resin layers to the feed block, the thickness of the transparent resin film and the resin layers constituting it can be adjusted. A transparent resin film was obtained as shown in Table 1 and by changing the conditions of the pressing pressure between the rolls from Example 4. The total light transmittance of the transparent resin film obtained by the above method was 51.9%.
　＜比較例１＞
　フィードブロックへの第１樹脂層用の樹脂組成物、並びに、第２及び第３樹脂層用の樹脂組成物の供給速度を調整することにより、透明樹脂フィルム及びこれを構成する樹脂層の厚みを表１に示されるとおりにするとともに、ロール間の押し付け圧の条件を実施例４から変更することにより、透明樹脂フィルムを得た。上記方法による透明樹脂フィルムの全光線透過率は、５１．９％であった。 <Comparative example 1>
By adjusting the feeding rate of the resin composition for the first resin layer and the resin composition for the second and third resin layers to the feed block, the thickness of the transparent resin film and the resin layers constituting it can be adjusted. A transparent resin film was obtained as shown in Table 1 and by changing the conditions of the pressing pressure between the rolls from Example 4. The total light transmittance of the transparent resin film obtained by the above method was 51.9%.
　上記＜測定及び評価＞に従う測定結果及び評価結果を表１に示す。Ａ（＝Ｔ１ＡＶ／Ｔ２ＡＶ）、Ｂ（＝Ｍ１／Ｍ２）、Ａ×Ｂ、Ａ’（＝Ｔ１ＡＶ／Ｔ３ＡＶ）、Ｂ’（＝Ｍ１／Ｍ３）及びＡ’×Ｂ’の値を併せて表１に示す。 Table 1 shows the measurement results and evaluation results according to the above <Measurement and Evaluation>. A (=T 1AV /T 2AV ), B (=M 1 /M 2 ), A×B, A' (=T 1AV /T 3AV ), B' (=M 1 /M 3 ), and A'×B The values of ' are also shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　１０　第１樹脂層、１５　無機粒子、２０　第２樹脂層、３０　第３樹脂層。  10 first resin layer, 15 inorganic particles, 20 second resin layer, 30 third resin layer.​

Claims (10)

  1. 　第１樹脂を含有する第１樹脂層と、
    　前記第１樹脂層の第１表面上に配置される樹脂層であって、第２樹脂を含有する第２樹脂層と、
    　前記第１樹脂層の前記第１表面と対向する第２表面上に配置される樹脂層であって、第３樹脂を含有する第３樹脂層と、
    を含む透明樹脂フィルムであって、
    　前記第１樹脂層は、無機粒子を含有し、
    　前記透明樹脂フィルムの厚みをＴ［μｍ］、前記第２樹脂層の厚みをＴ２［μｍ］、前記第３樹脂層の厚みをＴ３［μｍ］とするとき、Ｔ２／Ｔの標準偏差及びＴ３／Ｔの標準偏差がいずれも０．０１５以下である、透明樹脂フィルム。     a first resin layer containing a first resin;
    a second resin layer disposed on the first surface of the first resin layer, the second resin layer containing a second resin;
    a third resin layer disposed on a second surface of the first resin layer opposite to the first surface, the third resin layer containing a third resin;
    A transparent resin film comprising:
    The first resin layer contains inorganic particles,
    When the thickness of the transparent resin film is T [μm], the thickness of the second resin layer is T 2 [μm], and the thickness of the third resin layer is T 3 [μm], the standard deviation of T 2 /T is and a transparent resin film having a standard deviation of T 3 /T of 0.015 or less.
  2. 　Ｔ２／Ｔの標準偏差とＴ３／Ｔの標準偏差との和が０．０２０以下である、請求項１に記載の透明樹脂フィルム。 The transparent resin film according to claim 1, wherein the sum of the standard deviation of T 2 /T and the standard deviation of T 3 /T is 0.020 or less.
  3. 　前記第１樹脂層の平均厚みをＴ１ＡＶ［μｍ］、前記第２樹脂層の平均厚みをＴ２ＡＶ［μｍ］、前記第３樹脂層の平均厚みをＴ３ＡＶ［μｍ］とするとき、Ｔ１ＡＶ／Ｔ２ＡＶ及びＴ１ＡＶ／Ｔ３ＡＶがいずれも３０以下である、請求項１に記載の透明樹脂フィルム。 When the average thickness of the first resin layer is T 1AV [μm], the average thickness of the second resin layer is T 2AV [μm], and the average thickness of the third resin layer is T 3AV [μm], T 1AV The transparent resin film according to claim 1, wherein both of /T 2AV and T 1AV /T 3AV are 30 or less.
  4. 　前記無機粒子が光散乱剤を含む、請求項１に記載の透明樹脂フィルム。 The transparent resin film according to claim 1, wherein the inorganic particles contain a light scattering agent.
  5. 　前記第１樹脂、前記第２樹脂及び前記第３樹脂がそれぞれ熱可塑性樹脂である、請求項１に記載の透明樹脂フィルム。 The transparent resin film according to claim 1, wherein the first resin, the second resin, and the third resin are each thermoplastic resins.
  6. 　前記第１樹脂層に含まれる樹脂は前記第１樹脂からなり、前記第２樹脂層に含まれる樹脂は前記第２樹脂からなり、前記第３樹脂層に含まれる樹脂は前記第３樹脂からなる、請求項１に記載の透明樹脂フィルム。 The resin contained in the first resin layer is made of the first resin, the resin contained in the second resin layer is made of the second resin, and the resin contained in the third resin layer is made of the third resin. , The transparent resin film according to claim 1.
  7. 　前記第１樹脂と前記第２樹脂と前記第３樹脂とが同一である、請求項１に記載の透明樹脂フィルム。 The transparent resin film according to claim 1, wherein the first resin, the second resin, and the third resin are the same.
  8. 　前記無機粒子が半導体粒子を含む、請求項１に記載の透明樹脂フィルム。 The transparent resin film according to claim 1, wherein the inorganic particles include semiconductor particles.
  9. 　押出成形品である、請求項１に記載の透明樹脂フィルム。 The transparent resin film according to claim 1, which is an extrusion molded product.
  10. 　請求項１～９のいずれか１項に記載の透明樹脂フィルムを含む表示装置。 A display device comprising the transparent resin film according to any one of claims 1 to 9.
PCT/JP2023/000757 2022-03-31 2023-01-13 Transparent resin film and display device WO2023188689A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002001858A (en) * 2000-06-22 2002-01-08 Daicel Chem Ind Ltd Laminated film
JP2006212989A (en) * 2005-02-04 2006-08-17 Nippon Zeon Co Ltd Laminated film
JP2009211055A (en) * 2008-02-06 2009-09-17 Sumitomo Chemical Co Ltd Light-diffusing layered resin film, method of forming the same, antiglare film, antiglare polarizing plate, and image display
JP2020535247A (en) * 2017-09-18 2020-12-03 スリーエム イノベイティブ プロパティズ カンパニー Hydroxy Functional Polyamine Silicone Ligand Suitable for Quantum Dot Compositions and Articles
JP2021144210A (en) * 2020-03-10 2021-09-24 住友化学株式会社 Laminated optical film

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002001858A (en) * 2000-06-22 2002-01-08 Daicel Chem Ind Ltd Laminated film
JP2006212989A (en) * 2005-02-04 2006-08-17 Nippon Zeon Co Ltd Laminated film
JP2009211055A (en) * 2008-02-06 2009-09-17 Sumitomo Chemical Co Ltd Light-diffusing layered resin film, method of forming the same, antiglare film, antiglare polarizing plate, and image display
JP2020535247A (en) * 2017-09-18 2020-12-03 スリーエム イノベイティブ プロパティズ カンパニー Hydroxy Functional Polyamine Silicone Ligand Suitable for Quantum Dot Compositions and Articles
JP2021144210A (en) * 2020-03-10 2021-09-24 住友化学株式会社 Laminated optical film

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