WO2021152737A1 - Wavelength conversion member, backlight unit, and image display device - Google Patents

Wavelength conversion member, backlight unit, and image display device Download PDF

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Publication number
WO2021152737A1
WO2021152737A1 PCT/JP2020/003220 JP2020003220W WO2021152737A1 WO 2021152737 A1 WO2021152737 A1 WO 2021152737A1 JP 2020003220 W JP2020003220 W JP 2020003220W WO 2021152737 A1 WO2021152737 A1 WO 2021152737A1
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WO
WIPO (PCT)
Prior art keywords
wavelength conversion
meth
conversion member
acrylate
compound
Prior art date
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PCT/JP2020/003220
Other languages
French (fr)
Japanese (ja)
Inventor
雄麻 吉田
智之 中村
真弓 佐藤
太 及川
勝義 坂本
Original Assignee
昭和電工マテリアルズ株式会社
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Priority to PCT/JP2020/003220 priority Critical patent/WO2021152737A1/en
Publication of WO2021152737A1 publication Critical patent/WO2021152737A1/en

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
    • F21S2/00—Systems of lighting devices, not provided for in main groups F21S4/00 - F21S10/00 or F21S19/00, e.g. of modular construction
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V9/00—Elements for modifying spectral properties, polarisation or intensity of the light emitted, e.g. filters
    • F21V9/30—Elements containing photoluminescent material distinct from or spaced from the light source
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21Y—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO THE FORM OR THE KIND OF THE LIGHT SOURCES OR OF THE COLOUR OF THE LIGHT EMITTED
    • F21Y2115/00—Light-generating elements of semiconductor light sources
    • F21Y2115/10—Light-emitting diodes [LED]
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21Y—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO THE FORM OR THE KIND OF THE LIGHT SOURCES OR OF THE COLOUR OF THE LIGHT EMITTED
    • F21Y2115/00—Light-generating elements of semiconductor light sources
    • F21Y2115/30—Semiconductor lasers

Definitions

  • the present disclosure relates to a wavelength conversion member, a backlight unit, and an image display device.
  • the wavelength conversion member including the phosphor is arranged in, for example, the backlight unit of the image display device.
  • a wavelength conversion member including a quantum dot phosphor that emits red light and a quantum dot phosphor that emits green light when the wavelength conversion member is irradiated with blue light as excitation light, the quantum dot phosphor emits light.
  • White light can be obtained from the red light and green light produced and the blue light transmitted through the wavelength conversion member.
  • the wavelength conversion member containing a phosphor usually has a cured product obtained by curing a curable composition containing the phosphor.
  • the curable composition includes a thermosetting type and a photocurable type, and a photocurable type curable composition is preferably used from the viewpoint of productivity.
  • the wavelength conversion member containing a phosphor at least a part of the cured product containing the phosphor may be covered with a coating material.
  • a barrier film having a barrier property against oxygen may be provided on one side or both sides of the cured product containing a phosphor.
  • a film-shaped wavelength conversion member containing a phosphor has been cut into a single-wafer shape and used for transportation or storage.
  • the rolled wavelength conversion member is used by unwinding it in a plane in the subsequent punching process or the like.
  • the rolled wavelength conversion member has a curl during storage, and it is difficult to return it to a flat shape by its own weight.
  • the wavelength conversion member is not sufficiently rewound, the light transmitted through the wavelength conversion member may be blurred when used as a backlight of an image display device.
  • the wavelength conversion member is subjected to a high temperature, the optical characteristics of the quantum dot phosphor deteriorate. It was found by the present inventors that it would end up. Therefore, it is desirable that the wavelength conversion member can be efficiently rewound into a flat surface at a relatively low temperature (for example, 45 ° C. or lower) without subjecting the wavelength conversion member to a high temperature.
  • an object of the present disclosure is to provide a wavelength conversion member that can be easily rewound after rolling, and a backlight unit and an image display device using the wavelength conversion member.
  • Means for solving the above problems include the following aspects.
  • a wavelength conversion layer containing a phosphor is provided, and the coefficient of thermal expansion below the glass transition temperature is 30 ppm / min when measured with a thermomechanical analyzer under the conditions of a load of 0.05 N and a heating rate of 10 ° C./min.
  • the wavelength conversion member includes a coating material arranged on one surface side or both surface sides of the wavelength conversion layer, and has a load of 0.05 N and a heating rate of 10 ° C./min in a thermomechanical analyzer.
  • the wavelength conversion member according to ⁇ 1> wherein the coefficient of thermal expansion of the coating material at a glass transition temperature or higher when measured under conditions is 0 ppm / ° C. or lower.
  • the wavelength conversion member contains a coating material, and is measured by a thermomechanical analyzer under the conditions of a load of 0.05 N and a temperature rise rate of 10 ° C./min from the coefficient of thermal expansion of the wavelength conversion member below the glass transition temperature.
  • the wavelength conversion member according to ⁇ 1> or ⁇ 2> wherein the value obtained by subtracting the coefficient of thermal expansion below the glass transition temperature of the coating material is 10 ppm / ° C. or higher.
  • ⁇ 4> The wavelength according to any one of ⁇ 1> to ⁇ 3>, wherein the storage elastic modulus is 3.7 GPa or less when measured with a dynamic viscoelasticity measuring device under the conditions of a frequency of 10 Hz and a temperature of 30 ° C. Conversion member.
  • ⁇ 5> The wavelength conversion member according to any one of ⁇ 1> to ⁇ 4>, wherein the value measured by the following method is 6.0 mm or more: The wavelength conversion member processed into a rectangle having a width of 20 mm is arranged on the test table so as to project outward by 10 cm in length from the test table, and the height of the tip portion of the wavelength conversion member that hangs down by its own weight. , Measure the distance from the height of the reference plane of the test stand.
  • the wavelength conversion layer contains the phosphor, a thiol compound, at least one selected from the group consisting of a (meth) acrylic compound and a (meth) allyl compound, and a photopolymerization initiator.
  • ⁇ 9> The wavelength conversion member according to any one of ⁇ 1> to ⁇ 8>, which is formed in a roll shape.
  • a backlight unit including the wavelength conversion member according to any one of ⁇ 1> to ⁇ 8> and a light source.
  • An image display device including the backlight unit according to ⁇ 9>.
  • a wavelength conversion member that can be easily rewound after rolling, and a backlight unit and an image display device using the wavelength conversion member are provided.
  • each component may contain a plurality of applicable substances. When a plurality of substances corresponding to each component are present in the composition, the content or content of each component is the total content or content of the plurality of substances present in the composition unless otherwise specified. Means quantity.
  • a plurality of types of particles corresponding to each component may be contained.
  • the particle size of each component means a value for a mixture of the plurality of particles present in the composition unless otherwise specified.
  • the term “layer” or “membrane” is used only in a part of the region in addition to the case where the layer or the membrane is formed in the entire region when the region in which the layer or the membrane is present is observed. The case where it is formed is also included.
  • laminated refers to stacking layers, and two or more layers may be bonded or the two or more layers may be removable.
  • (meth) acrylate means at least one of acrylate and methacrylate
  • (meth) allyl means at least one of allyl and methallyl
  • (meth) acrylic means acrylic and methacrylic.
  • (meth) acryloyl means at least one of acryloyl and methacryloyl.
  • the wavelength conversion member of the present disclosure has a wavelength conversion layer containing a phosphor, and is equal to or lower than the glass transition temperature when measured by a thermomechanical analysis (TMA) apparatus under the conditions of a load of 0.05 N and a heating rate of 10 ° C./min.
  • TMA thermomechanical analysis
  • coefficient of thermal expansion when the member is measured under the above conditions is also simply referred to as "coefficient of thermal expansion".
  • the coefficient of thermal expansion of the member below the glass transition temperature shall be measured in an arbitrary temperature range of 20 ° C. in the range from the glass transition temperature of -100 ° C. to the glass transition temperature.
  • the coefficient of thermal expansion of the member above the glass transition temperature shall be measured in an arbitrary temperature range of 20 ° C. in the range from the glass transition temperature to the glass transition temperature + 100 ° C.
  • the coefficient of thermal expansion of the member can be measured by, for example, the method described in Examples.
  • the wavelength conversion member of the present disclosure According to the wavelength conversion member of the present disclosure, rewinding after rolling can be performed efficiently. Although the exact reason is not clear, a correlation was found between the above coefficient of thermal expansion and the ease of curl return after rolling. From this, it is suggested that the behavior of thermal expansion of the wavelength conversion member affects the easiness of curling or the easiness of returning. A large coefficient of thermal expansion below the glass transition temperature or a coefficient of thermal expansion above the glass transition temperature of 0 ppm / ° C. indicates that the free volume in the resin material is large, and winding after rolling. It is presumed that it is easy to return to the original shape when returning.
  • the coefficient of thermal expansion of the wavelength conversion member below the glass transition temperature is 30 ppm / ° C. or higher
  • the coefficient of thermal expansion may be 32 ppm / ° C. or higher, or 35 ppm / ° C. or higher.
  • the coefficient of thermal expansion of the wavelength conversion member below the glass transition temperature may be 60 ppm / ° C. or lower, 50 ppm / ° C. or lower, or 45 ppm / ° C. or lower. good.
  • the coefficient of thermal expansion of the wavelength conversion member above the glass transition temperature When the coefficient of thermal expansion of the wavelength conversion member above the glass transition temperature is 0 ppm / ° C or less, the coefficient of thermal expansion may be -10 ppm / ° C or less, -20 ppm / ° C or less, or-. It may be 30 ppm / ° C. or less. From the viewpoint of shape stability, the coefficient of thermal expansion of the wavelength conversion member above the glass transition temperature may be -60 ppm / ° C or higher, -50 ppm / ° C or higher, or ⁇ 45 ppm / ° C or higher. It may be.
  • the coefficient of thermal expansion of the coating material above the glass transition temperature is preferably 0 ppm / ° C. or less. It was found that when the coefficient of thermal expansion of the coating material was in the above range, the amount of curl when rewound after rolling tended to be smaller. The reason for this is not clear, but it is presumed that the softening of the coating material makes it easier to follow the wavelength conversion layer and suppresses the amount of curl.
  • the coefficient of thermal expansion of the coating material above the glass transition temperature may be -10 ppm / ° C or lower, -20 ppm / ° C or lower, -50 ppm / ° C or lower, or ⁇ 70 ppm / ° C. It may be as follows. From the viewpoint of shape stability, the coefficient of thermal expansion of the coating material above the glass transition temperature may be ⁇ 100 ppm / ° C. or higher.
  • the value obtained by subtracting the coefficient of thermal expansion of the coating material below the glass transition temperature from the coefficient of thermal expansion below the glass transition temperature of the coating material (also the difference in the coefficient of thermal expansion). It was found that when the value was 10 ppm / ° C. or higher, the amount of curl when rewound after rolling tended to be smaller. The reason for this is not clear, but the large difference in thermal expansion indicates that the coating material follows the wavelength conversion layer, and that the amount of curl is suppressed by the coating material following the wavelength conversion layer. Guessed.
  • the difference in the coefficient of thermal expansion may be 12 ppm / ° C. or higher, or 14 ppm / ° C. or higher. From the viewpoint of shape stability, the difference in the coefficient of thermal expansion may be 120 ppm / ° C. or less, or 110 ppm / ° C. or less.
  • Examples of the method of adjusting the coefficient of thermal expansion include a method of adjusting the material, thickness, elastic modulus, laminated structure, etc. of the wavelength conversion layer and the coating material to be used later as needed.
  • the rolled wavelength conversion member is rewound by, for example, the following method. After the rolled wavelength conversion member is unwound and punched, a plurality of sheet-fed wavelength conversion members are sandwiched between glass plates and the like, and the wavelength conversion member is allowed to stand in a constant temperature bath at a temperature of 60 ° C. or lower for a predetermined time. do.
  • the curl amount is within 8.0 mm. It is preferably within 5.0 mm, more preferably within 3.0 mm.
  • the curl amount (warp amount) is the maximum value measured at 6 points at arbitrary ends of the punched wavelength conversion member.
  • the wavelength conversion member may be formed in a roll shape.
  • the wavelength conversion member of the present disclosure is suitable for rolling. By rolling the wavelength conversion member, it is possible to improve the transportation efficiency and the storage efficiency. Further, it is considered that the end portion of the wavelength conversion member can be reduced as compared with the case where the wavelength conversion member is processed into a single-wafer shape and transported or stored, so that deterioration of the end portion can be suppressed.
  • the shape of the wavelength conversion member is preferably film-like. Since the wavelength conversion member is in the form of a film, it can be suitably used for a backlight unit and can be suitably rolled.
  • the width and length of the wavelength conversion member are not particularly limited, and can be appropriately set according to, for example, the size of the image display device to be applied.
  • the width of the wavelength conversion member can be appropriately adjusted according to the application, and may be, for example, 10 mm to 5000 mm.
  • the length of the wavelength conversion member can be appropriately adjusted according to the application, and may be, for example, 0.5 m to 1000 m.
  • the length of the wavelength conversion member means the length in the winding direction, and the length orthogonal to this is the width of the wavelength conversion member.
  • the width of the wavelength conversion member can be appropriately adjusted according to the application, for example, even if it is 10 mm to 5000 mm. good.
  • the length of the wavelength conversion member can be appropriately adjusted according to the application, for example, 10 mm to 5000 mm. May be good.
  • the length of the wavelength conversion member means the length in the longitudinal direction
  • the width of the wavelength conversion member means the length in the lateral direction.
  • the length of one side of the square is included in either the width or the length of the wavelength conversion member.
  • the average thickness of the wavelength conversion member is, for example, preferably 100 ⁇ m to 500 ⁇ m, more preferably 120 ⁇ m to 400 ⁇ m, and even more preferably 150 ⁇ m to 300 ⁇ m.
  • the average thickness of the wavelength conversion member is 100 ⁇ m or more, the wavelength conversion efficiency tends to be further improved, and when the average thickness is 500 ⁇ m or less, when the wavelength conversion member is applied to the backlight unit, the backlight unit is used. There is a tendency to make it thinner.
  • the average thickness of the wavelength conversion member is obtained as, for example, an arithmetic mean value of the thicknesses of any three points measured using a micrometer.
  • One or both surfaces of the wavelength conversion member may be roughened.
  • the surface roughness Ra may be, for example, 0.5 ⁇ m or more.
  • Surface roughness Ra refers to a value measured using a 3D microscope (for example, Olympus Corporation, model OLS4100, magnification 10 times).
  • the measurement range is a line roughness with a length of 1289 ⁇ m.
  • the analysis parameter is the roughness parameter
  • the cutoff is ⁇ C; none, ⁇ S; none, ⁇ f; none.
  • ⁇ C, ⁇ S, and ⁇ f are methods for calculating the contour curve for calculating Ra.
  • the contour curve includes a cross-section curve, a roughness curve, and a waviness curve.
  • the cross-sectional curve is a curve obtained by applying a low-frequency filter having a cutoff value of ⁇ S to the measured cross-sectional curve.
  • the roughness curve is a contour curve obtained by blocking long wavelength components from the cross-sectional curve by a high-frequency filter having a cutoff value of ⁇ C.
  • the waviness curve is a contour curve obtained by sequentially applying contour curve filters having cutoff values ⁇ f and ⁇ C to the cross-sectional curve.
  • the ⁇ f contour curve filter blocks the long wavelength component
  • the ⁇ C contour curve filter blocks the short wavelength component.
  • the wavelength conversion member preferably has a total light transmittance of 55% or more, more preferably 60% or more, and further preferably 65% or more.
  • the total light transmittance of the wavelength conversion member can be measured according to the measurement method of JIS K 7361-1: 1997.
  • the wavelength conversion member preferably has a haze of 10% to 60%, more preferably 10% to 55%, and 10% to 50% from the viewpoint of further improving the light utilization efficiency. Is even more preferable.
  • the haze of the wavelength conversion member can be measured according to the measurement method of JIS K 7136: 2000.
  • the storage elastic modulus of the wavelength conversion member measured under the conditions of a frequency of 10 Hz and a temperature of 30 ° C. is preferably 4.1 GPa or less, and is preferably 3.9 GPa or less. More preferably, it is more preferably 3.7 GPa or less, particularly preferably 3.6 GPa or less, extremely preferably 3.0 GPa or less, and even more preferably 2.5 GPa or less. From the viewpoint of handleability, the storage elastic modulus is preferably 1.0 GPa or more, more preferably 1.5 GPa or more, and further preferably 1.8 GPa or more.
  • the storage elastic modulus of the wavelength conversion member can be measured using a dynamic viscoelasticity measuring device (for example, Rheometric Scientific, Solid Analyzer RSA-III).
  • the method of adjusting the storage elastic modulus of the wavelength conversion member is not particularly limited, and examples thereof include a method of adjusting the material, thickness, laminated structure, etc. of the wavelength conversion layer and the coating material to be used later as needed.
  • a value measured by the following method (hereinafter, may be referred to as a specific value) may be adjusted.
  • the wavelength conversion member processed into a rectangle having a width of 20 mm is arranged on a test table having a height of 10 cm or more so as to project outward by 10 cm in length from the test table, and the wavelength conversion member hangs down by its own weight. Measure the distance between the height of the tip of the test table and the height of the reference surface of the test table.
  • the height of the reference plane means the height on the test table on which the remaining portion of the processed wavelength conversion member other than the protruding portion is arranged.
  • the test table is not particularly limited in shape and size as long as it can fix the remaining portion of the wavelength conversion member processed into a rectangle having a width of 20 mm other than the portion protruding from the test table.
  • the specific value of the wavelength conversion member measured by the above method is preferably 6.0 mm or more, more preferably 8.0 mm or more, and 10 It is more preferably 0.0 mm or more.
  • the specific value of the wavelength conversion member measured by the above method is preferably 35.0 mm or less, more preferably 25.0 mm or less, and further preferably 15.0 mm or less. preferable.
  • the method of adjusting the specific value of the wavelength conversion member measured by the above method is not particularly limited, and for example, the material, thickness, elastic modulus, laminated structure, etc. of the wavelength conversion layer and the coating material to be used later, which will be used as necessary, are not particularly limited. There is a method of adjustment. For example, by reducing the thickness of the wavelength conversion member, the specific value measured by the above method tends to increase. Further, when a covering material is used, the specific value measured by the above method tends to increase by reducing the thickness of the covering material. Even if the covering material has a multi-layer structure and the base material layer includes an adhesive layer, the specific value measured by the above method tends to increase.
  • the wavelength conversion member may have a covering material arranged on one surface side or both surface sides of the wavelength conversion layer.
  • the average thickness of the covering material is preferably 8 ⁇ m or more, and may be 15 ⁇ m or more, or 20 ⁇ m or more. When the average thickness of the covering material is 8 ⁇ m or more, the handleability of the wavelength conversion member is improved, and the functions such as barrier property tend to be sufficient.
  • the average thickness of the coating material is preferably 150 ⁇ m or less, more preferably 100 ⁇ m or less, and even more preferably 80 ⁇ m or less. When the average thickness of the covering material is 150 ⁇ m or less, the decrease in light transmittance tends to be suppressed. In addition, it tends to be easy to rewind after rolling.
  • the average thickness of the coating material is preferably 8 ⁇ m to 150 ⁇ m, more preferably 15 ⁇ m to 100 ⁇ m, and even more preferably 20 ⁇ m to 80 ⁇ m.
  • the average thickness of the covering material is obtained as, for example, an arithmetic mean value of the thicknesses of any three points measured using a micrometer.
  • the covering material may be roughened.
  • the surface roughness Ra may be 0.5 ⁇ m or more.
  • the material of the covering material is not particularly limited, and polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin such as polyethylene (PE) and polypropylene (PP), polyamide such as nylon, and ethylene-vinyl alcohol co-weight. It may be coalescence (EVOH) or the like. From the viewpoint of availability, polyethylene terephthalate is preferable as the material of the covering material.
  • the covering material may be one provided with a barrier layer for enhancing the barrier function (barrier film). Examples of the barrier layer include an inorganic layer containing an inorganic substance such as alumina and silica.
  • the coating material preferably has a barrier property against at least one of oxygen and water, and more preferably has a barrier property against both oxygen and water, from the viewpoint of suppressing a decrease in the luminous efficiency of the phosphor.
  • the coating material having a barrier property against at least one of oxygen and water is not particularly limited, and a barrier film having an inorganic layer or the like can be used.
  • Oxygen permeability of the dressing is preferably 0.5mL / (m 2 ⁇ 24h ⁇ atm) or less, more preferably 0.3mL / (m 2 ⁇ 24h ⁇ atm) or less, 0 and more preferably .1mL / (m 2 ⁇ 24h ⁇ atm) or less.
  • the oxygen permeability of the coating material can be measured using an oxygen permeability measuring device (for example, MOCON, OX-TRAN) under the conditions of a temperature of 23 ° C. and a relative humidity of 65%.
  • the water vapor permeability of the dressing for example, 5 ⁇ 10 -2 g / is preferably (m 2 ⁇ 24h ⁇ Pa) or less, 1 ⁇ 10 -2 g / ( m 2 ⁇ 24h ⁇ Pa) or less more preferably, even more preferably 5 ⁇ 10 -3 g / (m 2 ⁇ 24h ⁇ Pa) or less.
  • the water vapor permeability of the coating material can be measured using a water vapor permeability measuring device (for example, MOCON, AQUATRAN) under the conditions of a temperature of 40 ° C. and a relative humidity of 90%.
  • the covering material may be one in which a plurality of layers are laminated.
  • the covering material may be a laminated material such as a base material layer, a barrier layer, and a primer layer.
  • the wavelength conversion member of the present disclosure includes a wavelength conversion layer.
  • the wavelength conversion layer contains a phosphor.
  • the wavelength conversion layer may further contain a cured resin product, or may have a phosphor contained in the cured resin product. Further, the wavelength conversion layer may further contain a light diffusing material.
  • the wavelength conversion layer contains a phosphor that emits light when irradiated with light from a light source.
  • the type of the phosphor is not particularly limited, and examples thereof include an organic phosphor and an inorganic phosphor.
  • the organic phosphor include a naphthalimide compound and a perylene compound.
  • the inorganic phosphor include Y 3 O 3 : Eu, YVO 4 : Eu, Y 2 O 2 : Eu, 3.5 MgO / 0.5 MgF 2 , GeO 2 : Mn, (Y ⁇ Cd) BO 2 : Eu, etc.
  • Red light emitting inorganic phosphor ZnS: Cu ⁇ Al, (Zn ⁇ Cd) S: Cu ⁇ Al, ZnS: Cu ⁇ Au ⁇ Al, Zn 2 SiO 4 : Mn, ZnSiO 4 : Mn, ZnS: Ag ⁇ Cu, ( Zn ⁇ Cd) S: Cu, ZnS: Cu, GdOS: Tb, LaOS: Tb, YSiO 4 : Ce ⁇ Tb, ZnGeO 4 : Mn, GeMgAlO: Tb, SrGaS: Eu 2+ , ZnS: Cu ⁇ Co, MgO ⁇ nB 2 O 3 : Green luminescent inorganic phosphors such as Ge ⁇ Tb, LaOBr: Tb ⁇ Tm, La 2 O 2 S: Tb, ZnS: Ag, GaWO 4 , Y 2 SiO 6 : Ce, ZnS: Ag ⁇ Ga ⁇ Cl , Ca 2 B 4
  • a quantum dot phosphor is preferable from the viewpoint of excellent color reproducibility of the image display device.
  • the quantum dot phosphor is not particularly limited, and examples thereof include particles containing at least one selected from the group consisting of a group II-VI compound, a group III-V compound, a group IV-VI compound, and a group IV compound.
  • the quantum dot phosphor preferably contains a compound containing at least one of Cd and In.
  • II-VI group compounds include CdSe, CdTe, CdS, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSte, ZnSeS, ZnSeTe, ZnSte, HgSeS, ZnS.
  • Group III-V compounds include GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, COLP, GaNAs, PLACSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb.
  • IV-VI group compounds include SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSte, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbSe .
  • Specific examples of the Group IV compound include Si, Ge, SiC, SiGe and the like.
  • the quantum dot phosphor may have a core-shell structure.
  • core / shell By making the band gap of the compound constituting the shell wider than the band gap of the compound constituting the core, it is possible to further improve the quantum efficiency of the quantum dot phosphor.
  • core / shell examples include CdSe / ZnS, InP / ZnS, PbSe / PbS, CdSe / CdS, CdTe / CdS, and CdTe / ZnS.
  • the quantum dot phosphor may have a so-called core multi-shell structure in which the shell has a multi-layer structure.
  • the quantum efficiency of the quantum dot phosphor can be further improved. Is possible.
  • the wavelength conversion layer may contain one kind of quantum dot phosphor alone, or may contain two or more kinds of quantum dot phosphors in combination. May be good.
  • Examples of a mode in which two or more types of quantum dot phosphors are contained in combination include a mode in which two or more types of quantum dot phosphors having different components but the same average particle size are contained, and a mode in which the components are the same although the average particle size is different. Examples thereof include an embodiment containing two or more types of quantum dot phosphors, and an embodiment containing two or more types of quantum dot phosphors having different components and average particle diameters.
  • the emission center wavelength of the quantum dot phosphor can be changed by changing at least one of the components of the quantum dot phosphor and the average particle size.
  • the wavelength conversion layer contains a quantum dot phosphor G having an emission center wavelength in the green wavelength region of 520 nm to 560 nm and a quantum dot phosphor R having an emission center wavelength in the red wavelength region of 600 nm to 680 nm. You may be doing it.
  • the wavelength conversion layer containing the quantum dot phosphor G and the quantum dot phosphor R is irradiated with excitation light in the blue wavelength range of 430 nm to 480 nm, the quantum dot phosphor G and the quantum dot phosphor R are green, respectively. Light and red light are emitted. As a result, white light can be obtained by the green light and red light emitted from the quantum dot phosphor G and the quantum dot phosphor R and the blue light transmitted through the cured product.
  • the content of the phosphor in the wavelength conversion layer is preferably, for example, 0.01% by mass to 1.0% by mass, and 0.05% by mass to 0.5% by mass, based on the entire wavelength conversion layer. Is more preferable, and 0.1% by mass to 0.5% by mass is further preferable.
  • 0.01% by mass or more with respect to the entire wavelength conversion layer a sufficient wavelength conversion function tends to be obtained, and when the content of the phosphor is 1.0% by mass or less. , The aggregation of the phosphor tends to be suppressed.
  • the wavelength conversion layer may further contain a cured resin product.
  • the wavelength conversion layer may be a layer in which the above-mentioned phosphor is contained in the cured resin product.
  • the cured resin product preferably contains a sulfide structure from the viewpoint of adhesion to other members (coating material, etc.) of the cured resin product and suppression of wrinkles due to volume shrinkage during curing.
  • the cured resin composition containing a sulfide structure is obtained by curing a resin composition containing, for example, a thiol compound described later and a polymerizable compound having a carbon-carbon double bond that causes an enthiol reaction with a thiol group of the thiol compound. Obtainable.
  • the cured resin product preferably contains an alicyclic structure or an aromatic ring structure.
  • the cured resin product having an alicyclic structure or an aromatic ring structure can be obtained, for example, by curing a resin composition containing a polymer compound having an alicyclic structure or an aromatic ring structure, which will be described later.
  • the cured resin product preferably contains an alkyleneoxy group.
  • the polarity of the cured resin product increases, and non-polar oxygen tends to be difficult to dissolve in the components in the cured product.
  • the flexibility of the cured resin product tends to increase and the adhesion to the coating material tends to improve.
  • the cured resin product containing an alkyleneoxy group can be obtained, for example, by curing a resin composition containing a polymerizable compound having an alkyleneoxy group, which will be described later.
  • the wavelength conversion layer may be a cured product of a composition containing a phosphor, a polymerizable compound, and a photopolymerization initiator (hereinafter, also simply referred to as a resin composition).
  • the resin composition preferably contains a phosphor, a thiol compound, at least one selected from the group consisting of a (meth) acrylic compound and a (meth) allyl compound, and a photopolymerization initiator.
  • the resin composition may optionally contain other components. Hereinafter, each component of the resin composition will be described in detail.
  • the resin composition contains a phosphor.
  • the details of the phosphor are as described above.
  • the quantum dot phosphor may be used in the state of a quantum dot phosphor dispersion liquid dispersed in a dispersion medium.
  • the dispersion medium for dispersing the quantum dot phosphor include various organic solvents, silicone compounds, and monofunctional (meth) acrylate compounds.
  • the quantum dot phosphor may be used in the state of a quantum dot phosphor dispersion liquid by using a dispersant, if necessary.
  • the organic solvent that can be used as the dispersion medium is not particularly limited unless precipitation and aggregation of the quantum dot phosphor are confirmed, and acetonitrile, methanol, ethanol, acetone, 1-propanol, ethyl acetate, butyl acetate, etc. Examples thereof include toluene and hexane.
  • Silicone compounds that can be used as a dispersion medium include straight silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil; amino-modified silicone oil, epoxy-modified silicone oil, carboxy-modified silicone oil, and carbinol-modified silicone. Oil, mercapto-modified silicone oil, heterogeneous functional group-modified silicone oil, polyether-modified silicone oil, methylstyryl-modified silicone oil, hydrophilic special-modified silicone oil, higher alkoxy-modified silicone oil, higher fatty acid-modified silicone oil, fluorine-modified silicone oil, etc. Modified silicone oil and the like.
  • the monofunctional (meth) acrylate compound that can be used as a dispersion medium is not particularly limited as long as it is liquid at room temperature (25 ° C.), and is a monofunctional (meth) acrylate compound having an alicyclic structure (preferably). Isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate), methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, ethoxylated o-phenylphenol (meth) acrylate and the like can be mentioned.
  • dispersant used as needed examples include polyetheramine (JEFFAMINE M-1000, HUNTSMAN) and the like.
  • the mass-based ratio of the quantum dot phosphor to the quantum dot phosphor dispersion liquid is preferably 1% by mass to 20% by mass, and more preferably 1% by mass to 10% by mass.
  • the content of the quantum dot phosphor dispersion liquid in the resin composition is the total amount of the resin composition when the mass-based ratio of the quantum dot phosphor to the quantum dot phosphor dispersion liquid is 1% by mass to 20% by mass. On the other hand, for example, it is preferably 1% by mass to 10% by mass.
  • the content of the quantum dot phosphor in the resin composition is preferably, for example, 0.01% by mass to 1.0% by mass, preferably 0.05% by mass or more, based on the total amount of the resin composition. It is more preferably 0.5% by mass, and even more preferably 0.1% by mass to 0.5% by mass.
  • the content of the quantum dot phosphor is 0.01% by mass or more, sufficient emission intensity tends to be obtained when the cured product is irradiated with excitation light, and the content of the quantum dot phosphor is 1.0. When it is mass% or less, the aggregation of the quantum dot phosphor tends to be suppressed.
  • the resin composition contains a polymerizable compound.
  • the polymerizable compound contained in the resin composition is not particularly limited, and examples thereof include a thiol compound, a (meth) acrylic compound, and a (meth) allyl compound.
  • the (meth) allyl compound means a compound having a (meth) allyl group in the molecule
  • the (meth) acrylic compound means a compound having a (meth) acryloyl group in the molecule.
  • Compounds having both a (meth) allyl group and a (meth) acryloyl group in the molecule shall be classified as (meth) allyl compounds for convenience.
  • the resin composition is selected from the group consisting of a thiol compound, a (meth) acrylic compound and a (meth) allyl compound as a polymerizable compound at least. It is preferable to include one kind.
  • a cured product obtained by curing a resin composition containing a thiol compound as a polymerizable compound and at least one selected from the group consisting of a (meth) acrylic compound and a (meth) allyl compound has a thiol group and ( A sulfide structure (RSR', R and R'represents an organic group) formed by an enthiol reaction with a carbon-carbon double bond of a (meth) acryloyl group or a (meth) allyl group. include.
  • RSR', R and R' represents an organic group formed by an enthiol reaction with a carbon-carbon double bond of a (meth) acryloyl group or a (meth) allyl group.
  • the thiol compound may be a monofunctional thiol compound having one thiol group in one molecule, or a polyfunctional thiol compound having two or more thiol groups in one molecule.
  • the thiol compound contained in the resin composition may be only one kind or two or more kinds.
  • the thiol compound may or may not have a polymerizable group other than the thiol group (for example, (meth) acryloyl group, (meth) allyl group) in the molecule.
  • a compound containing a thiol group and a polymerizable group other than the thiol group in the molecule shall be classified as a "thiol compound”.
  • the monofunctional thiol compound examples include hexanethiol, 1-heptanethiol, 1-octanethiol, 1-nonanthiol, 1-decanethiol, 3-mercaptopropionic acid, methyl mercaptopropionate, methoxybutyl mercaptopropionate, and the like.
  • Examples thereof include octyl mercaptopropionate, tridecyl mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate and the like.
  • polyfunctional thiol compound examples include ethylene glycol bis (3-mercaptopropionate), diethylene glycol bis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), 1,2-.
  • the thiol compound preferably contains a polyfunctional thiol compound.
  • the ratio of the polyfunctional thiol compound to the total amount of the thiol compound is, for example, preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 100% by mass.
  • the thiol compound may be in the state of a thioether oligomer that has reacted with the (meth) acrylic compound.
  • the thioether oligomer can be obtained by addition polymerization of a thiol compound and a (meth) acrylic compound in the presence of a polymerization initiator.
  • the content of the thiol compound in the resin composition is preferably, for example, 5% by mass to 80% by mass, and 15% by mass, based on the total amount of the resin composition. It is more preferably to 70% by mass, and further preferably 18% by mass to 60% by mass.
  • the content of the thiol compound is 5% by mass or more, the adhesion of the wavelength conversion layer to the coating material tends to be further improved, and when the content of the thiol compound is 80% by mass or less, the wavelength conversion layer of the wavelength conversion layer tends to have better adhesion. Heat resistance and moisture heat resistance tend to be further improved.
  • the (meth) acrylic compound may be a monofunctional (meth) acrylic compound having one (meth) acryloyl group in one molecule, and two or more (meth) acrylic compounds in one molecule. It may be a polyfunctional (meth) acrylic compound having an acryloyl group.
  • the (meth) acrylic compound contained in the resin composition may be one kind or two or more kinds.
  • the monofunctional (meth) acrylic compound examples include (meth) acrylic acid; methyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and isononyl (meth).
  • Alkyl (meth) acrylate having an alkyl group having 1 to 18 carbon atoms such as acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate; benzyl (meth) acrylate, phenoxyethyl ( A (meth) acrylate compound having an aromatic ring such as a meta) acrylate; an alkoxyalkyl (meth) acrylate such as butoxyethyl (meth) acrylate; an aminoalkyl (meth) acrylate such as N, N-dimethylaminoethyl (meth) acrylate; Diethylene glycol monoethyl ether (meth) acrylate, triethylene glycol monobutyl ether (meth) acrylate, tetraethylene glycol monomethyl ether (meth) acrylate, hexaethylene glycol monomethyl ether (meth) acrylate
  • Acrylate Polyalkylene glycol monoaryl ether (meth) acrylate such as hexaethylene glycol monophenyl ether (meth) acrylate; cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, methylene oxide-added cyclo (Meta) acrylate compound having an alicyclic structure such as decatorien (meth) acrylate; (meth) acrylate compound having a heterocycle such as (meth) acryloylmorpholine and tetrahydrofurfuryl (meth) acrylate; heptadecafluorodecyl (meth) ) Alkyl fluoride (meth) acrylates such as acrylates; 2-hydroxyethyl (meth) acrylates, 3-hydroxypropyl (meth) acrylates, 4-hydroxybutyl (meth) acrylates, trietylene N
  • N-Isopropyl (meth) acrylamide N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide and other (meth) acrylamide compounds. ..
  • polyfunctional (meth) acrylic compound examples include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol di (meth) acrylate.
  • Polyalkylene glycol di (meth) acrylate Polyalkylene glycol di (meth) acrylate such as polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate; Trimethylol propantri (meth) acrylate, Trimethylol propantri with ethylene oxide (meth) Tri (meth) acrylate compounds such as meth) acrylate and tris (2-acryloyloxyethyl) isocyanurate; ethylene oxide-added pentaerythritol tetra (meth) acrylate, trimethylolpropanetetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like.
  • Tetra (meth) acrylate compounds tricyclodecanedimethanol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, 1,3-adamantan dimethanol di (meth) acrylate, hydrogenated bisphenol A (poly) ethoxydi ( Meta) acrylate, hydrogenated bisphenol A (poly) propoxydi (meth) acrylate, hydrogenated bisphenol F (poly) ethoxydi (meth) acrylate, hydrogenated bisphenol F (poly) propoxydi (meth) acrylate, hydrogenated bisphenol S (poly) Examples thereof include (meth) acrylate compounds having an alicyclic structure such as ethoxydi (meth) acrylate and hydrogenated bisphenol S (poly) propoxydi (meth) acrylate.
  • the (meth) acrylic compound is preferably a (meth) acrylate compound having an alicyclic structure or an aromatic ring structure from the viewpoint of further improving the heat resistance and moisture heat resistance of the cured product.
  • the alicyclic structure or aromatic ring structure include an isobornyl skeleton, a tricyclodecane skeleton, and a bisphenol skeleton.
  • the (meth) acrylic compound may have an alkyleneoxy group or may be a bifunctional (meth) acrylic compound having an alkyleneoxy group.
  • alkyleneoxy group for example, an alkyleneoxy group having 2 to 4 carbon atoms is preferable, an alkyleneoxy group having 2 or 3 carbon atoms is more preferable, and an alkyleneoxy group having 2 carbon atoms is further preferable.
  • the (meth) acrylic compound may have one type or two or more types of alkyleneoxy groups.
  • the alkyleneoxy group-containing compound may be a polyalkyleneoxy group-containing compound having a polyalkyleneoxy group containing a plurality of alkyleneoxy groups.
  • the number of alkyleneoxy groups in one molecule is preferably 2 to 30, more preferably 2 to 20, and 3 to 20. It is more preferably 10 pieces, and particularly preferably 3 to 5 pieces.
  • the (meth) acrylic compound When the (meth) acrylic compound has an alkyleneoxy group, it preferably has a bisphenol structure. As a result, the heat resistance of the cured product tends to be superior.
  • the bisphenol structure include a bisphenol A structure and a bisphenol F structure, and among them, the bisphenol A structure is preferable.
  • (meth) acrylic compound having an alkyleneoxy group examples include alkoxyalkyl (meth) acrylates such as butoxyethyl (meth) acrylates; diethylene glycol monoethyl ether (meth) acrylates, triethylene glycol monobutyl ether (meth) acrylates, and the like.
  • Examples thereof include bisphenol-type di (meth) acrylate compounds such as ethoxylated bisphenol A-type di (meth) acrylate, propoxylated bisphenol A-type di (meth) acrylate, and propoxylated ethoxylated bisphenol A-type di (meth) acrylate.
  • bisphenol-type di (meth) acrylate compounds such as ethoxylated bisphenol A-type di (meth) acrylate, propoxylated bisphenol A-type di (meth) acrylate, and propoxylated ethoxylated bisphenol A-type di (meth) acrylate.
  • the content of the (meth) acrylic compound in the resin composition is, for example, 40% by mass to 90% by mass with respect to the total amount of the resin composition. It may be 50% by mass to 80% by mass.
  • the (meth) allyl compound may be a monofunctional (meth) allyl compound having one (meth) allyl group in one molecule, and two or more (meth) allyl compounds in one molecule. It may be a polyfunctional (meth) allyl compound having an allyl group.
  • the (meth) allyl compound contained in the resin composition may be only one kind or two or more kinds.
  • the (meth) allyl compound may or may not have a polymerizable group (for example, (meth) acryloyl group) other than the (meth) allyl group in the molecule.
  • a (meth) allyl compound (excluding a thiol compound) having a polymerizable group other than the (meth) allyl group in the molecule shall be classified as a "(meth) allyl compound".
  • the monofunctional (meth) allyl compound examples include (meth) allyl acetate, (meth) allyl n-propionate, (meth) allyl benzoate, (meth) allyl phenyl acetate, (meth) allyl phenoxy acetate, and (meth). Examples thereof include allyl methyl ether and (meth) allyl glycidyl ether.
  • polyfunctional (meth) allyl compound examples include di (meth) allyl benzenedicarboxylate, di (meth) allyl cyclohexanedicarboxylate, di (meth) allylmaleate, di (meth) allyl adipate, and di (meth).
  • Examples of the (meth) allyl compound include compounds having an isocyanurate skeleton such as tri (meth) allyl isocyanurate, tri (meth) allyl cyanurate, and benzenedicarboxylic acid di (meth) from the viewpoint of heat resistance and moisture heat resistance of the cured product.
  • At least one selected from the group consisting of allyl and di (meth) allyl cyclohexanedicarboxylic acid is preferable, a compound having an isocyanurate skeleton is more preferable, and tri (meth) allyl isocyanurate is further preferable.
  • the content of the (meth) allyl compound in the resin composition is, for example, 10% by mass to 50% by mass with respect to the total amount of the resin composition. It may be 15% by mass to 45% by mass.
  • the polymerizable compound may include a thioether oligomer as a thiol compound and a (meth) allyl compound (preferably a polyfunctional (meth) allyl compound).
  • the polymerizable compound contains a thioether oligomer and a (meth) allyl compound as a thiol compound and a quantum dot phosphor is used as a phosphor
  • the quantum dot phosphor is in a state of a dispersion liquid dispersed in a silicone compound as a dispersion medium. Is preferable.
  • the polymerizable compound comprises a thiol compound that is not in the form of a thioether oligomer and a (meth) acrylic compound (preferably a polyfunctional (meth) acrylic compound, more preferably a bifunctional (meth) acrylic compound). It may include.
  • the quantum dot phosphor is a (meth) acrylic as a dispersion medium. It is preferably in the form of a compound, preferably a monofunctional (meth) acrylic compound, more preferably a dispersion dispersed in isobornyl (meth) acrylate.
  • the type of photopolymerization initiator contained in the resin composition is not particularly limited, and examples thereof include compounds that generate radicals when irradiated with active energy rays such as ultraviolet rays.
  • the photopolymerization initiator include benzophenone, N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-Methyl-1- [4- (Methylthio) Phenyl] -2-morpholino-propanone-1, 4,4'-bis (dimethylamino) benzophenone (also referred to as "Michler ketone”), 4,4'-bis (Diethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 1-hydroxycyclohexylphenylketone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4- (4-) (2-Hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy
  • At least one selected from the group consisting of an acylphosphine oxide compound, an aromatic ketone compound, and an oxime ester compound is preferable from the viewpoint of curability, and from the acylphosphine oxide compound and the aromatic ketone compound. At least one selected from the above group is more preferable, and an acylphosphine oxide compound is further preferable.
  • the content of the photopolymerization initiator in the resin composition is preferably, for example, 0.1% by mass to 5% by mass, preferably 0.1% by mass to 3% by mass, based on the total amount of the resin composition. It is more preferably 0.1% by mass to 1.5% by mass.
  • the content of the photopolymerization initiator is 0.1% by mass or more, the sensitivity of the resin composition tends to be sufficient, and when the content of the photopolymerization initiator is 5% by mass or less, the resin The influence of the composition on the hue and the decrease in storage stability tend to be suppressed.
  • the resin composition may further contain a light diffusing material.
  • the light diffusing material include titanium oxide, barium sulfate, zinc oxide, calcium carbonate and the like.
  • the light diffusing material is preferably titanium oxide from the viewpoint of light scattering efficiency.
  • the titanium oxide may be rutile-type titanium oxide or anatase-type titanium oxide, and is preferably rutile-type titanium oxide.
  • the average particle size of the light diffusing material is preferably 0.1 ⁇ m to 1 ⁇ m, more preferably 0.2 ⁇ m to 0.8 ⁇ m, and even more preferably 0.2 ⁇ m to 0.5 ⁇ m.
  • the average particle size of the light diffusing material can be measured as follows.
  • the extracted light diffusing material is dispersed in purified water containing a surfactant to obtain a dispersion liquid.
  • the volume-based particle size distribution measured by a laser diffraction type particle size distribution measuring device for example, Shimadzu Corporation, SALD-3000J
  • the value when the integration from the small diameter side is 50% (for example).
  • the median diameter (D50)) is defined as the average particle size of the light diffusing material.
  • the resin composition can be obtained by diluting the resin composition with a liquid medium, precipitating the light diffusing material by centrifugation or the like, and distributing the light diffusing material.
  • the average particle size of the light diffusing material in the cured product obtained by curing the resin composition containing the light diffusing material is the equivalent circle diameter (major axis) of 50 particles by observing the particles using a scanning electron microscope.
  • the geometric mean of the minor axis) can be calculated and calculated as the arithmetic mean value.
  • the light diffusing material preferably has an organic substance layer containing an organic substance on at least a part of the surface thereof.
  • the organic substances contained in the organic substance layer include organic silane, organosiloxane, fluorosilane, organic phosphonate, organic phosphoric acid compound, organic phosphinate, organic sulfonic acid compound, carboxylic acid, carboxylic acid ester, carboxylic acid derivative, amide, and hydrocarbon.
  • the organic substance contained in the organic substance layer preferably contains a polyol, an organic silane, or the like, and more preferably contains at least one of the polyol or the organic silane.
  • organic silanes include octyltriethoxysilane, nonyltriethoxysilane, decyltriethoxysilane, dodecyltriethoxysilane, tridecyltriethoxysilane, tetradecyltriethoxysilane, pentadecyltriethoxysilane, and hexadecyltriethoxysilane.
  • Examples thereof include silane, heptadecyltriethoxysilane, and octadecyltriethoxysilane.
  • organosiloxane examples include polydimethylsiloxane (PDMS) terminated with a trimethylsilyl group, polymethylhydrosiloxane (PMHS), polysiloxane induced by functionalization of PMHS with an olefin (by hydrosilylation), and the like.
  • organic phosphonates include n-octylphosphonic acid and its ester, n-decylphosphonic acid and its ester, 2-ethylhexylphosphonic acid and its ester, and camphyl phosphonic acid and its ester.
  • organic phosphoric acid compound examples include organic acidic phosphate, organic pyrophosphate, organic polyphosphate, organic metaphosphate, salts thereof and the like.
  • organic phosphinate examples include n-hexylphosphinic acid and its ester, n-octylphosphinic acid and its ester, di-n-hexylphosphinic acid and its ester, and di-n-octylphosphinic acid and its ester. Can be mentioned.
  • organic sulfonic acid compound examples include alkyl sulfonic acids such as hexyl sulfonic acid, octyl sulfonic acid, and 2-ethylhexyl sulfonic acid, these alkyl sulfonic acids, metal ions such as sodium, calcium, magnesium, aluminum, and titanium, and ammonium. Examples thereof include salts with ions and organic ammonium ions such as triethanolamine.
  • carboxylic acid include maleic acid, malonic acid, fumaric acid, benzoic acid, phthalic acid, stearic acid, oleic acid, linoleic acid and the like.
  • carboxylic acid ester examples include the above carboxylic acid, ethylene glycol, propylene glycol, trimethylolpropane, diethanolamine, triethanolamine, glycerol, hexanetriol, erythritol, mannitol, sorbitol, pentaerythritol, bisphenol A, hydroquinone, and flo.
  • Specific examples of the amide include stearic acid amide, oleic acid amide, and erucic acid amide.
  • polyolefin and its copolymer examples include a copolymer of polyethylene, polypropylene, ethylene and one or more compounds selected from propylene, butylene, vinyl acetate, acrylate, acrylamide and the like.
  • polyol examples include glycerol, trimethylolethane, trimethylolpropane and the like.
  • alkanolamine examples include diethanolamine and triethanolamine.
  • organic dispersant include high molecular weight organic dispersants having functional groups such as citric acid, polyacrylic acid, polymethacrylic acid, anionic, cationic, bipolar and nonionic.
  • the light diffusing material may have a metal oxide layer containing a metal oxide on at least a part of the surface thereof.
  • the metal oxide contained in the metal oxide layer include silicon dioxide, aluminum oxide, zirconia, phosphoria, and boria.
  • the metal oxide layer may be one layer or two or more layers.
  • the light diffusing material has two metal oxide layers, it preferably contains a first metal oxide layer containing silicon dioxide and a second metal oxide layer containing aluminum oxide.
  • the light diffusing material has a metal oxide layer, the dispersibility of the light diffusing material in the cured product tends to be improved.
  • the metal oxide layer and the organic material layer are provided on the surface of the light diffusing material in the order of the metal oxide layer and the organic material layer.
  • the light diffusing material has an organic material layer and two metal oxide layers, a first metal oxide layer containing silicon dioxide and a second metal oxide layer containing aluminum oxide are formed on the surface of the light diffusing material. It is preferable that the organic material layer is provided in the order of the first metal oxide layer, the second metal oxide layer, and the organic material layer (the organic material layer is the outermost layer).
  • the content of the light diffusing material in the wavelength conversion layer formed by curing the light diffusing material is, for example, 0.1% by mass to 1% by mass with respect to the total amount of the wavelength conversion layer. It is preferably 0.0% by mass, more preferably 0.2% by mass to 1.0% by mass, and even more preferably 0.3% by mass to 1.0% by mass.
  • the resin composition may further contain a liquid medium.
  • the liquid medium means a medium in a liquid state at room temperature (25 ° C.).
  • liquid medium examples include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl-n-pentyl ketone, methyl-n-hexyl ketone, diethyl ketone, and the like.
  • Ketone solvents such as dipropyl ketone, diisobutyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentandione, acetonylacetone; diethyl ether, methyl ethyl ether, methyl-n-propyl ether, diisopropyl Ether, tetrahydrofuran, methyl tetrahydrofuran, dioxane, dimethyl dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di-n-propyl ether, ethylene glycol di-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, Diethylene glycol methyl-n-propyl ether, diethylene glycol methyl-n-butyl ether
  • Solvents methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, t-pentanol , 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, n-decanol , Se-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, cyclohexanol, methylcyclohexanol,
  • Diethylene glycol mono-n-hexyl ether Diethylene glycol mono-n-hexyl ether, triethylene glycol monoethyl ether, tetraethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, etc.
  • Glycol monoether solvent such as terpinene, terpineol, milsen, aloosimene, limonene, dipentene, pinene, carboxylic, ossimen, ferlandrene; straight silicone oil such as dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil; Amino-modified silicone oil, epoxy-modified silicone oil, cal Boxy-modified silicone oil, carbinol-modified silicone oil, mercapto-modified silicone oil, heterologous functional group-modified silicone oil, polyether-modified silicone oil, methylstyryl-modified silicone oil, hydrophilic special-modified silicone oil, higher alkoxy-modified silicone oil, higher fatty acids Modified silicone oils such as modified silicone oils, fluorine-modified silicone oils; butanoic acid, pentanoic acid, hexanoic acid, heptanic acid, octanoic acid, nona
  • the content of the liquid medium in the resin composition is preferably, for example, 1% by mass to 10% by mass, and 4% by mass, based on the total amount of the resin composition. It is more preferably about 10% by mass, and even more preferably 4% by mass to 7% by mass.
  • the resin composition may further contain components other than the above-mentioned components.
  • the resin composition may further contain components such as a polymerization inhibitor, a silane coupling agent, a surfactant, an adhesion imparting agent, an antioxidant, and a carboxylic acid such as acetic acid.
  • a polymerization inhibitor such as a silane coupling agent, a surfactant, an adhesion imparting agent, an antioxidant, and a carboxylic acid such as acetic acid.
  • the resin composition can be prepared by mixing a phosphor, a polymerizable compound, a photopolymerization initiator, and if necessary, other components by a conventional method.
  • the wavelength conversion layer may be one obtained by curing one kind of resin composition, or may be one obtained by curing two or more kinds of resin compositions.
  • the wavelength conversion layer has different light emitting characteristics from the first cured product layer obtained by curing the resin composition containing the first phosphor and the first phosphor.
  • a resin composition containing a second phosphor may be laminated with a second cured product layer obtained by curing the resin composition.
  • the average thickness of the wavelength conversion layer is not particularly limited, and is preferably, for example, 50 ⁇ m to 200 ⁇ m, more preferably 50 ⁇ m to 150 ⁇ m, and even more preferably 70 ⁇ m to 120 ⁇ m.
  • the average thickness of the wavelength conversion layer is 50 ⁇ m or more, the wavelength conversion efficiency tends to be further improved, and when the average thickness of the wavelength conversion layer is 200 ⁇ m or less, when the wavelength conversion member is applied to the backlight unit described later. In addition, there is a tendency that the backlight unit can be made thinner.
  • the average thickness of the wavelength conversion layer is obtained as, for example, an arithmetic mean value of the thicknesses of any three points measured using a micrometer.
  • the wavelength conversion layer preferably has a loss tangent (tan ⁇ ) of 0.4 to 1.5 measured under the conditions of a frequency of 10 Hz and a temperature of 25 ° C. by dynamic viscoelasticity measurement. It is more preferably 0.4 to 1.2, and even more preferably 0.4 to 0.6.
  • the loss tangent (tan ⁇ ) of the wavelength conversion layer can be measured using a dynamic viscoelasticity measuring device (for example, Rheometric Scientific, Solid Analyzer RSA-III).
  • the wavelength conversion layer preferably has a glass transition temperature (Tg) of 85 ° C. or higher, more preferably 85 ° C. to 160 ° C., and 90 ° C., from the viewpoint of further improving adhesion, heat resistance, and moist heat resistance. It is more preferably ° C. to 120 ° C.
  • the glass transition temperature (Tg) of the wavelength conversion layer can be measured under the condition of a frequency of 10 Hz using a dynamic viscoelasticity measuring device (for example, Rheometric Scientific, Solid Analyzer RSA-III).
  • the wavelength conversion layer has a storage elastic modulus of 1 ⁇ 10 7 Pa to 1 ⁇ 10 10 Pa measured under the conditions of a frequency of 10 Hz and a temperature of 25 ° C. from the viewpoint of further improving adhesion, heat resistance, and moisture heat resistance. It is preferably 5 ⁇ 10 7 Pa to 1 ⁇ 10 10 Pa, more preferably 5 ⁇ 10 7 Pa to 5 ⁇ 10 9 Pa.
  • the storage elastic modulus of the cured resin product can be measured using a dynamic viscoelasticity measuring device (for example, Rheometric Scientific, Solid Analyzer RSA-III).
  • the wavelength conversion layer can be obtained, for example, by forming a coating film, a molded product, or the like of a resin composition, performing a drying treatment as necessary, and then irradiating with active energy rays such as ultraviolet rays.
  • the wavelength and irradiation amount of the active energy rays can be appropriately set according to the composition of the resin composition. In one aspect, it is irradiated with ultraviolet rays having a wavelength of 280 nm ⁇ 400 nm at an irradiation amount of 100mJ / cm 2 ⁇ 5000mJ / cm 2.
  • Examples of the ultraviolet source include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, and the like.
  • FIG. 1 shows an example of the schematic configuration of the wavelength conversion member.
  • the wavelength conversion member of the present disclosure is not limited to the configuration shown in FIG.
  • the wavelength conversion member 10 shown in FIG. 1 has a wavelength conversion layer 11 which is a film-like cured product, and film-like coating materials 12A and 12B provided on both sides of the wavelength conversion layer 11.
  • the types and average thicknesses of the covering material 12A and the covering material 12B may be the same or different.
  • the covering materials 12A and 12B may be roughened.
  • the wavelength conversion member having the configuration shown in FIG. 1 can be manufactured by, for example, the following manufacturing method.
  • a resin composition for forming a wavelength conversion layer is applied to the surface of a film-like coating material (hereinafter, also referred to as "first coating material") that is continuously conveyed to form a coating film.
  • first coating material a film-like coating material
  • the method for applying the resin composition is not particularly limited, and examples thereof include a die coating method, a curtain coating method, an extrusion coating method, a rod coating method, and a roll coating method.
  • a film-like coating material (hereinafter, also referred to as “second coating material”) that is continuously conveyed is attached onto the coating film of the resin composition.
  • the coating film is cured and a cured product layer is formed by irradiating the active energy rays from the side of the first coating material and the second coating material that can transmit the active energy rays. Then, by cutting out to a specified size, a wavelength conversion member having the configuration shown in FIG. 1 can be obtained.
  • the coating film is irradiated with the active energy rays before the second coating material is bonded to form a cured product layer. May be formed, and then a second covering material may be attached.
  • the backlight unit of the present disclosure includes a light source and a wavelength conversion member of the present disclosure.
  • the backlight unit is preferably a multi-wavelength light source from the viewpoint of improving color reproducibility.
  • blue light having an emission center wavelength in the wavelength range of 430 nm to 480 nm and having an emission intensity peak having a half-value width of 100 nm or less, and emission center wavelength in the wavelength range of 520 nm to 560 nm.
  • the light unit can be mentioned.
  • the half-value width of the emission intensity peak means the peak width at a height of 1/2 of the peak height.
  • the emission center wavelength of the blue light emitted by the backlight unit is preferably in the range of 440 nm to 475 nm.
  • the emission center wavelength of the green light emitted by the backlight unit is preferably in the range of 520 nm to 545 nm.
  • the emission center wavelength of the red light emitted by the backlight unit is preferably in the range of 610 nm to 640 nm.
  • the half-value width of each emission intensity peak of the blue light, green light, and red light emitted by the backlight unit is preferably 80 nm or less, preferably 50 nm or less. It is more preferably 40 nm or less, particularly preferably 30 nm or less, and extremely preferably 25 nm or less.
  • the light source of the backlight unit for example, a light source that emits blue light having a emission center wavelength in the wavelength range of 430 nm to 480 nm can be used.
  • the light source include an LED (Light Emitting Diode) and a laser.
  • the wavelength conversion member preferably includes at least a quantum dot phosphor R that emits red light and a quantum dot phosphor G that emits green light.
  • white light can be obtained from the red light and green light emitted from the wavelength conversion member and the blue light transmitted through the wavelength conversion member.
  • the light source of the backlight unit for example, a light source that emits ultraviolet light having a emission center wavelength in the wavelength range of 300 nm to 430 nm can be used.
  • the light source include LEDs and lasers.
  • the wavelength conversion member preferably includes a quantum dot phosphor B that is excited by excitation light and emits blue light, together with a quantum dot phosphor R and a quantum dot phosphor G. As a result, white light can be obtained from the red light, green light, and blue light emitted from the wavelength conversion member.
  • the backlight unit of the present disclosure may be an edge light type or a direct type.
  • Fig. 2 shows an example of the schematic configuration of the edge light type backlight unit.
  • the backlight unit 20 shown in FIG. 2 includes a light source 21 for emitting the blue light L B, a light guide plate 22 to be emitted guiding the blue light L B emitted from the light source 21, the light guide plate 22 and disposed to face
  • the wavelength conversion member 10 is provided with a retroreflective member 23 arranged to face the light source plate 22 via the wavelength conversion member 10, and a reflection plate 24 arranged to face the wavelength conversion member 10 via the light guide plate 22. ..
  • Wavelength conversion member 10 emits the red light L R and the green light L G part of the blue light L B as the excitation light, the red light L and R and the green light L G, the blue light was not the excitation light L B is emitted.
  • the red light L R, the green light L G, and the blue light L B, the white light L W is emitted from the retroreflective member 23.
  • the image display device of the present disclosure includes the backlight unit of the present disclosure described above.
  • the image display device is not particularly limited, and examples thereof include a liquid crystal display device.
  • FIG. 3 shows an example of the schematic configuration of the liquid crystal display device.
  • the liquid crystal display device 30 shown in FIG. 3 includes a backlight unit 20 and a liquid crystal cell unit 31 arranged to face the backlight unit 20.
  • the liquid crystal cell unit 31 has a configuration in which the liquid crystal cell 32 is arranged between the polarizing plate 33A and the polarizing plate 33B.
  • the drive method of the liquid crystal cell 32 is not particularly limited, and is a TN (Twisted Nematic) method, an STN (Super Twisted Nematic) method, a VA (Vertical Birefringence) method, an IPS (In-Plane-Switching) method, an OCB (Optical Birefringence) method.
  • TN Transmission Nematic
  • STN Super Twisted Nematic
  • VA Very Birefringence
  • IPS In-Plane-Switching
  • OCB Optical Birefringence
  • Examples of the (meth) acrylic compound include tricyclodecanedimethanol diacrylate (Shin-Nakamura Chemical Industry Co., Ltd., A-DCP) and ethoxylated bisphenol A diacrylate (Shin-Nakamura Chemical Industry Co., Ltd., ABE-300; alkyleneoxy). A group-containing compound) was used.
  • thiol compound pentaerythritol tetrakis (3-mercaptopropionate) (SC Organic Chemistry Co., Ltd., PEMP) was used.
  • UV-polymerization initiator 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (BASF, IRGACURE TPO) was used.
  • a CdSe / ZnS (core / shell) dispersion liquid (Nanosys, Gen3.5 QD Concentrate) was used.
  • Isobornyl acrylate (IBOA) was used as the dispersion medium for the CdSe / ZnS (core / shell) dispersion.
  • the CdSe / ZnS (core / shell) dispersion contains 86% by mass or more of isobornyl acrylate.
  • Acetic acid was used as the carboxylic acid.
  • Titanium oxide (The Chemours Company, Typure R-706, particle size 0.36 ⁇ m) was used as the light diffusing material.
  • a first metal oxide layer containing silicon oxide, a second metal oxide layer containing aluminum oxide, and an organic substance layer containing a polyol compound are formed as a first metal oxide layer and a second metal oxide layer. And the organic layer are provided in this order.
  • Barrier film 1 Barrier film with an average thickness of 75 ⁇ m (a PET film with a barrier component deposited on one side)
  • Barrier film 2 Barrier film with an average thickness of 25 ⁇ m (a PET film sputtered with a barrier component on one side)
  • Barrier film 3 Barrier film with an average thickness of 103 ⁇ m (a PET film coated on one side with a barrier component)
  • an ultraviolet irradiation device Igraphics Co., Ltd.
  • thermomechanical analysis was performed by a tensile method using a thermomechanical analysis (TMA) device (manufactured by TA Instruments, trade name: Q400). The thermomechanical analysis is performed twice in succession under the conditions of a load of 0.05 N and a heating rate of 10 ° C./min after mounting the cured product for evaluation in the device in the MD direction, and the thermomechanical analysis is performed from 30 ° C. to 50 in the second analysis. The average coefficient of thermal expansion from ° C. and 120 ° C. to 140 ° C. was calculated and used as the value of the coefficient of thermal expansion. The coefficient of thermal expansion of the barrier film was similarly measured using a thermomechanical analysis (TMA) device.
  • TMA thermomechanical analysis
  • Each wavelength conversion member obtained above was cut into dimensions having a width of 20 mm and a length of 20 cm to obtain a wavelength conversion member for evaluation.
  • One end of the processed wavelength conversion member is fixed to a table having a height of 10 cm or more so as to protrude 10 cm from the table, and the tip of the protruding wavelength conversion member is several mm below the horizontal plane of the table.
  • the measured specific values are shown in Table 2.
  • Each wavelength conversion member obtained above was wound around a winding core having a diameter of 6 inches, allowed to stand at 25 ° C. for 1000 hours, punched into a rectangle of 1470 mm ⁇ 850 mm, and 50 sheets were stacked and sandwiched between glass plates.
  • a wavelength conversion member for evaluation was obtained by allowing to stand at 45 ° C. for 24 hours, 60 ° C. for 4 hours, 60 ° C. for 10 hours, or 85 ° C. for 4 hours.
  • the curl amount (warp amount) is the maximum value measured at 6 points at the ends of the punched wavelength conversion member. The results are shown in Table 2.
  • Each wavelength conversion member obtained above is wound around a winding core having a diameter of 6 inches, allowed to stand at 25 ° C. for 1000 hours, punched into a rectangle of 1470 mm ⁇ 850 mm, and a spectroradiometer (PHOTO RESEARCH, PR-655). ) was used to measure the brightness. After measuring the brightness, 50 punched wavelength conversion members were stacked and sandwiched between glass plates, and allowed to stand at 45 ° C. for 24 hours, 60 ° C. for 4 hours, 60 ° C. for 10 hours, or 85 ° C. for 4 hours.
  • the curl amount was suppressed under any of the conditions of 45 ° C. for 24 hours, 60 ° C. for 4 hours, and 60 ° C. for 10 hours, and the change in optical characteristics was also suppressed. It had been. Under the condition of 85 ° C. for 4 hours, the amount of curl was small in Examples and Comparative Examples, but a change in optical characteristics was observed.

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Abstract

A wavelength conversion member having a wavelength conversion layer that contains a phosphor, the wavelenght conversion member being such that, when measured under a load of 0.05 N and at a temperature rise rate of 10°C/minute by a thermomechanical analysis device, the thermal expansion coefficient at the glass transition temperature or less is 30 ppm/°C or greater, the thermal expansion coefficient at the glass transition temperature or greater is 0 ppm/°C or less, or both of these are satisfied.

Description

波長変換部材、バックライトユニット、及び画像表示装置Wavelength conversion member, backlight unit, and image display device
　本開示は、波長変換部材、バックライトユニット、及び画像表示装置に関する。 The present disclosure relates to a wavelength conversion member, a backlight unit, and an image display device.
　近年、液晶表示装置等の画像表示装置の分野において、ディスプレイの色再現性を向上させることが求められている。色再現性を向上させる手段として、特表２０１３－５４４０１８号公報及び国際公開第２０１６／０５２６２５号に記載のように、量子ドット蛍光体を含む波長変換部材が注目を集めている。 In recent years, in the field of image display devices such as liquid crystal display devices, it has been required to improve the color reproducibility of displays. As a means for improving color reproducibility, a wavelength conversion member containing a quantum dot phosphor has attracted attention as described in Japanese Patent Application Laid-Open No. 2013-544018 and International Publication No. 2016/0526225.
　蛍光体を含む波長変換部材は、例えば、画像表示装置のバックライトユニットに配置される。赤色光を発光する量子ドット蛍光体及び緑色光を発光する量子ドット蛍光体を含む波長変換部材を用いる場合、波長変換部材に対して励起光としての青色光を照射すると、量子ドット蛍光体から発光された赤色光及び緑色光と、波長変換部材を透過した青色光とにより、白色光を得ることができる。量子ドット蛍光体を含む波長変換部材の開発により、ディスプレイの色再現性は、従来のＮＴＳＣ（Ｎａｔｉｏｎａｌ　Ｔｅｌｅｖｉｓｉｏｎ　Ｓｙｓｔｅｍ　Ｃｏｍｍｉｔｔｅｅ）比７２％からＮＴＳＣ比１００％へと拡大している。 The wavelength conversion member including the phosphor is arranged in, for example, the backlight unit of the image display device. When a wavelength conversion member including a quantum dot phosphor that emits red light and a quantum dot phosphor that emits green light is used, when the wavelength conversion member is irradiated with blue light as excitation light, the quantum dot phosphor emits light. White light can be obtained from the red light and green light produced and the blue light transmitted through the wavelength conversion member. With the development of wavelength conversion members containing quantum dot phosphors, the color reproducibility of displays has been expanded from 72% of the conventional NTSC (National Television System Committee) ratio to 100% of the NTSC ratio.
　蛍光体を含む波長変換部材は、通常、蛍光体を含む硬化性組成物を硬化させた硬化物を有する。硬化性組成物としては熱硬化型及び光硬化型があり、生産性の観点からは光硬化型の硬化性組成物が好ましく用いられる。 The wavelength conversion member containing a phosphor usually has a cured product obtained by curing a curable composition containing the phosphor. The curable composition includes a thermosetting type and a photocurable type, and a photocurable type curable composition is preferably used from the viewpoint of productivity.
　また、蛍光体を含む波長変換部材では、蛍光体を含む硬化物の少なくとも一部が被覆材によって被覆される場合がある。例えば、フィルム状の波長変換部材の場合、蛍光体を含む硬化物の片面又は両面に、酸素に対するバリア性を有するバリアフィルムが設けられることがある。 Further, in the wavelength conversion member containing a phosphor, at least a part of the cured product containing the phosphor may be covered with a coating material. For example, in the case of a film-shaped wavelength conversion member, a barrier film having a barrier property against oxygen may be provided on one side or both sides of the cured product containing a phosphor.
　従来、蛍光体を含むフィルム状の波長変換部材は、裁断して枚葉状に形成し、輸送又は保管に供されていた。一方、輸送又は保管の効率を向上する観点からは、波長変換部材をロール状に巻いた状態とする、すなわちロール化することが望ましい。 Conventionally, a film-shaped wavelength conversion member containing a phosphor has been cut into a single-wafer shape and used for transportation or storage. On the other hand, from the viewpoint of improving the efficiency of transportation or storage, it is desirable to wind the wavelength conversion member in a roll shape, that is, to roll it.
　ロール化された波長変換部材は、その後の打ち抜き加工等において平面状に巻き出して使用される。しかしながら、ロール化された波長変換部材は、保管中に巻き癖がついてしまい、自重で平面状に戻すことが困難である。また、波長変換部材の巻き戻しが不十分であると、画像表示装置のバックライトに使用したときに、波長変換部材を透過した光がぼやける等の影響がでる可能性がある。ここで、波長変換部材を例えば８５℃程度の高温下に静置することで平面状に戻すことは可能であるが、波長変換部材を高温に供すると、量子ドット蛍光体の光学特性が劣化してしまうことが本発明者らによって見出された。そのため、波長変換部材を高温に供しなくとも、比較的低温（例えば４５℃以下）で、効率的に平面状に巻き戻し可能であることが望ましい。 The rolled wavelength conversion member is used by unwinding it in a plane in the subsequent punching process or the like. However, the rolled wavelength conversion member has a curl during storage, and it is difficult to return it to a flat shape by its own weight. Further, if the wavelength conversion member is not sufficiently rewound, the light transmitted through the wavelength conversion member may be blurred when used as a backlight of an image display device. Here, it is possible to return the wavelength conversion member to a flat surface by allowing it to stand at a high temperature of, for example, about 85 ° C. However, when the wavelength conversion member is subjected to a high temperature, the optical characteristics of the quantum dot phosphor deteriorate. It was found by the present inventors that it would end up. Therefore, it is desirable that the wavelength conversion member can be efficiently rewound into a flat surface at a relatively low temperature (for example, 45 ° C. or lower) without subjecting the wavelength conversion member to a high temperature.
　上記事情に鑑み、本開示は、ロール化後の巻き戻しが容易である波長変換部材、並びに当該波長変換部材を用いたバックライトユニット及び画像表示装置を提供することを目的とする。 In view of the above circumstances, an object of the present disclosure is to provide a wavelength conversion member that can be easily rewound after rolling, and a backlight unit and an image display device using the wavelength conversion member.
　上記課題を解決するための手段は、以下の態様を含む。
＜１＞　蛍光体を含む波長変換層を有し、熱機械分析装置で荷重０．０５Ｎ、昇温速度１０℃／分の条件で測定したときのガラス転移温度以下での熱膨張係数が３０ｐｐｍ／℃以上であるか、ガラス転移温度以上での熱膨張係数が０ｐｐｍ／℃以下であるか、又はこれらの両方を満たす、波長変換部材。
＜２＞　前記波長変換部材が、前記波長変換層の一方の面側又は両方の面側に配置される被覆材を含み、熱機械分析装置で荷重０．０５Ｎ、昇温速度１０℃／分の条件で測定したときの前記被覆材のガラス転移温度以上での熱膨張係数が０ｐｐｍ／℃以下である＜１＞に記載の波長変換部材。
＜３＞　前記波長変換部材が被覆材を含み、前記波長変換部材のガラス転移温度以下での熱膨張係数から、熱機械分析装置で荷重０．０５Ｎ、昇温速度１０℃／分の条件で測定したときの前記被覆材のガラス転移温度以下での熱膨張係数を引いた値が１０ｐｐｍ／℃以上である、＜１＞又は＜２＞に記載の波長変換部材。
＜４＞　動的粘弾性測定装置で周波数１０Ｈｚかつ温度３０℃の条件で測定したときの貯蔵弾性率が３．７ＧＰａ以下である、＜１＞～＜３＞のいずれか１項に記載の波長変換部材。
＜５＞　以下の方法により測定される値が６．０ｍｍ以上である、＜１＞～＜４＞のいずれか１項に記載の波長変換部材：
　試験台上に、幅２０ｍｍの矩形に加工された前記波長変換部材を、前記試験台から外側に、長さ１０ｃｍ突出するように配置し、自重で下垂した前記波長変換部材の先端部の高さと、前記試験台の基準面の高さと、の距離を測定する。
＜６＞　前記蛍光体が量子ドット蛍光体を含む、＜１＞～＜５＞のいずれか１項に記載の波長変換部材。
＜７＞　前記量子ドット蛍光体がＣｄ及びＩｎの少なくとも一方を含む、＜６＞に記載の波長変換部材。
＜８＞　前記波長変換層が、前記蛍光体と、チオール化合物と、（メタ）アクリル化合物及び（メタ）アリル化合物からなる群より選択される少なくとも１種と、光重合開始剤と、を含有する樹脂組成物の硬化物を含む、＜１＞～＜７＞のいずれか１項に記載の波長変換部材。
＜９＞　ロール状に形成されている、＜１＞～＜８＞のいずれか１項に記載の波長変換部材。
＜１０＞　＜１＞～＜８＞のいずれか１項に記載の波長変換部材と、光源と、を備えるバックライトユニット。
＜１１＞　＜９＞に記載のバックライトユニットを備える画像表示装置。 Means for solving the above problems include the following aspects.
<1> A wavelength conversion layer containing a phosphor is provided, and the coefficient of thermal expansion below the glass transition temperature is 30 ppm / min when measured with a thermomechanical analyzer under the conditions of a load of 0.05 N and a heating rate of 10 ° C./min. A wavelength conversion member having a coefficient of thermal expansion of 0 ppm / ° C. or higher at a temperature of ° C. or higher, a glass transition temperature or higher, or both.
<2> The wavelength conversion member includes a coating material arranged on one surface side or both surface sides of the wavelength conversion layer, and has a load of 0.05 N and a heating rate of 10 ° C./min in a thermomechanical analyzer. The wavelength conversion member according to <1>, wherein the coefficient of thermal expansion of the coating material at a glass transition temperature or higher when measured under conditions is 0 ppm / ° C. or lower.
<3> The wavelength conversion member contains a coating material, and is measured by a thermomechanical analyzer under the conditions of a load of 0.05 N and a temperature rise rate of 10 ° C./min from the coefficient of thermal expansion of the wavelength conversion member below the glass transition temperature. The wavelength conversion member according to <1> or <2>, wherein the value obtained by subtracting the coefficient of thermal expansion below the glass transition temperature of the coating material is 10 ppm / ° C. or higher.
<4> The wavelength according to any one of <1> to <3>, wherein the storage elastic modulus is 3.7 GPa or less when measured with a dynamic viscoelasticity measuring device under the conditions of a frequency of 10 Hz and a temperature of 30 ° C. Conversion member.
<5> The wavelength conversion member according to any one of <1> to <4>, wherein the value measured by the following method is 6.0 mm or more:
The wavelength conversion member processed into a rectangle having a width of 20 mm is arranged on the test table so as to project outward by 10 cm in length from the test table, and the height of the tip portion of the wavelength conversion member that hangs down by its own weight. , Measure the distance from the height of the reference plane of the test stand.
<6> The wavelength conversion member according to any one of <1> to <5>, wherein the phosphor contains a quantum dot phosphor.
<7> The wavelength conversion member according to <6>, wherein the quantum dot phosphor contains at least one of Cd and In.
<8> The wavelength conversion layer contains the phosphor, a thiol compound, at least one selected from the group consisting of a (meth) acrylic compound and a (meth) allyl compound, and a photopolymerization initiator. The wavelength conversion member according to any one of <1> to <7>, which comprises a cured product of the resin composition.
<9> The wavelength conversion member according to any one of <1> to <8>, which is formed in a roll shape.
<10> A backlight unit including the wavelength conversion member according to any one of <1> to <8> and a light source.
<11> An image display device including the backlight unit according to <9>.
　本開示によれば、ロール化後の巻き戻しが容易である波長変換部材、並びに当該波長変換部材を用いたバックライトユニット及び画像表示装置が提供される。 According to the present disclosure, a wavelength conversion member that can be easily rewound after rolling, and a backlight unit and an image display device using the wavelength conversion member are provided.
波長変換部材の概略構成の一例を示す模式断面図である。It is a schematic cross-sectional view which shows an example of the schematic structure of the wavelength conversion member. バックライトユニットの概略構成の一例を示す図である。It is a figure which shows an example of the schematic structure of the backlight unit. 液晶表示装置の概略構成の一例を示す図である。It is a figure which shows an example of the schematic structure of the liquid crystal display device.
　以下、本開示の実施形態について詳細に説明する。但し、本開示の実施形態は以下の実施形態に限定されるものではない。以下の実施形態において、その構成要素（要素ステップ等も含む）は、特に明示した場合を除き、必須ではない。数値及びその範囲についても同様であり、本開示の実施形態を制限するものではない。 Hereinafter, embodiments of the present disclosure will be described in detail. However, the embodiments of the present disclosure are not limited to the following embodiments. In the following embodiments, the components (including element steps and the like) are not essential unless otherwise specified. The same applies to the numerical values and their ranges, and does not limit the embodiments of the present disclosure.
　本開示において「～」を用いて示された数値範囲には、「～」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。
　本開示中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
　本開示において各成分は該当する物質を複数種含んでいてもよい。組成物中に各成分に該当する物質が複数種存在する場合、各成分の含有率又は含有量は、特に断らない限り、組成物中に存在する当該複数種の物質の合計の含有率又は含有量を意味する。
　本開示において各成分に該当する粒子は複数種含んでいてもよい。組成物中に各成分に該当する粒子が複数種存在する場合、各成分の粒子径は、特に断らない限り、組成物中に存在する当該複数種の粒子の混合物についての値を意味する。
　本開示において「層」又は「膜」との語には、当該層又は膜が存在する領域を観察したときに、当該領域の全体に形成されている場合に加え、当該領域の一部にのみ形成されている場合も含まれる。
　本開示において「積層」との語は、層を積み重ねることを示し、二以上の層が結合されていてもよく、二以上の層が着脱可能であってもよい。
　本開示において「（メタ）アクリレート」とはアクリレート及びメタクリレートの少なくとも一方を意味し、「（メタ）アリル」とはアリルとメタアリルの少なくとも一方を意味し、「（メタ）アクリル」とはアクリル及びメタクリルの少なくとも一方を表し、「（メタ）アクリロイル」とは、アクリロイル及びメタクリロイルの少なくとも一方を意味する。
　本開示において実施形態を図面を参照して説明する場合、当該実施形態の構成は図面に示された構成に限定されない。また、各図における部材の大きさは概念的なものであり、部材間の大きさの相対的な関係はこれに限定されない。また、各図面において、実質的に同じ機能を有する部材には、全図面同じ符号を付与し、重複する説明は省略する場合がある。 The numerical range indicated by using "-" in the present disclosure includes the numerical values before and after "-" as the minimum value and the maximum value, respectively.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. .. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present disclosure, each component may contain a plurality of applicable substances. When a plurality of substances corresponding to each component are present in the composition, the content or content of each component is the total content or content of the plurality of substances present in the composition unless otherwise specified. Means quantity.
In the present disclosure, a plurality of types of particles corresponding to each component may be contained. When a plurality of particles corresponding to each component are present in the composition, the particle size of each component means a value for a mixture of the plurality of particles present in the composition unless otherwise specified.
In the present disclosure, the term "layer" or "membrane" is used only in a part of the region in addition to the case where the layer or the membrane is formed in the entire region when the region in which the layer or the membrane is present is observed. The case where it is formed is also included.
In the present disclosure, the term "laminated" refers to stacking layers, and two or more layers may be bonded or the two or more layers may be removable.
In the present disclosure, "(meth) acrylate" means at least one of acrylate and methacrylate, "(meth) allyl" means at least one of allyl and methallyl, and "(meth) acrylic" means acrylic and methacrylic. And "(meth) acryloyl" means at least one of acryloyl and methacryloyl.
When the embodiment is described in the present disclosure with reference to the drawings, the configuration of the embodiment is not limited to the configuration shown in the drawings. Further, the size of the members in each figure is conceptual, and the relative relationship between the sizes of the members is not limited to this. Further, in each drawing, members having substantially the same function may be given the same reference numerals in all drawings, and duplicate description may be omitted.
≪波長変換部材≫
　本開示の波長変換部材は、蛍光体を含む波長変換層を有し、熱機械分析（ＴＭＡ）装置で荷重０．０５Ｎ、昇温速度１０℃／分の条件で測定したときのガラス転移温度以下での熱膨張係数が３０ｐｐｍ／℃以上であるか、ガラス転移温度以上での熱膨張係数が０ｐｐｍ／℃以下であるか、又はこれらの両方を満たす。以下、本開示において、上記条件で部材を測定したときの熱膨張係数を単に「熱膨張係数」ともいう。
　部材のガラス転移温度以下での熱膨張係数は、ガラス転移温度－１００℃から当該ガラス転移温度までの範囲における任意の２０℃の温度幅で測定するものとする。部材のガラス転移温度以上での熱膨張係数は、ガラス転移温度からガラス転移温度＋１００℃までの範囲における任意の２０℃の温度幅で測定するものとする。具体的には、部材の熱膨張係数は、例えば実施例に記載の方法により測定することができる。 ≪Wavelength conversion member≫
The wavelength conversion member of the present disclosure has a wavelength conversion layer containing a phosphor, and is equal to or lower than the glass transition temperature when measured by a thermomechanical analysis (TMA) apparatus under the conditions of a load of 0.05 N and a heating rate of 10 ° C./min. The coefficient of thermal expansion at 30 ppm / ° C. or higher, the coefficient of thermal expansion above the glass transition temperature is 0 ppm / ° C. or lower, or both are satisfied. Hereinafter, in the present disclosure, the coefficient of thermal expansion when the member is measured under the above conditions is also simply referred to as "coefficient of thermal expansion".
The coefficient of thermal expansion of the member below the glass transition temperature shall be measured in an arbitrary temperature range of 20 ° C. in the range from the glass transition temperature of -100 ° C. to the glass transition temperature. The coefficient of thermal expansion of the member above the glass transition temperature shall be measured in an arbitrary temperature range of 20 ° C. in the range from the glass transition temperature to the glass transition temperature + 100 ° C. Specifically, the coefficient of thermal expansion of the member can be measured by, for example, the method described in Examples.
　本開示の波長変換部材によれば、ロール化後の巻き戻しを効率的に行うことができる。明確な理由は明らかではないが、上記の熱膨張係数と、ロール化後のカールの戻りやすさとの間に相関が見出された。このことから、波長変換部材の熱膨張の挙動がカールの生じやすさ又は戻りやすさに影響していることが示唆される。ガラス転移温度以下の熱膨張係数が大きい、又はガラス転移温度以上での熱膨張係数が０ｐｐｍ／℃以下になることは、樹脂材料中の自由体積が大きいことを示しており、ロール化後の巻き戻し時に元の形状に戻りやすいものと推測される。 According to the wavelength conversion member of the present disclosure, rewinding after rolling can be performed efficiently. Although the exact reason is not clear, a correlation was found between the above coefficient of thermal expansion and the ease of curl return after rolling. From this, it is suggested that the behavior of thermal expansion of the wavelength conversion member affects the easiness of curling or the easiness of returning. A large coefficient of thermal expansion below the glass transition temperature or a coefficient of thermal expansion above the glass transition temperature of 0 ppm / ° C. indicates that the free volume in the resin material is large, and winding after rolling. It is presumed that it is easy to return to the original shape when returning.
　波長変換部材のガラス転移温度以下での熱膨張係数が３０ｐｐｍ／℃以上である場合、当該熱膨張係数は３２ｐｐｍ／℃以上であってもよく、３５ｐｐｍ／℃以上であってもよい。形状安定性の観点からは、波長変換部材のガラス転移温度以下での熱膨張係数は６０ｐｐｍ／℃以下であってもよく、５０ｐｐｍ／℃以下であってもよく、４５ｐｐｍ／℃以下であってもよい。
　波長変換部材のガラス転移温度以上での熱膨張係数が０ｐｐｍ／℃以下である場合、当該熱膨張係数は－１０ｐｐｍ／℃以下であってもよく、－２０ｐｐｍ／℃以下であってもよく、－３０ｐｐｍ／℃以下であってもよい。形状安定性の観点からは、波長変換部材のガラス転移温度以上での熱膨張係数は、－６０ｐｐｍ／℃以上であってもよく、－５０ｐｐｍ／℃以上であってもよく、－４５ｐｐｍ／℃以上であってもよい。 When the coefficient of thermal expansion of the wavelength conversion member below the glass transition temperature is 30 ppm / ° C. or higher, the coefficient of thermal expansion may be 32 ppm / ° C. or higher, or 35 ppm / ° C. or higher. From the viewpoint of shape stability, the coefficient of thermal expansion of the wavelength conversion member below the glass transition temperature may be 60 ppm / ° C. or lower, 50 ppm / ° C. or lower, or 45 ppm / ° C. or lower. good.
When the coefficient of thermal expansion of the wavelength conversion member above the glass transition temperature is 0 ppm / ° C or less, the coefficient of thermal expansion may be -10 ppm / ° C or less, -20 ppm / ° C or less, or-. It may be 30 ppm / ° C. or less. From the viewpoint of shape stability, the coefficient of thermal expansion of the wavelength conversion member above the glass transition temperature may be -60 ppm / ° C or higher, -50 ppm / ° C or higher, or −45 ppm / ° C or higher. It may be.
　波長変換部材が被覆材を含む場合、被覆材のガラス転移温度以上での熱膨張係数は０ｐｐｍ／℃以下であることが好ましい。被覆材の熱膨張係数が上記範囲であると、ロール化後に巻き戻したときのカール量がより少ない傾向にあることが見出された。この理由は定かではないが、被覆材が軟化することで波長変換層に追従しやすくなりカール量が抑制されるためと推測される。
　被覆材のガラス転移温度以上での熱膨張係数は－１０ｐｐｍ／℃以下であってもよく、－２０ｐｐｍ／℃以下であってもよく、－５０ｐｐｍ／℃以下であってもよく、－７０ｐｐｍ／℃以下であってもよい。また、形状安定性の観点からは、被覆材のガラス転移温度以上での熱膨張係数は－１００ｐｐｍ／℃以上であってもよい。 When the wavelength conversion member contains a coating material, the coefficient of thermal expansion of the coating material above the glass transition temperature is preferably 0 ppm / ° C. or less. It was found that when the coefficient of thermal expansion of the coating material was in the above range, the amount of curl when rewound after rolling tended to be smaller. The reason for this is not clear, but it is presumed that the softening of the coating material makes it easier to follow the wavelength conversion layer and suppresses the amount of curl.
The coefficient of thermal expansion of the coating material above the glass transition temperature may be -10 ppm / ° C or lower, -20 ppm / ° C or lower, -50 ppm / ° C or lower, or −70 ppm / ° C. It may be as follows. From the viewpoint of shape stability, the coefficient of thermal expansion of the coating material above the glass transition temperature may be −100 ppm / ° C. or higher.
　波長変換部材が被覆材を含む場合、前記波長変換部材のガラス転移温度以下での熱膨張係数から、前記被覆材のガラス転移温度以下での熱膨張係数を引いた値（熱膨張係数の差ともいう）が１０ｐｐｍ／℃以上であると、ロール化後に巻き戻したときのカール量がより少ない傾向にあることが見出された。この理由は定かではないが、熱膨張差が大きいことは被覆材が波長変換層に追従していることを示しており、被覆材が波長変換層に追従することでカール量が抑制されると推測される。上記熱膨張係数の差は１２ｐｐｍ／℃以上であってもよく、１４ｐｐｍ／℃以上であってもよい。形状安定性の観点からは、上記熱膨張係数の差は１２０ｐｐｍ／℃以下であってもよく、１１０ｐｐｍ／℃以下であってもよい。 When the wavelength conversion member contains a coating material, the value obtained by subtracting the coefficient of thermal expansion of the coating material below the glass transition temperature from the coefficient of thermal expansion below the glass transition temperature of the coating material (also the difference in the coefficient of thermal expansion). It was found that when the value was 10 ppm / ° C. or higher, the amount of curl when rewound after rolling tended to be smaller. The reason for this is not clear, but the large difference in thermal expansion indicates that the coating material follows the wavelength conversion layer, and that the amount of curl is suppressed by the coating material following the wavelength conversion layer. Guessed. The difference in the coefficient of thermal expansion may be 12 ppm / ° C. or higher, or 14 ppm / ° C. or higher. From the viewpoint of shape stability, the difference in the coefficient of thermal expansion may be 120 ppm / ° C. or less, or 110 ppm / ° C. or less.
　熱膨張係数を調節する方法としては、例えば、波長変換層及び必要に応じて用いられる後述の被覆材の材質、厚み、弾性率、積層構造等を調整する方法が挙げられる。 Examples of the method of adjusting the coefficient of thermal expansion include a method of adjusting the material, thickness, elastic modulus, laminated structure, etc. of the wavelength conversion layer and the coating material to be used later as needed.
　ロール化された波長変換部材の巻き戻しは、例えば以下の方法で行う。ロール化された波長変換部材を巻きだして、打ち抜き加工を行った後、枚葉状に複数枚重ねた波長変換部材をガラス板等に挟み、６０℃以下の条件で恒温槽内に所定時間静置する。例えば、１４７０ｍｍ×８５０ｍｍの矩形に打ち抜き加工した波長変換部材を５０枚重ねてガラス板に挟み、４５℃の条件で２４時間静置したときに、カール量（反り量）は８．０ｍｍ以内であることが好ましく、５．０ｍｍ以内であることがより好ましく、３．０ｍｍ以内であることがさらに好ましい。カール量（反り量）は、打ち抜き加工された波長変換部材の任意の端部６点にて測定したときの最大値とする。 The rolled wavelength conversion member is rewound by, for example, the following method. After the rolled wavelength conversion member is unwound and punched, a plurality of sheet-fed wavelength conversion members are sandwiched between glass plates and the like, and the wavelength conversion member is allowed to stand in a constant temperature bath at a temperature of 60 ° C. or lower for a predetermined time. do. For example, when 50 wavelength conversion members punched into a rectangle of 1470 mm × 850 mm are stacked and sandwiched between glass plates and allowed to stand for 24 hours under the condition of 45 ° C., the curl amount (warp amount) is within 8.0 mm. It is preferably within 5.0 mm, more preferably within 3.0 mm. The curl amount (warp amount) is the maximum value measured at 6 points at arbitrary ends of the punched wavelength conversion member.
　波長変換部材はロール状に形成されていてもよい。本開示の波長変換部材はロール化に適している。波長変換部材のロール化によれば、輸送効率及び保管効率を向上させることができる。さらに、波長変換部材を枚葉状に加工して輸送又は保存する場合と比べて、波長変換部材の端部を少なくすることができるため、端部劣化を抑制できると考えられる。 The wavelength conversion member may be formed in a roll shape. The wavelength conversion member of the present disclosure is suitable for rolling. By rolling the wavelength conversion member, it is possible to improve the transportation efficiency and the storage efficiency. Further, it is considered that the end portion of the wavelength conversion member can be reduced as compared with the case where the wavelength conversion member is processed into a single-wafer shape and transported or stored, so that deterioration of the end portion can be suppressed.
　波長変換部材の形状は、フィルム状であることが好ましい。波長変換部材がフィルム状であることで、バックライトユニットに好適に使用することができ、また、好適にロール化することができる。 The shape of the wavelength conversion member is preferably film-like. Since the wavelength conversion member is in the form of a film, it can be suitably used for a backlight unit and can be suitably rolled.
　波長変換部材の幅及び長さは特に制限されず、例えば、適用する画像表示装置のサイズ等に応じて適宜設定することができる。 The width and length of the wavelength conversion member are not particularly limited, and can be appropriately set according to, for example, the size of the image display device to be applied.
　ロール化された波長変換部材の場合、波長変換部材の幅は用途に応じて適宜調整することができ、例えば１０ｍｍ～５０００ｍｍであってもよい。
　ロール化された波長変換部材の場合、波長変換部材の長さは用途に応じて適宜調整することができ、例えば０．５ｍ～１０００ｍであってもよい。
　ロール化された波長変換部材の場合、波長変換部材の長さとは巻き方向への長さをいい、これに直交する長さを波長変換部材の幅とする。 In the case of the rolled wavelength conversion member, the width of the wavelength conversion member can be appropriately adjusted according to the application, and may be, for example, 10 mm to 5000 mm.
In the case of the rolled wavelength conversion member, the length of the wavelength conversion member can be appropriately adjusted according to the application, and may be, for example, 0.5 m to 1000 m.
In the case of a rolled wavelength conversion member, the length of the wavelength conversion member means the length in the winding direction, and the length orthogonal to this is the width of the wavelength conversion member.
　ロール化された波長変換部材を巻きだして、打ち抜き加工を行った後の波長変換部材の場合、波長変換部材の幅は用途に応じて適宜調整することができ、例えば１０ｍｍ～５０００ｍｍであってもよい。
　ロール化された波長変換部材を巻きだして、打ち抜き加工を行った後の波長変換部材の場合、波長変換部材の長さは用途に応じて適宜調整することができ、例えば１０ｍｍ～５０００ｍｍであってもよい。 In the case of the wavelength conversion member after the rolled wavelength conversion member is unwound and punched, the width of the wavelength conversion member can be appropriately adjusted according to the application, for example, even if it is 10 mm to 5000 mm. good.
In the case of the wavelength conversion member after the rolled wavelength conversion member is unwound and punched, the length of the wavelength conversion member can be appropriately adjusted according to the application, for example, 10 mm to 5000 mm. May be good.
　打ち抜き加工を行った後の波長変換部材の場合、波長変換部材の長さとは長手方向の長さをいい、波長変換部材の幅とは短手方向の長さをいうものとする。波長変換部材が正方形である場合には、当該正方形の一辺の長さが上記波長変換部材の幅又は長さのいずれかの範囲に含まれていることが好ましい。 In the case of a wavelength conversion member after punching, the length of the wavelength conversion member means the length in the longitudinal direction, and the width of the wavelength conversion member means the length in the lateral direction. When the wavelength conversion member is square, it is preferable that the length of one side of the square is included in either the width or the length of the wavelength conversion member.
　波長変換部材の平均厚みは、例えば、１００μｍ～５００μｍであることが好ましく、１２０μｍ～４００μｍであることがより好ましく、１５０μｍ～３００μｍであることがさらに好ましい。波長変換部材の平均厚みが１００μｍ以上であると、波長変換効率がより向上する傾向にあり、平均厚みが５００μｍ以下であると、波長変換部材をバックライトユニットに適用した場合に、バックライトユニットをより薄型化できる傾向にある。
　波長変換部材の平均厚みは、例えば、マイクロメータを用いて測定した任意の３箇所の厚みの算術平均値として求められる。 The average thickness of the wavelength conversion member is, for example, preferably 100 μm to 500 μm, more preferably 120 μm to 400 μm, and even more preferably 150 μm to 300 μm. When the average thickness of the wavelength conversion member is 100 μm or more, the wavelength conversion efficiency tends to be further improved, and when the average thickness is 500 μm or less, when the wavelength conversion member is applied to the backlight unit, the backlight unit is used. There is a tendency to make it thinner.
The average thickness of the wavelength conversion member is obtained as, for example, an arithmetic mean value of the thicknesses of any three points measured using a micrometer.
　波長変換部材は、一方又は両方の面が粗面化されていてもよい。表面粗さＲａは例えば０．５μｍ以上であってもよい。波長変換部材が粗面化されていると、取扱い性に優れ、隣接する部材と波長変換部材が密着することによる干渉縞を抑制することができる傾向にある。 One or both surfaces of the wavelength conversion member may be roughened. The surface roughness Ra may be, for example, 0.5 μm or more. When the wavelength conversion member has a roughened surface, it is easy to handle, and there is a tendency that interference fringes due to close contact between the adjacent member and the wavelength conversion member can be suppressed.
　表面粗さＲａは、３Ｄ顕微鏡（例えば、オリンパス株式会社、型式ＯＬＳ４１００、倍率１０倍）を用いて測定される値をいう。測定範囲は、１２８９μｍ長さでの線粗さとする。解析方法は、解析パラメーターを粗さパラメーターとし、カットオフはλＣ；なし、λＳ；なし、λｆ；なしとする。
　ここで、λＣ、λＳ、λｆは、Ｒａを算出するための輪郭曲線の算出方法である。輪郭曲線には、断面曲線、粗さ曲線及びうねり曲線がある。断面曲線は、測定断面曲線にカットオフ値λＳの低域フィルタを適用して得られる曲線である。粗さ曲線は、カットオフ値λＣの高域フィルタによって、断面曲線から長波長成分を遮断して得た輪郭曲線である。うねり曲線は、断面曲線にカットオフ値λｆ及びλＣの輪郭曲線フィルタを順次かけることによって得られる輪郭曲線である。λｆ輪郭曲線フィルタによって長波長成分を遮断し、λＣ輪郭曲線フィルタによって短波長成分を遮断している。 Surface roughness Ra refers to a value measured using a 3D microscope (for example, Olympus Corporation, model OLS4100, magnification 10 times). The measurement range is a line roughness with a length of 1289 μm. In the analysis method, the analysis parameter is the roughness parameter, and the cutoff is λC; none, λS; none, λf; none.
Here, λC, λS, and λf are methods for calculating the contour curve for calculating Ra. The contour curve includes a cross-section curve, a roughness curve, and a waviness curve. The cross-sectional curve is a curve obtained by applying a low-frequency filter having a cutoff value of λS to the measured cross-sectional curve. The roughness curve is a contour curve obtained by blocking long wavelength components from the cross-sectional curve by a high-frequency filter having a cutoff value of λC. The waviness curve is a contour curve obtained by sequentially applying contour curve filters having cutoff values λf and λC to the cross-sectional curve. The λf contour curve filter blocks the long wavelength component, and the λC contour curve filter blocks the short wavelength component.
　波長変換部材は、光の利用効率をより向上させる観点から、全光線透過率が５５％以上であることが好ましく、６０％以上であることがより好ましく、６５％以上であることがさらに好ましい。波長変換部材の全光線透過率は、ＪＩＳ　Ｋ　７３６１－１：１９９７の測定法に準拠して測定することができる。 From the viewpoint of further improving the light utilization efficiency, the wavelength conversion member preferably has a total light transmittance of 55% or more, more preferably 60% or more, and further preferably 65% or more. The total light transmittance of the wavelength conversion member can be measured according to the measurement method of JIS K 7361-1: 1997.
　また、波長変換部材は、光の利用効率をより向上させる観点から、ヘーズが１０％～６０％であることが好ましく、１０％～５５％であることがより好ましく、１０％～５０％であることがさらに好ましい。波長変換部材のヘーズは、ＪＩＳ　Ｋ　７１３６：２０００の測定法に準拠して測定することができる。 Further, the wavelength conversion member preferably has a haze of 10% to 60%, more preferably 10% to 55%, and 10% to 50% from the viewpoint of further improving the light utilization efficiency. Is even more preferable. The haze of the wavelength conversion member can be measured according to the measurement method of JIS K 7136: 2000.
　ロール化後の巻き戻しの容易性の観点からは、周波数１０Ｈｚかつ温度３０℃の条件で測定した波長変換部材の貯蔵弾性率は、４．１ＧＰａ以下であることが好ましく、３．９ＧＰａ以下であることがより好ましく、３．７ＧＰａ以下であることがさらに好ましく、３．６ＧＰａ以下であることが特に好ましく、３．０ＧＰａ以下であることが極めて好ましく、２．５ＧＰａ以下であることがより極めて好ましい。取扱い性の観点からは、上記貯蔵弾性率は１．０ＧＰａ以上であることが好ましく、１．５ＧＰａ以上であることがより好ましく、１．８ＧＰａ以上であることがさらに好ましい。波長変換部材の貯蔵弾性率は、動的粘弾性測定装置（例えば、Ｒｈｅｏｍｅｔｒｉｃ　Ｓｃｉｅｎｔｉｆｉｃ社、Ｓｏｌｉｄ　Ａｎａｌｙｚｅｒ　ＲＳＡ－ＩＩＩ）を用いて測定することができる。 From the viewpoint of ease of rewinding after rolling, the storage elastic modulus of the wavelength conversion member measured under the conditions of a frequency of 10 Hz and a temperature of 30 ° C. is preferably 4.1 GPa or less, and is preferably 3.9 GPa or less. More preferably, it is more preferably 3.7 GPa or less, particularly preferably 3.6 GPa or less, extremely preferably 3.0 GPa or less, and even more preferably 2.5 GPa or less. From the viewpoint of handleability, the storage elastic modulus is preferably 1.0 GPa or more, more preferably 1.5 GPa or more, and further preferably 1.8 GPa or more. The storage elastic modulus of the wavelength conversion member can be measured using a dynamic viscoelasticity measuring device (for example, Rheometric Scientific, Solid Analyzer RSA-III).
　波長変換部材の貯蔵弾性率を調整する方法は特に制限されず、例えば、波長変換層及び必要に応じて用いられる後述の被覆材の材質、厚み、積層構造等を調整する方法が挙げられる。 The method of adjusting the storage elastic modulus of the wavelength conversion member is not particularly limited, and examples thereof include a method of adjusting the material, thickness, laminated structure, etc. of the wavelength conversion layer and the coating material to be used later as needed.
　波長変換部材において、以下の方法で測定される値（以下、特定値ということがある）を調整してもよい。高さが１０ｃｍ以上ある試験台上に、幅２０ｍｍの矩形に加工された前記波長変換部材を、当該試験台から外側に、長さ１０ｃｍ突出するように配置し、自重で下垂した前記波長変換部材の先端部の高さと、前記試験台の基準面の高さと、の距離を測定する。ここで基準面の高さとは、前記加工された波長変換部材の、前記突出させた部分以外の残りの部分が配置されている試験台上の高さをいう。試験台は、幅２０ｍｍの矩形に加工された波長変換部材の、前記試験台から突出させた部分以外の残りの部分を固定できるものであればよく、その形状及び大きさは特に制限されない。
　ロール化後の巻き戻しの容易性の観点からは、波長変換部材の上記方法で測定される特定値は、６．０ｍｍ以上であることが好ましく、８．０ｍｍ以上であることがより好ましく、１０．０ｍｍ以上であることがさらに好ましい。取扱い性の観点からは、波長変換部材の上記方法で測定される特定値は３５．０ｍｍ以下であることが好ましく、２５．０ｍｍ以下であることがより好ましく、１５．０ｍｍ以下であることがさらに好ましい。 In the wavelength conversion member, a value measured by the following method (hereinafter, may be referred to as a specific value) may be adjusted. The wavelength conversion member processed into a rectangle having a width of 20 mm is arranged on a test table having a height of 10 cm or more so as to project outward by 10 cm in length from the test table, and the wavelength conversion member hangs down by its own weight. Measure the distance between the height of the tip of the test table and the height of the reference surface of the test table. Here, the height of the reference plane means the height on the test table on which the remaining portion of the processed wavelength conversion member other than the protruding portion is arranged. The test table is not particularly limited in shape and size as long as it can fix the remaining portion of the wavelength conversion member processed into a rectangle having a width of 20 mm other than the portion protruding from the test table.
From the viewpoint of ease of rewinding after rolling, the specific value of the wavelength conversion member measured by the above method is preferably 6.0 mm or more, more preferably 8.0 mm or more, and 10 It is more preferably 0.0 mm or more. From the viewpoint of handleability, the specific value of the wavelength conversion member measured by the above method is preferably 35.0 mm or less, more preferably 25.0 mm or less, and further preferably 15.0 mm or less. preferable.
　波長変換部材の上記方法で測定される特定値を調整する方法は特に制限されず、例えば、波長変換層及び必要に応じて用いられる後述の被覆材の材質、厚み、弾性率、積層構造等を調整する方法が挙げられる。例えば、波長変換部材の厚みを小さくすることによって上記方法で測定される特定値が大きくなる傾向にある。また、被覆材を用いる場合には、被覆材の厚みを小さくすることによって上記方法で測定される特定値が大きくなる傾向にある。被覆材を多層構造とし、基材層に接着層を含めることによっても、上記方法で測定される特定値が大きくなる傾向にある。 The method of adjusting the specific value of the wavelength conversion member measured by the above method is not particularly limited, and for example, the material, thickness, elastic modulus, laminated structure, etc. of the wavelength conversion layer and the coating material to be used later, which will be used as necessary, are not particularly limited. There is a method of adjustment. For example, by reducing the thickness of the wavelength conversion member, the specific value measured by the above method tends to increase. Further, when a covering material is used, the specific value measured by the above method tends to increase by reducing the thickness of the covering material. Even if the covering material has a multi-layer structure and the base material layer includes an adhesive layer, the specific value measured by the above method tends to increase.
＜被覆材＞
　波長変換部材は、波長変換層の一方の面側又は両方の面側に配置される被覆材を有してもよい。 <Coating material>
The wavelength conversion member may have a covering material arranged on one surface side or both surface sides of the wavelength conversion layer.
　被覆材の平均厚みは、８μｍ以上であることが好ましく、１５μｍ以上であってもよく、２０μｍ以上であってもよい。被覆材の平均厚みが８μｍ以上であると、波長変換部材の取扱い性が向上し、バリア性等の機能が充分なものとなる傾向にある。また、被覆材の平均厚みは、１５０μｍ以下であることが好ましく、１００μｍ以下であることがより好ましく、８０μｍ以下であることがさらに好ましい。被覆材の平均厚みが１５０μｍ以下であると、光透過率の低下が抑えられる傾向にある。また、ロール化後の巻き戻しが容易となる傾向にある。以上の観点から、被覆材の平均厚みは、８μｍ～１５０μｍであることが好ましく、１５μｍ～１００μｍであることがより好ましく、２０μｍ～８０μｍであることがさらに好ましい。
　被覆材の平均厚みは、例えば、マイクロメータを用いて測定した任意の３箇所の厚みの算術平均値として求められる。 The average thickness of the covering material is preferably 8 μm or more, and may be 15 μm or more, or 20 μm or more. When the average thickness of the covering material is 8 μm or more, the handleability of the wavelength conversion member is improved, and the functions such as barrier property tend to be sufficient. The average thickness of the coating material is preferably 150 μm or less, more preferably 100 μm or less, and even more preferably 80 μm or less. When the average thickness of the covering material is 150 μm or less, the decrease in light transmittance tends to be suppressed. In addition, it tends to be easy to rewind after rolling. From the above viewpoint, the average thickness of the coating material is preferably 8 μm to 150 μm, more preferably 15 μm to 100 μm, and even more preferably 20 μm to 80 μm.
The average thickness of the covering material is obtained as, for example, an arithmetic mean value of the thicknesses of any three points measured using a micrometer.
　被覆材は粗面化されていてもよい。この場合、波長変換層の一方の面側に配置される被覆材の、波長変換層とは対向しない側の面、又は波長変換層の両方の面側に配置される被覆材の、波長変換層とは対向しない側の面の少なくとも一方が、粗面化されていてもよい。例えば、表面粗さＲａは、０．５μｍ以上であってもよい。波長変換部材が被覆材を有するとき、被覆材が粗面化されていると、画像変換部材の取扱い性に優れ、隣接する部材と波長変換部材が密着することによる干渉縞を抑制することができる傾向にある。 The covering material may be roughened. In this case, the wavelength conversion layer of the coating material arranged on one surface side of the wavelength conversion layer, the surface on the side not facing the wavelength conversion layer, or the coating material arranged on both surface sides of the wavelength conversion layer. At least one of the surfaces on the side not facing the surface may be roughened. For example, the surface roughness Ra may be 0.5 μm or more. When the wavelength conversion member has a covering material, if the covering material is roughened, the handling of the image conversion member is excellent, and interference fringes due to the adjacent member and the wavelength conversion member coming into close contact with each other can be suppressed. There is a tendency.
　被覆材の材質は特に制限されず、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）等のポリエステル、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）等のポリオレフィン、ナイロン等のポリアミド、エチレン－ビニルアルコール共重合体（ＥＶＯＨ）などであってもよい。入手容易性の観点からは、被覆材の材質はポリエチレンテレフタレートが好ましい。
　被覆材は、バリア機能を高めるためのバリア層を備えたもの（バリアフィルム）であってもよい。バリア層としては、アルミナ、シリカ等の無機物を含む無機層が挙げられる。 The material of the covering material is not particularly limited, and polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin such as polyethylene (PE) and polypropylene (PP), polyamide such as nylon, and ethylene-vinyl alcohol co-weight. It may be coalescence (EVOH) or the like. From the viewpoint of availability, polyethylene terephthalate is preferable as the material of the covering material.
The covering material may be one provided with a barrier layer for enhancing the barrier function (barrier film). Examples of the barrier layer include an inorganic layer containing an inorganic substance such as alumina and silica.
　被覆材は、蛍光体の発光効率の低下を抑える観点から、酸素及び水の少なくとも一方に対するバリア性を有することが好ましく、酸素及び水の両方に対するバリア性を有することがより好ましい。酸素及び水の少なくとも一方に対するバリア性を有する被覆材としては特に制限されず、無機層を有するバリアフィルム等を用いることができる。 The coating material preferably has a barrier property against at least one of oxygen and water, and more preferably has a barrier property against both oxygen and water, from the viewpoint of suppressing a decrease in the luminous efficiency of the phosphor. The coating material having a barrier property against at least one of oxygen and water is not particularly limited, and a barrier film having an inorganic layer or the like can be used.
　被覆材の酸素透過率は、例えば、０．５ｍＬ／（ｍ２・２４ｈ・ａｔｍ）以下であることが好ましく、０．３ｍＬ／（ｍ２・２４ｈ・ａｔｍ）以下であることがより好ましく、０．１ｍＬ／（ｍ２・２４ｈ・ａｔｍ）以下であることがさらに好ましい。被覆材の酸素透過率は、酸素透過率測定装置（例えば、ＭＯＣＯＮ社、ＯＸ－ＴＲＡＮ）を用いて、温度２３℃かつ相対湿度６５％の条件で測定することができる。 Oxygen permeability of the dressing, for example, is preferably 0.5mL / (m 2 · 24h · atm) or less, more preferably 0.3mL / (m 2 · 24h · atm) or less, 0 and more preferably .1mL / (m 2 · 24h · atm) or less. The oxygen permeability of the coating material can be measured using an oxygen permeability measuring device (for example, MOCON, OX-TRAN) under the conditions of a temperature of 23 ° C. and a relative humidity of 65%.
　また、被覆材の水蒸気透過率は、例えば、５×１０－２ｇ／（ｍ２・２４ｈ・Ｐａ）以下であることが好ましく、１×１０－２ｇ／（ｍ２・２４ｈ・Ｐａ）以下であることがより好ましく、５×１０－３ｇ／（ｍ２・２４ｈ・Ｐａ）以下であることがさらに好ましい。被覆材の水蒸気透過率は、水蒸気透過率測定装置（例えば、ＭＯＣＯＮ社、ＡＱＵＡＴＲＡＮ）を用いて、温度４０℃かつ相対湿度９０％の条件で測定することができる。 Further, the water vapor permeability of the dressing, for example, 5 × 10 -2 g / is preferably (m 2 · 24h · Pa) or less, 1 × 10 -2 g / ( m 2 · 24h · Pa) or less more preferably, even more preferably 5 × 10 -3 g / (m 2 · 24h · Pa) or less. The water vapor permeability of the coating material can be measured using a water vapor permeability measuring device (for example, MOCON, AQUATRAN) under the conditions of a temperature of 40 ° C. and a relative humidity of 90%.
　被覆材は、複数の層が積層されたものであってもよい。例えば、被覆材は、基材層、バリア層、プライマ層等が積層されたものであってもよい。 The covering material may be one in which a plurality of layers are laminated. For example, the covering material may be a laminated material such as a base material layer, a barrier layer, and a primer layer.
＜波長変換層＞
　本開示の波長変換部材は波長変換層を含む。波長変換層は、蛍光体を含む。波長変換層は、樹脂硬化物をさらに含んでもよく、蛍光体が樹脂硬化物に含まれた状態であってもよい。また、波長変換層は光拡散材をさらに含んでもよい。 <Wavelength conversion layer>
The wavelength conversion member of the present disclosure includes a wavelength conversion layer. The wavelength conversion layer contains a phosphor. The wavelength conversion layer may further contain a cured resin product, or may have a phosphor contained in the cured resin product. Further, the wavelength conversion layer may further contain a light diffusing material.
〔蛍光体〕
　波長変換層は、光源から光を照射されることで発光する蛍光体を含む。蛍光体の種類は特に限定されるものではなく、例えば、有機蛍光体及び無機蛍光体を挙げることができる。
　有機蛍光体としては、ナフタルイミド化合物、ペリレン化合物等が挙げられる。
　無機蛍光体としては、Ｙ３Ｏ３：Ｅｕ、ＹＶＯ４：Ｅｕ、Ｙ２Ｏ２：Ｅｕ、３．５ＭｇＯ・０．５ＭｇＦ２、ＧｅＯ２：Ｍｎ、（Ｙ・Ｃｄ）ＢＯ２：Ｅｕ等の赤色発光無機蛍光体、ＺｎＳ：Ｃｕ・Ａｌ、（Ｚｎ・Ｃｄ）Ｓ：Ｃｕ・Ａｌ、ＺｎＳ：Ｃｕ・Ａｕ・Ａｌ、Ｚｎ２ＳｉＯ４：Ｍｎ、ＺｎＳｉＯ４：Ｍｎ、ＺｎＳ：Ａｇ・Ｃｕ、（Ｚｎ・Ｃｄ）Ｓ：Ｃｕ、ＺｎＳ：Ｃｕ、ＧｄＯＳ：Ｔｂ、ＬａＯＳ：Ｔｂ、ＹＳｉＯ４：Ｃｅ・Ｔｂ、ＺｎＧｅＯ４：Ｍｎ、ＧｅＭｇＡｌＯ：Ｔｂ、ＳｒＧａＳ：Ｅｕ２＋、ＺｎＳ：Ｃｕ・Ｃｏ、ＭｇＯ・ｎＢ２Ｏ３：Ｇｅ・Ｔｂ、ＬａＯＢｒ：Ｔｂ・Ｔｍ、Ｌａ２Ｏ２Ｓ：Ｔｂ等の緑色発光無機蛍光体、ＺｎＳ：Ａｇ、ＧａＷＯ４、Ｙ２ＳｉＯ６：Ｃｅ、ＺｎＳ：Ａｇ・Ｇａ・Ｃｌ、Ｃａ２Ｂ４ＯＣｌ：Ｅｕ２＋、ＢａＭｇＡｌ４Ｏ３：Ｅｕ２＋等の青色発光無機蛍光体、量子ドット蛍光体などが挙げられる。 [Fluorescent material]
The wavelength conversion layer contains a phosphor that emits light when irradiated with light from a light source. The type of the phosphor is not particularly limited, and examples thereof include an organic phosphor and an inorganic phosphor.
Examples of the organic phosphor include a naphthalimide compound and a perylene compound.
Examples of the inorganic phosphor include Y 3 O 3 : Eu, YVO 4 : Eu, Y 2 O 2 : Eu, 3.5 MgO / 0.5 MgF 2 , GeO 2 : Mn, (Y · Cd) BO 2 : Eu, etc. Red light emitting inorganic phosphor, ZnS: Cu · Al, (Zn · Cd) S: Cu · Al, ZnS: Cu · Au · Al, Zn 2 SiO 4 : Mn, ZnSiO 4 : Mn, ZnS: Ag · Cu, ( Zn · Cd) S: Cu, ZnS: Cu, GdOS: Tb, LaOS: Tb, YSiO 4 : Ce · Tb, ZnGeO 4 : Mn, GeMgAlO: Tb, SrGaS: Eu 2+ , ZnS: Cu · Co, MgO · nB 2 O 3 : Green luminescent inorganic phosphors such as Ge · Tb, LaOBr: Tb · Tm, La 2 O 2 S: Tb, ZnS: Ag, GaWO 4 , Y 2 SiO 6 : Ce, ZnS: Ag · Ga · Cl , Ca 2 B 4 OCl: Eu 2+ , BaMgAl 4 O 3 : Eu 2+ and other blue light emitting inorganic phosphors, quantum dot phosphors and the like can be mentioned.
　蛍光体としては、画像表示装置の色再現性に優れる観点から、量子ドット蛍光体が好ましい。
　量子ドット蛍光体としては特に制限されず、ＩＩ－ＶＩ族化合物、ＩＩＩ－Ｖ族化合物、ＩＶ－ＶＩ族化合物、及びＩＶ族化合物からなる群より選択される少なくとも１種を含む粒子が挙げられる。発光効率の観点からは、量子ドット蛍光体は、Ｃｄ及びＩｎの少なくとも一方を含む化合物を含むことが好ましい。 As the phosphor, a quantum dot phosphor is preferable from the viewpoint of excellent color reproducibility of the image display device.
The quantum dot phosphor is not particularly limited, and examples thereof include particles containing at least one selected from the group consisting of a group II-VI compound, a group III-V compound, a group IV-VI compound, and a group IV compound. From the viewpoint of luminous efficiency, the quantum dot phosphor preferably contains a compound containing at least one of Cd and In.
　ＩＩ－ＶＩ族化合物の具体例としては、ＣｄＳｅ、ＣｄＴｅ、ＣｄＳ、ＺｎＳ、ＺｎＳｅ、ＺｎＴｅ、ＺｎＯ、ＨｇＳ、ＨｇＳｅ、ＨｇＴｅ、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等が挙げられる。
　ＩＩＩ－Ｖ族化合物の具体例としては、ＧａＮ、ＧａＰ、ＧａＡｓ、ＧａＳｂ、ＡｌＮ、ＡｌＰ、ＡｌＡｓ、ＡｌＳｂ、ＩｎＮ、ＩｎＰ、ＩｎＡｓ、ＩｎＳｂ、ＧａＮＰ、ＧａＮＡｓ、ＧａＮＳｂ、ＧａＰＡｓ、ＧａＰＳｂ、ＡｌＮＰ、ＡｌＮＡｓ、ＡｌＮＳｂ、ＡｌＰＡｓ、ＡｌＰＳｂ、ＩｎＮＰ、ＩｎＮＡｓ、ＩｎＮＳｂ、ＩｎＰＡｓ、ＩｎＰＳｂ、ＧａＡｌＮＰ、ＧａＡｌＮＡｓ、ＧａＡｌＮＳｂ、ＧａＡｌＰＡｓ、ＧａＡｌＰＳｂ、ＧａＩｎＮＰ、ＧａＩｎＮＡｓ、ＧａＩｎＮＳｂ、ＧａＩｎＰＡｓ、ＧａＩｎＰＳｂ、ＩｎＡｌＮＰ、ＩｎＡｌＮＡｓ、ＩｎＡｌＮＳｂ、ＩｎＡｌＰＡｓ、ＩｎＡｌＰＳｂ等が挙げられる。
　ＩＶ－ＶＩ族化合物の具体例としては、ＳｎＳ、ＳｎＳｅ、ＳｎＴｅ、ＰｂＳ、ＰｂＳｅ、ＰｂＴｅ、ＳｎＳｅＳ、ＳｎＳｅＴｅ、ＳｎＳＴｅ、ＰｂＳｅＳ、ＰｂＳｅＴｅ、ＰｂＳＴｅ、ＳｎＰｂＳ、ＳｎＰｂＳｅ、ＳｎＰｂＴｅ、ＳｎＰｂＳＳｅ、ＳｎＰｂＳｅＴｅ、ＳｎＰｂＳＴｅ等が挙げられる。
　ＩＶ族化合物の具体例としては、Ｓｉ、Ｇｅ、ＳｉＣ、ＳｉＧｅ等が挙げられる。 Specific examples of the II-VI group compounds include CdSe, CdTe, CdS, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSte, ZnSeS, ZnSeTe, ZnSte, HgSeS, ZnS. , CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSeTe
Specific examples of the Group III-V compounds include GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, COLP, GaNAs, PLACSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb. , AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInNSb, GaInPAs, GaInPSb, InNAAl
Specific examples of the IV-VI group compounds include SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSte, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbSe ..
Specific examples of the Group IV compound include Si, Ge, SiC, SiGe and the like.
　量子ドット蛍光体としては、コアシェル構造を有するものであってもよい。コアを構成する化合物のバンドギャップよりもシェルを構成する化合物のバンドギャップを広くすることで、量子ドット蛍光体の量子効率をより向上させることが可能となる。コア及びシェルの組み合わせ（コア／シェル）としては、ＣｄＳｅ／ＺｎＳ、ＩｎＰ／ＺｎＳ、ＰｂＳｅ／ＰｂＳ、ＣｄＳｅ／ＣｄＳ、ＣｄＴｅ／ＣｄＳ、ＣｄＴｅ／ＺｎＳ等が挙げられる。 The quantum dot phosphor may have a core-shell structure. By making the band gap of the compound constituting the shell wider than the band gap of the compound constituting the core, it is possible to further improve the quantum efficiency of the quantum dot phosphor. Examples of the combination of core and shell (core / shell) include CdSe / ZnS, InP / ZnS, PbSe / PbS, CdSe / CdS, CdTe / CdS, and CdTe / ZnS.
　また、量子ドット蛍光体としては、シェルが多層構造である、いわゆるコアマルチシェル構造を有するものであってもよい。バンドギャップの広いコアにバンドギャップの狭いシェルを１層又は２層以上積層し、さらにこのシェルの上にバンドギャップの広いシェルを積層することで、量子ドット蛍光体の量子効率をさらに向上させることが可能となる。 Further, the quantum dot phosphor may have a so-called core multi-shell structure in which the shell has a multi-layer structure. By stacking one or more layers of shells with a narrow bandgap on a core with a wide bandgap, and further stacking a shell with a wide bandgap on top of this shell, the quantum efficiency of the quantum dot phosphor can be further improved. Is possible.
　波長変換層が量子ドット蛍光体を含有する場合、波長変換層は、１種類の量子ドット蛍光体を単独で含有していてもよく、２種類以上の量子ドット蛍光体を組み合わせて含有していてもよい。２種類以上の量子ドット蛍光体を組み合わせて含有する態様としては、例えば、成分は異なるものの平均粒子径を同じくする量子ドット蛍光体を２種類以上含有する態様、平均粒子径は異なるものの成分を同じくする量子ドット蛍光体を２種類以上含有する態様、並びに成分及び平均粒子径の異なる量子ドット蛍光体を２種類以上含有する態様が挙げられる。量子ドット蛍光体の成分及び平均粒子径の少なくとも一方を変更することで、量子ドット蛍光体の発光中心波長を変更することができる。 When the wavelength conversion layer contains a quantum dot phosphor, the wavelength conversion layer may contain one kind of quantum dot phosphor alone, or may contain two or more kinds of quantum dot phosphors in combination. May be good. Examples of a mode in which two or more types of quantum dot phosphors are contained in combination include a mode in which two or more types of quantum dot phosphors having different components but the same average particle size are contained, and a mode in which the components are the same although the average particle size is different. Examples thereof include an embodiment containing two or more types of quantum dot phosphors, and an embodiment containing two or more types of quantum dot phosphors having different components and average particle diameters. The emission center wavelength of the quantum dot phosphor can be changed by changing at least one of the components of the quantum dot phosphor and the average particle size.
　例えば、波長変換層は、５２０ｎｍ～５６０ｎｍの緑色の波長域に発光中心波長を有する量子ドット蛍光体Ｇと、６００ｎｍ～６８０ｎｍの赤色の波長域に発光中心波長を有する量子ドット蛍光体Ｒとを含有していてもよい。量子ドット蛍光体Ｇと量子ドット蛍光体Ｒとを含有する波長変換層に対して４３０ｎｍ～４８０ｎｍの青色の波長域の励起光を照射すると、量子ドット蛍光体Ｇ及び量子ドット蛍光体Ｒからそれぞれ緑色光及び赤色光が発光される。その結果、量子ドット蛍光体Ｇ及び量子ドット蛍光体Ｒから発光される緑色光及び赤色光と、硬化物を透過する青色光とにより、白色光を得ることができる。 For example, the wavelength conversion layer contains a quantum dot phosphor G having an emission center wavelength in the green wavelength region of 520 nm to 560 nm and a quantum dot phosphor R having an emission center wavelength in the red wavelength region of 600 nm to 680 nm. You may be doing it. When the wavelength conversion layer containing the quantum dot phosphor G and the quantum dot phosphor R is irradiated with excitation light in the blue wavelength range of 430 nm to 480 nm, the quantum dot phosphor G and the quantum dot phosphor R are green, respectively. Light and red light are emitted. As a result, white light can be obtained by the green light and red light emitted from the quantum dot phosphor G and the quantum dot phosphor R and the blue light transmitted through the cured product.
　波長変換層中の蛍光体の含有率は、波長変換層全体に対して、例えば、０．０１質量％～１．０質量％であることが好ましく、０．０５質量％～０．５質量％であることがより好ましく、０．１質量％～０．５質量％であることがさらに好ましい。蛍光体の含有率が波長変換層全体に対して０．０１質量％以上であると、充分な波長変換機能が得られる傾向にあり、蛍光体の含有率が１．０質量％以下であると、蛍光体の凝集が抑えられる傾向にある。 The content of the phosphor in the wavelength conversion layer is preferably, for example, 0.01% by mass to 1.0% by mass, and 0.05% by mass to 0.5% by mass, based on the entire wavelength conversion layer. Is more preferable, and 0.1% by mass to 0.5% by mass is further preferable. When the content of the phosphor is 0.01% by mass or more with respect to the entire wavelength conversion layer, a sufficient wavelength conversion function tends to be obtained, and when the content of the phosphor is 1.0% by mass or less. , The aggregation of the phosphor tends to be suppressed.
〔樹脂硬化物〕
　波長変換層は、樹脂硬化物をさらに含んでもよい。波長変換層は、上述の蛍光体が樹脂硬化物に含まれた状態の層であってもよい。 [Resin cured product]
The wavelength conversion layer may further contain a cured resin product. The wavelength conversion layer may be a layer in which the above-mentioned phosphor is contained in the cured resin product.
　樹脂硬化物の他部材（被覆材等）に対する密着性、及び硬化時の体積収縮によるシワの発生の抑制の観点からは、樹脂硬化物はスルフィド構造を含有することが好ましい。スルフィド構造を含有する樹脂硬化物は、例えば、後述するチオール化合物と、当該チオール化合物のチオール基とエンチオール反応を生じる炭素炭素二重結合を有する重合性化合物と、を含む樹脂組成物を硬化させて得ることができる。 The cured resin product preferably contains a sulfide structure from the viewpoint of adhesion to other members (coating material, etc.) of the cured resin product and suppression of wrinkles due to volume shrinkage during curing. The cured resin composition containing a sulfide structure is obtained by curing a resin composition containing, for example, a thiol compound described later and a polymerizable compound having a carbon-carbon double bond that causes an enthiol reaction with a thiol group of the thiol compound. Obtainable.
　波長変換層の耐熱性及び耐湿熱性の観点からは、樹脂硬化物は脂環式構造又は芳香環構造を含有することが好ましい。脂環式構造又は芳香環構造を有する樹脂硬化物は、例えば、後述する重合性化合物として脂環式構造又は芳香環構造を有するものを含む樹脂組成物を硬化させて得ることができる。 From the viewpoint of heat resistance and moisture heat resistance of the wavelength conversion layer, the cured resin product preferably contains an alicyclic structure or an aromatic ring structure. The cured resin product having an alicyclic structure or an aromatic ring structure can be obtained, for example, by curing a resin composition containing a polymer compound having an alicyclic structure or an aromatic ring structure, which will be described later.
　蛍光体と酸素との接触を抑制する観点からは、樹脂硬化物はアルキレンオキシ基を含有することが好ましい。樹脂硬化物がアルキレンオキシ基を含有すると、樹脂硬化物の極性が増大し、非極性の酸素が硬化物中の成分に溶解しにくくなる傾向にある。また、樹脂硬化物の柔軟性が増して被覆材との密着性が向上する傾向にある。 From the viewpoint of suppressing contact between the phosphor and oxygen, the cured resin product preferably contains an alkyleneoxy group. When the cured resin product contains an alkyleneoxy group, the polarity of the cured resin product increases, and non-polar oxygen tends to be difficult to dissolve in the components in the cured product. In addition, the flexibility of the cured resin product tends to increase and the adhesion to the coating material tends to improve.
　アルキレンオキシ基を含有する樹脂硬化物は、例えば、後述する重合性化合物としてアルキレンオキシ基を有するものを含む樹脂組成物を硬化させて得ることができる。 The cured resin product containing an alkyleneoxy group can be obtained, for example, by curing a resin composition containing a polymerizable compound having an alkyleneoxy group, which will be described later.
－樹脂組成物－
　波長変換層は、蛍光体と、重合性化合物と、光重合開始剤と、を含む組成物（以下、単に樹脂組成物ともいう）の硬化物であってもよい。樹脂組成物は、蛍光体と、チオール化合物と、（メタ）アクリル化合物及び（メタ）アリル化合物からなる群より選択される少なくとも１種と、光重合開始剤と、を含有することが好ましい。樹脂組成物は、任意でその他の成分を含有していてもよい。
　以下、樹脂組成物の各成分について詳述する。 -Resin composition-
The wavelength conversion layer may be a cured product of a composition containing a phosphor, a polymerizable compound, and a photopolymerization initiator (hereinafter, also simply referred to as a resin composition). The resin composition preferably contains a phosphor, a thiol compound, at least one selected from the group consisting of a (meth) acrylic compound and a (meth) allyl compound, and a photopolymerization initiator. The resin composition may optionally contain other components.
Hereinafter, each component of the resin composition will be described in detail.
（蛍光体）
　樹脂組成物は、蛍光体を含有する。蛍光体の詳細は、上述のとおりである。 (Fluorescent material)
The resin composition contains a phosphor. The details of the phosphor are as described above.
　蛍光体として量子ドット蛍光体を用いる場合、量子ドット蛍光体は、分散媒体に分散された量子ドット蛍光体分散液の状態で用いてもよい。量子ドット蛍光体を分散する分散媒体としては、各種有機溶剤、シリコーン化合物、及び単官能（メタ）アクリレート化合物が挙げられる。量子ドット蛍光体は、必要に応じて分散剤を用いて量子ドット蛍光体分散液の状態で用いてもよい。 When a quantum dot phosphor is used as the phosphor, the quantum dot phosphor may be used in the state of a quantum dot phosphor dispersion liquid dispersed in a dispersion medium. Examples of the dispersion medium for dispersing the quantum dot phosphor include various organic solvents, silicone compounds, and monofunctional (meth) acrylate compounds. The quantum dot phosphor may be used in the state of a quantum dot phosphor dispersion liquid by using a dispersant, if necessary.
　分散媒体として使用可能な有機溶剤としては、量子ドット蛍光体の沈降及び凝集が確認されなければ特に限定されるものではなく、アセトニトリル、メタノール、エタノール、アセトン、１－プロパノール、酢酸エチル、酢酸ブチル、トルエン、ヘキサン等が挙げられる。 The organic solvent that can be used as the dispersion medium is not particularly limited unless precipitation and aggregation of the quantum dot phosphor are confirmed, and acetonitrile, methanol, ethanol, acetone, 1-propanol, ethyl acetate, butyl acetate, etc. Examples thereof include toluene and hexane.
　分散媒体として使用可能なシリコーン化合物としては、ジメチルシリコーンオイル、メチルフェニルシリコーンオイル、メチルハイドロジェンシリコーンオイル等のストレートシリコーンオイル；アミノ変性シリコーンオイル、エポキシ変性シリコーンオイル、カルボキシ変性シリコーンオイル、カルビノール変性シリコーンオイル、メルカプト変性シリコーンオイル、異種官能基変性シリコーンオイル、ポリエーテル変性シリコーンオイル、メチルスチリル変性シリコーンオイル、親水性特殊変性シリコーンオイル、高級アルコキシ変性シリコーンオイル、高級脂肪酸変性シリコーンオイル、フッ素変性シリコーンオイル等の変性シリコーンオイルなどが挙げられる。 Silicone compounds that can be used as a dispersion medium include straight silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil; amino-modified silicone oil, epoxy-modified silicone oil, carboxy-modified silicone oil, and carbinol-modified silicone. Oil, mercapto-modified silicone oil, heterogeneous functional group-modified silicone oil, polyether-modified silicone oil, methylstyryl-modified silicone oil, hydrophilic special-modified silicone oil, higher alkoxy-modified silicone oil, higher fatty acid-modified silicone oil, fluorine-modified silicone oil, etc. Modified silicone oil and the like.
　分散媒体として使用可能な単官能（メタ）アクリレート化合物としては、室温（２５℃）において液体であれば特に限定されるものではなく、脂環式構造を有する単官能（メタ）アクリレート化合物（好ましくはイソボルニル（メタ）アクリレート、及びジシクロペンタニル（メタ）アクリレート）、メトキシポリエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、エトキシ化ｏ－フェニルフェノール（メタ）アクリレート等が挙げられる。 The monofunctional (meth) acrylate compound that can be used as a dispersion medium is not particularly limited as long as it is liquid at room temperature (25 ° C.), and is a monofunctional (meth) acrylate compound having an alicyclic structure (preferably). Isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate), methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, ethoxylated o-phenylphenol (meth) acrylate and the like can be mentioned.
　必要に応じて用いられる分散剤としては、ポリエーテルアミン（ＪＥＦＦＡＭＩＮＥ　Ｍ－１０００、ＨＵＮＴＳＭＡＮ社）等が挙げられる。 Examples of the dispersant used as needed include polyetheramine (JEFFAMINE M-1000, HUNTSMAN) and the like.
　量子ドット蛍光体分散液に占める量子ドット蛍光体の質量基準の割合は、１質量％～２０質量％であることが好ましく、１質量％～１０質量％であることがより好ましい。 The mass-based ratio of the quantum dot phosphor to the quantum dot phosphor dispersion liquid is preferably 1% by mass to 20% by mass, and more preferably 1% by mass to 10% by mass.
　樹脂組成物中の量子ドット蛍光体分散液の含有率は、量子ドット蛍光体分散液に占める量子ドット蛍光体の質量基準の割合が１質量％～２０質量％である場合、樹脂組成物の全量に対して、例えば、１質量％～１０質量％であることが好ましい。
　また、樹脂組成物中の量子ドット蛍光体の含有率は、樹脂組成物の全量に対して、例えば、０．０１質量％～１．０質量％であることが好ましく、０．０５質量％～０．５質量％であることがより好ましく、０．１質量％～０．５質量％であることがさらに好ましい。量子ドット蛍光体の含有率が０．０１質量％以上であると、硬化物に励起光を照射する際に充分な発光強度が得られる傾向にあり、量子ドット蛍光体の含有率が１．０質量％以下であると、量子ドット蛍光体の凝集が抑えられる傾向にある。 The content of the quantum dot phosphor dispersion liquid in the resin composition is the total amount of the resin composition when the mass-based ratio of the quantum dot phosphor to the quantum dot phosphor dispersion liquid is 1% by mass to 20% by mass. On the other hand, for example, it is preferably 1% by mass to 10% by mass.
The content of the quantum dot phosphor in the resin composition is preferably, for example, 0.01% by mass to 1.0% by mass, preferably 0.05% by mass or more, based on the total amount of the resin composition. It is more preferably 0.5% by mass, and even more preferably 0.1% by mass to 0.5% by mass. When the content of the quantum dot phosphor is 0.01% by mass or more, sufficient emission intensity tends to be obtained when the cured product is irradiated with excitation light, and the content of the quantum dot phosphor is 1.0. When it is mass% or less, the aggregation of the quantum dot phosphor tends to be suppressed.
（重合性化合物）
　樹脂組成物は、重合性化合物を含有する。樹脂組成物に含まれる重合性化合物は特に制限されず、チオール化合物、（メタ）アクリル化合物、（メタ）アリル化合物等が挙げられる。なお、（メタ）アリル化合物は、分子中に（メタ）アリル基を有する化合物を意味し、（メタ）アクリル化合物は、分子中に（メタ）アクリロイル基を有する化合物を意味する。分子中に（メタ）アリル基及び（メタ）アクリロイル基の両方を有する化合物は、便宜上、（メタ）アリル化合物に分類するものとする。 (Polymerizable compound)
The resin composition contains a polymerizable compound. The polymerizable compound contained in the resin composition is not particularly limited, and examples thereof include a thiol compound, a (meth) acrylic compound, and a (meth) allyl compound. The (meth) allyl compound means a compound having a (meth) allyl group in the molecule, and the (meth) acrylic compound means a compound having a (meth) acryloyl group in the molecule. Compounds having both a (meth) allyl group and a (meth) acryloyl group in the molecule shall be classified as (meth) allyl compounds for convenience.
　波長変換層の他部材（被覆材等）に対する密着性の観点からは、樹脂組成物は重合性化合物としてチオール化合物と、（メタ）アクリル化合物及び（メタ）アリル化合物からなる群より選択される少なくとも１種と、を含むことが好ましい。 From the viewpoint of adhesion of the wavelength conversion layer to other members (coating material, etc.), the resin composition is selected from the group consisting of a thiol compound, a (meth) acrylic compound and a (meth) allyl compound as a polymerizable compound at least. It is preferable to include one kind.
　重合性化合物としてチオール化合物と、（メタ）アクリル化合物及び（メタ）アリル化合物からなる群より選択される少なくとも１種と、を含む樹脂組成物を硬化して得られる硬化物は、チオール基と（メタ）アクリロイル基又は（メタ）アリル基の炭素炭素二重結合との間でエンチオール反応が進行して形成されるスルフィド構造（Ｒ－Ｓ－Ｒ’、Ｒ及びＲ’は有機基を表す）を含む。これにより、波長変換層と被覆材との密着性が向上する傾向にある。また、波長変換層の光学特性がより向上する傾向にある。
　以下、チオール化合物、（メタ）アクリル化合物、及び（メタ）アリル化合物について詳述する。 A cured product obtained by curing a resin composition containing a thiol compound as a polymerizable compound and at least one selected from the group consisting of a (meth) acrylic compound and a (meth) allyl compound has a thiol group and ( A sulfide structure (RSR', R and R'represents an organic group) formed by an enthiol reaction with a carbon-carbon double bond of a (meth) acryloyl group or a (meth) allyl group. include. As a result, the adhesion between the wavelength conversion layer and the coating material tends to be improved. Further, the optical characteristics of the wavelength conversion layer tend to be further improved.
Hereinafter, the thiol compound, the (meth) acrylic compound, and the (meth) allyl compound will be described in detail.
Ａ．チオール化合物
　チオール化合物は、１分子中に１個のチオール基を有する単官能チオール化合物であってもよく、１分子中に２個以上のチオール基を有する多官能チオール化合物であってもよい。樹脂組成物に含まれるチオール化合物は、１種のみでも２種以上であってもよい。 A. Thiol compound The thiol compound may be a monofunctional thiol compound having one thiol group in one molecule, or a polyfunctional thiol compound having two or more thiol groups in one molecule. The thiol compound contained in the resin composition may be only one kind or two or more kinds.
　チオール化合物は、分子中にチオール基以外の重合性基（例えば、（メタ）アクリロイル基、（メタ）アリル基）を有していても、有していなくてもよい。
　本開示において分子中にチオール基と、チオール基以外の重合性基を含む化合物は、「チオール化合物」に分類するものとする。 The thiol compound may or may not have a polymerizable group other than the thiol group (for example, (meth) acryloyl group, (meth) allyl group) in the molecule.
In the present disclosure, a compound containing a thiol group and a polymerizable group other than the thiol group in the molecule shall be classified as a "thiol compound".
　単官能チオール化合物の具体例としては、ヘキサンチオール、１－ヘプタンチオール、１－オクタンチオール、１－ノナンチオール、１－デカンチオール、３－メルカプトプロピオン酸、メルカプトプロピオン酸メチル、メルカプトプロピオン酸メトキシブチル、メルカプトプロピオン酸オクチル、メルカプトプロピオン酸トリデシル、２－エチルヘキシル－３－メルカプトプロピオネート、ｎ－オクチル－３－メルカプトプロピオネート等が挙げられる。 Specific examples of the monofunctional thiol compound include hexanethiol, 1-heptanethiol, 1-octanethiol, 1-nonanthiol, 1-decanethiol, 3-mercaptopropionic acid, methyl mercaptopropionate, methoxybutyl mercaptopropionate, and the like. Examples thereof include octyl mercaptopropionate, tridecyl mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate and the like.
　多官能チオール化合物の具体例としては、エチレングリコールビス（３－メルカプトプロピオネート）、ジエチレングリコールビス（３－メルカプトプロピオネート）、テトラエチレングリコールビス（３－メルカプトプロピオネート）、１，２－プロピレングリコールビス（３－メルカプトプロピオネート）、ジエチレングリコールビス（３－メルカプトブチレート）、１，４－ブタンジオールビス（３－メルカプトプロピオネート）、１，４－ブタンジオールビス（３－メルカプトブチレート）、１，８－オクタンジオールビス（３－メルカプトプロピオネート）、１，８－オクタンジオールビス（３－メルカプトブチレート）、ヘキサンジオールビスチオグリコレート、トリメチロールプロパントリス（３－メルカプトプロピオネート）、トリメチロールプロパントリス（３－メルカプトブチレート）、トリメチロールプロパントリス（３－メルカプトイソブチレート）、トリメチロールプロパントリス（２－メルカプトイソブチレート）、トリメチロールプロパントリスチオグリコレート、トリス－［（３－メルカプトプロピオニルオキシ）－エチル］－イソシアヌレート、トリメチロールエタントリス（３－メルカプトブチレート）、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、ペンタエリスリトールテトラキス（３－メルカプトイソブチレート）、ペンタエリスリトールテトラキス（２－メルカプトイソブチレート）、ジペンタエリスリトールヘキサキス（３－メルカプトプロピオネート）、ジペンタエリスリトールヘキサキス（２－メルカプトプロピオネート）、ジペンタエリスリトールヘキサキス（３－メルカプトブチレート）、ジペンタエリスリトールヘキサキス（３－メルカプトイソブチレート）、ジペンタエリスリトールヘキサキス（２－メルカプトイソブチレート）、ペンタエリスリトールテトラキスチオグリコレート、ジペンタエリスリトールヘキサキスチオグリコレート等が挙げられる。 Specific examples of the polyfunctional thiol compound include ethylene glycol bis (3-mercaptopropionate), diethylene glycol bis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), 1,2-. Propropylene glycol bis (3-mercaptopropionate), diethylene glycol bis (3-mercaptobutyrate), 1,4-butanediol bis (3-mercaptopropionate), 1,4-butanediol bis (3-mercaptobutyrate) Rate), 1,8-octanediol bis (3-mercaptopropionate), 1,8-octanediol bis (3-mercaptobutyrate), hexanediol bisthioglycolate, trimethylolpropanthris (3-mercaptopro) Pionate), trimethylolpropanetris (3-mercaptobutyrate), trimethylolpropanetris (3-mercaptoisobutyrate), trimethylolpropanetris (2-mercaptoisobutyrate), trimethylolpropanetristhioglycolate, Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, trimethyl ethanetris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate) ), Pentaerythritol tetrakis (3-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol hexakis (2-mercaptopro) Pionate), dipentaerythritol hexakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptoisobutyrate), dipentaerythritol hexakis (2-mercaptoisobutyrate), pentaerythritol tetrakisthioglycol Rate, dipentaerythritol hexaxthioglycolate and the like can be mentioned.
　波長変換層と被覆材との密着性、耐熱性、及び耐湿熱性をより向上させる観点からは、チオール化合物は、多官能チオール化合物を含むことが好ましい。チオール化合物の全量に対する多官能チオール化合物の割合は、例えば、８０質量％以上であることが好ましく、９０質量％以上であることがより好ましく、１００質量％であることがさらに好ましい。 From the viewpoint of further improving the adhesion between the wavelength conversion layer and the coating material, heat resistance, and moist heat resistance, the thiol compound preferably contains a polyfunctional thiol compound. The ratio of the polyfunctional thiol compound to the total amount of the thiol compound is, for example, preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 100% by mass.
　チオール化合物は、（メタ）アクリル化合物と反応したチオエーテルオリゴマーの状態であってもよい。チオエーテルオリゴマーは、チオール化合物と（メタ）アクリル化合物とを重合開始剤の存在下で付加重合させることにより得ることができる。 The thiol compound may be in the state of a thioether oligomer that has reacted with the (meth) acrylic compound. The thioether oligomer can be obtained by addition polymerization of a thiol compound and a (meth) acrylic compound in the presence of a polymerization initiator.
　樹脂組成物がチオール化合物を含有する場合、樹脂組成物中のチオール化合物の含有率は、樹脂組成物の全量に対して、例えば、５質量％～８０質量％であることが好ましく、１５質量％～７０質量％であることがより好ましく、１８質量％～６０質量％であることがさらに好ましい。
　チオール化合物の含有率が５質量％以上であると、波長変換層の被覆材との密着性がより向上する傾向にあり、チオール化合物の含有率が８０質量％以下であると、波長変換層の耐熱性及び耐湿熱性がより向上する傾向にある。 When the resin composition contains a thiol compound, the content of the thiol compound in the resin composition is preferably, for example, 5% by mass to 80% by mass, and 15% by mass, based on the total amount of the resin composition. It is more preferably to 70% by mass, and further preferably 18% by mass to 60% by mass.
When the content of the thiol compound is 5% by mass or more, the adhesion of the wavelength conversion layer to the coating material tends to be further improved, and when the content of the thiol compound is 80% by mass or less, the wavelength conversion layer of the wavelength conversion layer tends to have better adhesion. Heat resistance and moisture heat resistance tend to be further improved.
Ｂ．（メタ）アクリル化合物
　（メタ）アクリル化合物は、１分子中に１個の（メタ）アクリロイル基を有する単官能（メタ）アクリル化合物であってもよく、１分子中に２個以上の（メタ）アクリロイル基を有する多官能（メタ）アクリル化合物であってもよい。樹脂組成物に含まれる（メタ）アクリル化合物は、１種でも２種以上であってもよい。 B. (Meta) Acrylic Compound The (meth) acrylic compound may be a monofunctional (meth) acrylic compound having one (meth) acryloyl group in one molecule, and two or more (meth) acrylic compounds in one molecule. It may be a polyfunctional (meth) acrylic compound having an acryloyl group. The (meth) acrylic compound contained in the resin composition may be one kind or two or more kinds.
　単官能（メタ）アクリル化合物の具体例としては、（メタ）アクリル酸；メチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソノニル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート等のアルキル基の炭素数が１～１８であるアルキル（メタ）アクリレート；ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート等の芳香環を有する（メタ）アクリレート化合物；ブトキシエチル（メタ）アクリレート等のアルコキシアルキル（メタ）アクリレート；Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート等のアミノアルキル（メタ）アクリレート；ジエチレングリコールモノエチルエーテル（メタ）アクリレート、トリエチレングリコールモノブチルエーテル（メタ）アクリレート、テトラエチレングリコールモノメチルエーテル（メタ）アクリレート、ヘキサエチレングリコールモノメチルエーテル（メタ）アクリレート、オクタエチレングリコールモノメチルエーテル（メタ）アクリレート、ノナエチレングリコールモノメチルエーテル（メタ）アクリレート、ジプロピレングリコールモノメチルエーテル（メタ）アクリレート、ヘプタプロピレングリコールモノメチルエーテル（メタ）アクリレート、テトラエチレングリコールモノエチルエーテル（メタ）アクリレート等のポリアルキレングリコールモノアルキルエーテル（メタ）アクリレート；ヘキサエチレングリコールモノフェニルエーテル（メタ）アクリレート等のポリアルキレングリコールモノアリールエーテル（メタ）アクリレート；シクロヘキシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、メチレンオキシド付加シクロデカトリエン（メタ）アクリレート等の脂環構造を有する（メタ）アクリレート化合物；（メタ）アクリロイルモルホリン、テトラヒドロフルフリル（メタ）アクリレート等の複素環を有する（メタ）アクリレート化合物；ヘプタデカフルオロデシル（メタ）アクリレート等のフッ化アルキル（メタ）アクリレート；２－ヒドロキシエチル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、トリエチレングリコールモノ（メタ）アクリレート、テトラエチレングリコールモノ（メタ）アクリレート、ヘキサエチレングリコールモノ（メタ）アクリレート、オクタプロピレングリコールモノ（メタ）アクリレート等の水酸基を有する（メタ）アクリレート化合物；グリシジル（メタ）アクリレート等のグリシジル基を有する（メタ）アクリレート化合物；２－（２－（メタ）アクリロイルオキシエチルオキシ）エチルイソシアネート、２－（メタ）アクリロイルオキシエチルイソシアネート等のイソシアネート基を有する（メタ）アクリレート化合物；テトラエチレングリコールモノ（メタ）アクリレート、ヘキサエチレングリコールモノ（メタ）アクリレート、オクタプロピレングリコールモノ（メタ）アクリレート等のポリアルキレングリコールモノ（メタ）アクリレート；（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ－イソプロピル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、２－ヒドロキシエチル（メタ）アクリルアミド等の（メタ）アクリルアミド化合物などが挙げられる。 Specific examples of the monofunctional (meth) acrylic compound include (meth) acrylic acid; methyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and isononyl (meth). ) Alkyl (meth) acrylate having an alkyl group having 1 to 18 carbon atoms such as acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate; benzyl (meth) acrylate, phenoxyethyl ( A (meth) acrylate compound having an aromatic ring such as a meta) acrylate; an alkoxyalkyl (meth) acrylate such as butoxyethyl (meth) acrylate; an aminoalkyl (meth) acrylate such as N, N-dimethylaminoethyl (meth) acrylate; Diethylene glycol monoethyl ether (meth) acrylate, triethylene glycol monobutyl ether (meth) acrylate, tetraethylene glycol monomethyl ether (meth) acrylate, hexaethylene glycol monomethyl ether (meth) acrylate, octaethylene glycol monomethyl ether (meth) acrylate, nona Polyalkylene glycol monoalkyl ether (meth) such as ethylene glycol monomethyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, heptapropylene glycol monomethyl ether (meth) acrylate, and tetraethylene glycol monoethyl ether (meth) acrylate. Acrylate: Polyalkylene glycol monoaryl ether (meth) acrylate such as hexaethylene glycol monophenyl ether (meth) acrylate; cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, methylene oxide-added cyclo (Meta) acrylate compound having an alicyclic structure such as decatorien (meth) acrylate; (meth) acrylate compound having a heterocycle such as (meth) acryloylmorpholine and tetrahydrofurfuryl (meth) acrylate; heptadecafluorodecyl (meth) ) Alkyl fluoride (meth) acrylates such as acrylates; 2-hydroxyethyl (meth) acrylates, 3-hydroxypropyl (meth) acrylates, 4-hydroxybutyl (meth) acrylates, trietylene Nglycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate and other (meth) acrylate compounds having hydroxyl groups; glycidyl (meth) acrylate A (meth) acrylate compound having a glycidyl group such as 2- (2- (meth) acryloyloxyethyloxy) ethyl isocyanate, a (meth) acrylate compound having an isocyanate group such as 2- (meth) acryloyloxyethyl isocyanate; tetra Polyalkylene glycol mono (meth) acrylates such as ethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide. , N-Isopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide and other (meth) acrylamide compounds. ..
　多官能（メタ）アクリル化合物の具体例としては、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート等のアルキレングリコールジ（メタ）アクリレート；ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート等のポリアルキレングリコールジ（メタ）アクリレート；トリメチロールプロパントリ（メタ）アクリレート、エチレンオキシド付加トリメチロールプロパントリ（メタ）アクリレート、トリス（２－アクリロイルオキシエチル）イソシアヌレート等のトリ（メタ）アクリレート化合物；エチレンオキシド付加ペンタエリスリトールテトラ（メタ）アクリレート、トリメチロールプロパンテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート等のテトラ（メタ）アクリレート化合物；トリシクロデカンジメタノールジ（メタ）アクリレート、シクロヘキサンジメタノールジ（メタ）アクリレート、１，３－アダマンタンジメタノールジ（メタ）アクリレート、水添ビスフェノールＡ（ポリ）エトキシジ（メタ）アクリレート、水添ビスフェノールＡ（ポリ）プロポキシジ（メタ）アクリレート、水添ビスフェノールＦ（ポリ）エトキシジ（メタ）アクリレート、水添ビスフェノールＦ（ポリ）プロポキシジ（メタ）アクリレート、水添ビスフェノールＳ（ポリ）エトキシジ（メタ）アクリレート、水添ビスフェノールＳ（ポリ）プロポキシジ（メタ）アクリレート等の脂環構造を有する（メタ）アクリレート化合物などが挙げられる。 Specific examples of the polyfunctional (meth) acrylic compound include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol di (meth) acrylate. Polyalkylene glycol di (meth) acrylate; Polyalkylene glycol di (meth) acrylate such as polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate; Trimethylol propantri (meth) acrylate, Trimethylol propantri with ethylene oxide (meth) Tri (meth) acrylate compounds such as meth) acrylate and tris (2-acryloyloxyethyl) isocyanurate; ethylene oxide-added pentaerythritol tetra (meth) acrylate, trimethylolpropanetetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like. Tetra (meth) acrylate compounds; tricyclodecanedimethanol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, 1,3-adamantan dimethanol di (meth) acrylate, hydrogenated bisphenol A (poly) ethoxydi ( Meta) acrylate, hydrogenated bisphenol A (poly) propoxydi (meth) acrylate, hydrogenated bisphenol F (poly) ethoxydi (meth) acrylate, hydrogenated bisphenol F (poly) propoxydi (meth) acrylate, hydrogenated bisphenol S (poly) Examples thereof include (meth) acrylate compounds having an alicyclic structure such as ethoxydi (meth) acrylate and hydrogenated bisphenol S (poly) propoxydi (meth) acrylate.
　（メタ）アクリル化合物は、硬化物の耐熱性及び耐湿熱性をより向上させる観点からは、脂環構造又は芳香環構造を有する（メタ）アクリレート化合物が好ましい。脂環構造又は芳香環構造としては、イソボルニル骨格、トリシクロデカン骨格、ビスフェノール骨格等が挙げられる。 The (meth) acrylic compound is preferably a (meth) acrylate compound having an alicyclic structure or an aromatic ring structure from the viewpoint of further improving the heat resistance and moisture heat resistance of the cured product. Examples of the alicyclic structure or aromatic ring structure include an isobornyl skeleton, a tricyclodecane skeleton, and a bisphenol skeleton.
　（メタ）アクリル化合物は、アルキレンオキシ基を有するものであってもよく、アルキレンオキシ基を有する２官能（メタ）アクリル化合物であってもよい。 The (meth) acrylic compound may have an alkyleneoxy group or may be a bifunctional (meth) acrylic compound having an alkyleneoxy group.
　アルキレンオキシ基としては、例えば、炭素数が２～４のアルキレンオキシ基が好ましく、炭素数が２又は３のアルキレンオキシ基がより好ましく、炭素数が２のアルキレンオキシ基がさらに好ましい。
　（メタ）アクリル化合物が有するアルキレンオキシ基は、１種でも２種以上であってもよい。 As the alkyleneoxy group, for example, an alkyleneoxy group having 2 to 4 carbon atoms is preferable, an alkyleneoxy group having 2 or 3 carbon atoms is more preferable, and an alkyleneoxy group having 2 carbon atoms is further preferable.
The (meth) acrylic compound may have one type or two or more types of alkyleneoxy groups.
　アルキレンオキシ基含有化合物は、複数個のアルキレンオキシ基を含むポリアルキレンオキシ基を有するポリアルキレンオキシ基含有化合物であってもよい。 The alkyleneoxy group-containing compound may be a polyalkyleneoxy group-containing compound having a polyalkyleneoxy group containing a plurality of alkyleneoxy groups.
　（メタ）アクリル化合物がアルキレンオキシ基を有する場合、一分子中のアルキレンオキシ基の数は、２個～３０個であることが好ましく、２個～２０個であることがより好ましく、３個～１０個であることがさらに好ましく、３個～５個であることが特に好ましい。 When the (meth) acrylic compound has an alkyleneoxy group, the number of alkyleneoxy groups in one molecule is preferably 2 to 30, more preferably 2 to 20, and 3 to 20. It is more preferably 10 pieces, and particularly preferably 3 to 5 pieces.
　（メタ）アクリル化合物がアルキレンオキシ基を有する場合、ビスフェノール構造を有することが好ましい。これにより、硬化物の耐熱性により優れる傾向にある。ビスフェノール構造としては、例えば、ビスフェノールＡ構造及びビスフェノールＦ構造が挙げられ、中でも、ビスフェノールＡ構造が好ましい。 When the (meth) acrylic compound has an alkyleneoxy group, it preferably has a bisphenol structure. As a result, the heat resistance of the cured product tends to be superior. Examples of the bisphenol structure include a bisphenol A structure and a bisphenol F structure, and among them, the bisphenol A structure is preferable.
　アルキレンオキシ基を有する（メタ）アクリル化合物の具体例としては、ブトキシエチル（メタ）アクリレート等のアルコキシアルキル（メタ）アクリレート；ジエチレングリコールモノエチルエーテル（メタ）アクリレート、トリエチレングリコールモノブチルエーテル（メタ）アクリレート、テトラエチレングリコールモノメチルエーテル（メタ）アクリレート、ヘキサエチレングリコールモノメチルエーテル（メタ）アクリレート、オクタエチレングリコールモノメチルエーテル（メタ）アクリレート、ノナエチレングリコールモノメチルエーテル（メタ）アクリレート、ジプロピレングリコールモノメチルエーテル（メタ）アクリレート、ヘプタプロピレングリコールモノメチルエーテル（メタ）アクリレート、テトラエチレングリコールモノエチルエーテル（メタ）アクリレート等のポリアルキレングリコールモノアルキルエーテル（メタ）アクリレート；ヘキサエチレングリコールモノフェニルエーテル（メタ）アクリレート等のポリアルキレングリコールモノアリールエーテル（メタ）アクリレート；テトラヒドロフルフリル（メタ）アクリレート等の複素環を有する（メタ）アクリレート化合物；トリエチレングリコールモノ（メタ）アクリレート、テトラエチレングリコールモノ（メタ）アクリレート、ヘキサエチレングリコールモノ（メタ）アクリレート、オクタプロピレングリコールモノ（メタ）アクリレート等の水酸基を有する（メタ）アクリレート化合物；グリシジル（メタ）アクリレート等のグリシジル基を有する（メタ）アクリレート化合物；ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート等のポリアルキレングリコールジ（メタ）アクリレート；エチレンオキシド付加トリメチロールプロパントリ（メタ）アクリレート等のトリ（メタ）アクリレート化合物；エチレンオキシド付加ペンタエリスリトールテトラ（メタ）アクリレート等のテトラ（メタ）アクリレート化合物；エトキシ化ビスフェノールＡ型ジ（メタ）アクリレート、プロポキシ化ビスフェノールＡ型ジ（メタ）アクリレート、プロポキシ化エトキシ化ビスフェノールＡ型ジ（メタ）アクリレート等のビスフェノール型ジ（メタ）アクリレート化合物などが挙げられる。
　アルキレンオキシ基含有化合物としては、中でも、エトキシ化ビスフェノールＡ型ジ（メタ）アクリレート、プロポキシ化ビスフェノールＡ型ジ（メタ）アクリレート及びプロポキシ化エトキシ化ビスフェノールＡ型ジ（メタ）アクリレートが好ましく、エトキシ化ビスフェノールＡ型ジ（メタ）アクリレートがより好ましい。 Specific examples of the (meth) acrylic compound having an alkyleneoxy group include alkoxyalkyl (meth) acrylates such as butoxyethyl (meth) acrylates; diethylene glycol monoethyl ether (meth) acrylates, triethylene glycol monobutyl ether (meth) acrylates, and the like. Tetraethylene glycol monomethyl ether (meth) acrylate, hexaethylene glycol monomethyl ether (meth) acrylate, octaethylene glycol monomethyl ether (meth) acrylate, nonaethylene glycol monomethyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, Polyalkylene glycol monoalkyl ether (meth) acrylates such as heptapropylene glycol monomethyl ether (meth) acrylates and tetraethylene glycol monoethyl ether (meth) acrylates; polyalkylene glycol monoaryls such as hexaethylene glycol monophenyl ether (meth) acrylates. Ether (meth) acrylate; (meth) acrylate compound having a heterocycle such as tetrahydrofurfuryl (meth) acrylate; triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) (Meta) acrylate compound having a hydroxyl group such as acrylate and octapropylene glycol mono (meth) acrylate; (meth) acrylate compound having a glycidyl group such as glycidyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di ( Polyalkylene glycol di (meth) acrylates such as meta) acrylates; tri (meth) acrylate compounds such as ethylene oxide-added trimethylol propantri (meth) acrylates; tetra (meth) acrylate compounds such as ethylene oxide-added pentaerythritol tetra (meth) acrylates. Examples thereof include bisphenol-type di (meth) acrylate compounds such as ethoxylated bisphenol A-type di (meth) acrylate, propoxylated bisphenol A-type di (meth) acrylate, and propoxylated ethoxylated bisphenol A-type di (meth) acrylate.
As the alkyleneoxy group-containing compound, ethoxylated bisphenol A type di (meth) acrylate, propoxylated bisphenol A type di (meth) acrylate and propoxylated ethoxylated bisphenol A type di (meth) acrylate are preferable, and ethoxylated bisphenol A-type di (meth) acrylate is more preferable.
　樹脂組成物が（メタ）アクリル化合物を含有する場合、樹脂組成物中の（メタ）アクリル化合物の含有率は、樹脂組成物の全量に対して、例えば、４０質量％～９０質量％であってもよく、５０質量％～８０質量％であってもよい。 When the resin composition contains a (meth) acrylic compound, the content of the (meth) acrylic compound in the resin composition is, for example, 40% by mass to 90% by mass with respect to the total amount of the resin composition. It may be 50% by mass to 80% by mass.
Ｃ．（メタ）アリル化合物
　（メタ）アリル化合物は、１分子中に１個の（メタ）アリル基を有する単官能（メタ）アリル化合物であってもよく、１分子中に２個以上の（メタ）アリル基を有する多官能（メタ）アリル化合物であってもよい。樹脂組成物に含まれる（メタ）アリル化合物は、１種のみでも２種以上であってもよい。 C. (Meta) Allyl Compound The (meth) allyl compound may be a monofunctional (meth) allyl compound having one (meth) allyl group in one molecule, and two or more (meth) allyl compounds in one molecule. It may be a polyfunctional (meth) allyl compound having an allyl group. The (meth) allyl compound contained in the resin composition may be only one kind or two or more kinds.
　（メタ）アリル化合物は、分子中に（メタ）アリル基以外の重合性基（例えば、（メタ）アクリロイル基）を有していても、有していなくてもよい。
　本開示において分子中に（メタ）アリル基以外の重合性基を有する（メタ）アリル化合物（ただし、チオール化合物を除く）は、「（メタ）アリル化合物」に分類するものとする。 The (meth) allyl compound may or may not have a polymerizable group (for example, (meth) acryloyl group) other than the (meth) allyl group in the molecule.
In the present disclosure, a (meth) allyl compound (excluding a thiol compound) having a polymerizable group other than the (meth) allyl group in the molecule shall be classified as a "(meth) allyl compound".
　単官能（メタ）アリル化合物の具体例としては、（メタ）アリルアセテート、（メタ）アリルｎ－プロピオネート、（メタ）アリルベンゾエート、（メタ）アリルフェニルアセテート、（メタ）アリルフェノキシアセテート、（メタ）アリルメチルエーテル、（メタ）アリルグリシジルエーテル等が挙げられる。 Specific examples of the monofunctional (meth) allyl compound include (meth) allyl acetate, (meth) allyl n-propionate, (meth) allyl benzoate, (meth) allyl phenyl acetate, (meth) allyl phenoxy acetate, and (meth). Examples thereof include allyl methyl ether and (meth) allyl glycidyl ether.
　多官能（メタ）アリル化合物の具体例としては、ベンゼンジカルボン酸ジ（メタ）アリル、シクロヘキサンジカルボン酸ジ（メタ）アリル、ジ（メタ）アリルマレエート、ジ（メタ）アリルアジペート、ジ（メタ）アリルフタレート、ジ（メタ）アリルイソフタレート、ジ（メタ）アリルテレフタレート、グリセリンジ（メタ）アリルエーテル、トリメチロールプロパンジ（メタ）アリルエーテル、ペンタエリスリトールジ（メタ）アリルエーテル、１，３－ジ（メタ）アリル－５－グリシジルイソシアヌレート、トリ（メタ）アリルシアヌレート、トリ（メタ）アリルイソシアヌレート、トリ（メタ）アリルトリメリテート、テトラ（メタ）アリルピロメリテート、１，３，４，６－テトラ（メタ）アリルグリコールウリル、１，３，４，６－テトラ（メタ）アリル－３ａ－メチルグリコールウリル、１，３，４，６－テトラ（メタ）アリル－３ａ，６ａ－ジメチルグリコールウリル等が挙げられる。 Specific examples of the polyfunctional (meth) allyl compound include di (meth) allyl benzenedicarboxylate, di (meth) allyl cyclohexanedicarboxylate, di (meth) allylmaleate, di (meth) allyl adipate, and di (meth). Allyl phthalate, di (meth) allyl isophthalate, di (meth) allyl terephthalate, glycerin di (meth) allyl ether, trimethylpropandi (meth) allyl ether, pentaerythritol di (meth) allyl ether, 1,3-di (Meta) allyl-5-glycidyl isocyanurate, tri (meth) allyl cyanurate, tri (meth) allyl isocyanurate, tri (meth) allyl trimellitate, tetra (meth) allyl pyromeritate, 1,3,4 , 6-Tetra (meth) allyl glycol uryl, 1,3,4,6-tetra (meth) allyl-3a-methylglycoluryl, 1,3,4,6-tetra (meth) allyl-3a, 6a-dimethyl Glycol-uryl and the like can be mentioned.
　（メタ）アリル化合物としては、硬化物の耐熱性及び耐湿熱性の観点から、トリ（メタ）アリルイソシアヌレート等のイソシアヌレート骨格を有する化合物、トリ（メタ）アリルシアヌレート、ベンゼンジカルボン酸ジ（メタ）アリル、及びシクロヘキサンジカルボン酸ジ（メタ）アリルからなる群より選択される少なくとも１種が好ましく、イソシアヌレート骨格を有する化合物がより好ましく、トリ（メタ）アリルイソシアヌレートがさらに好ましい。 Examples of the (meth) allyl compound include compounds having an isocyanurate skeleton such as tri (meth) allyl isocyanurate, tri (meth) allyl cyanurate, and benzenedicarboxylic acid di (meth) from the viewpoint of heat resistance and moisture heat resistance of the cured product. ) At least one selected from the group consisting of allyl and di (meth) allyl cyclohexanedicarboxylic acid is preferable, a compound having an isocyanurate skeleton is more preferable, and tri (meth) allyl isocyanurate is further preferable.
　樹脂組成物が（メタ）アリル化合物を含有する場合、樹脂組成物中の（メタ）アリル化合物の含有率は、樹脂組成物の全量に対して、例えば、１０質量％～５０質量％であってもよく、１５質量％～４５質量％であってもよい。 When the resin composition contains a (meth) allyl compound, the content of the (meth) allyl compound in the resin composition is, for example, 10% by mass to 50% by mass with respect to the total amount of the resin composition. It may be 15% by mass to 45% by mass.
　ある実施態様では、重合性化合物はチオール化合物としてチオエーテルオリゴマーと、（メタ）アリル化合物（好ましくは、多官能（メタ）アリル化合物）とを含むものであってもよい。 In some embodiments, the polymerizable compound may include a thioether oligomer as a thiol compound and a (meth) allyl compound (preferably a polyfunctional (meth) allyl compound).
　重合性化合物がチオール化合物としてチオエーテルオリゴマーと（メタ）アリル化合物とを含み、蛍光体として量子ドット蛍光体を使用する場合、量子ドット蛍光体は、分散媒体としてシリコーン化合物に分散された分散液の状態であることが好ましい。 When the polymerizable compound contains a thioether oligomer and a (meth) allyl compound as a thiol compound and a quantum dot phosphor is used as a phosphor, the quantum dot phosphor is in a state of a dispersion liquid dispersed in a silicone compound as a dispersion medium. Is preferable.
　ある実施態様では、重合性化合物はチオール化合物としてチオエーテルオリゴマーの状態ではないものと、（メタ）アクリル化合物（好ましくは多官能（メタ）アクリル化合物、より好ましくは２官能（メタ）アクリル化合物）とを含むものであってもよい。 In some embodiments, the polymerizable compound comprises a thiol compound that is not in the form of a thioether oligomer and a (meth) acrylic compound (preferably a polyfunctional (meth) acrylic compound, more preferably a bifunctional (meth) acrylic compound). It may include.
　重合性化合物がチオール化合物としてチオエーテルオリゴマーの状態ではないものと、（メタ）アクリル化合物とを含み、蛍光体として量子ドット蛍光体を使用する場合、量子ドット蛍光体は、分散媒体として（メタ）アクリル化合物、好ましくは、単官能（メタ）アクリル化合物、より好ましくはイソボルニル（メタ）アクリレートに分散された分散液の状態であることが好ましい。 When the polymerizable compound contains a thiol compound that is not in the state of a thioether oligomer and a (meth) acrylic compound and a quantum dot phosphor is used as the phosphor, the quantum dot phosphor is a (meth) acrylic as a dispersion medium. It is preferably in the form of a compound, preferably a monofunctional (meth) acrylic compound, more preferably a dispersion dispersed in isobornyl (meth) acrylate.
（光重合開始剤）
　樹脂組成物に含まれる光重合開始剤の種類は特に制限されず、紫外線等の活性エネルギー線の照射によりラジカルを発生する化合物が挙げられる。 (Photopolymerization initiator)
The type of photopolymerization initiator contained in the resin composition is not particularly limited, and examples thereof include compounds that generate radicals when irradiated with active energy rays such as ultraviolet rays.
　光重合開始剤の具体例としては、ベンゾフェノン、Ｎ，Ｎ’－テトラアルキル－４，４’－ジアミノベンゾフェノン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－ブタノン－１、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノ－プロパノン－１、４，４’－ビス（ジメチルアミノ）ベンゾフェノン（「ミヒラーケトン」とも称される）、４，４’－ビス（ジエチルアミノ）ベンゾフェノン、４－メトキシ－４’－ジメチルアミノベンゾフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、１－（４－イソプロピルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン、１－（４－（２－ヒドロキシエトキシ）－フェニル）－２－ヒドロキシ－２－メチル－１－プロパン－１－オン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン等の芳香族ケトン化合物；アルキルアントラキノン、フェナントレンキノン等のキノン化合物；ベンゾイン、アルキルベンゾイン等のベンゾイン化合物；ベンゾインアルキルエーテル、ベンゾインフェニルエーテル等のベンゾインエーテル化合物；ベンジルジメチルケタール等のベンジル誘導体；２－（ｏ－クロロフェニル）－４，５－ジフェニルイミダゾール二量体、２－（ｏ－クロロフェニル）－４，５－ジ（ｍ－メトキシフェニル）イミダゾール二量体、２－（ｏ－フルオロフェニル）－４，５－ジフェニルイミダゾール二量体、２－（ｏ－メトキシフェニル）－４，５－ジフェニルイミダゾール二量体、２，４－ジ（ｐ－メトキシフェニル）－５－フェニルイミダゾール二量体、２－（２，４－ジメトキシフェニル）－４，５－ジフェニルイミダゾール二量体等の２，４，５－トリアリールイミダゾール二量体；９－フェニルアクリジン、１，７－（９，９’－アクリジニル）ヘプタン等のアクリジン誘導体；１，２－オクタンジオン１－［４－（フェニルチオ）－２－（Ｏ－ベンゾイルオキシム）］、エタノン１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－１－（Ｏ－アセチルオキシム）等のオキシムエステル化合物；７－ジエチルアミノ－４－メチルクマリン等のクマリン化合物；２，４－ジエチルチオキサントン等のチオキサントン化合物；２，４，６－トリメチルベンゾイル－ジフェニル－ホスフィンオキサイド、２，４，６－トリメチルベンゾイル－フェニル－エトキシ－ホスフィンオキサイド等のアシルホスフィンオキサイド化合物などが挙げられる。樹脂組成物は、１種類の光重合開始剤を単独で含有していてもよく、２種類以上の光重合開始剤を組み合わせて含有していてもよい。 Specific examples of the photopolymerization initiator include benzophenone, N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-Methyl-1- [4- (Methylthio) Phenyl] -2-morpholino-propanone-1, 4,4'-bis (dimethylamino) benzophenone (also referred to as "Michler ketone"), 4,4'-bis (Diethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 1-hydroxycyclohexylphenylketone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4- (4-) (2-Hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one and other aromatic ketone compounds; alkyl Kinone compounds such as anthraquinone and phenanthrenquinone; benzoin compounds such as benzoin and alkylbenzoin; benzoin ether compounds such as benzoin alkyl ether and benzoin phenyl ether; benzyl derivatives such as benzyl dimethyl ketal; 2- (o-chlorophenyl) -4,5 -Diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-Phenylphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl)- 2,4,5-Triarylimidazole dimer such as 4,5-diphenylimidazole dimer; aclysine derivatives such as 9-phenylaclysine, 1,7- (9,9'-acridinyl) heptane; 1,2 -Octanedione 1- [4- (Phenylthio) -2- (O-benzoyloxime)], Etanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- Oxyme ester compounds such as (O-acetyloxime); coumarin compounds such as 7-diethylamino-4-methylkumarin; thioxanthone compounds such as 2,4-diethylthioxanthone; 2,4,6-trimethylbenzoyl-diphenyl-phosphenyl oxide, 2,4,6-trimethylbenzoyl Examples thereof include acylphosphine oxide compounds such as -phenyl-ethoxy-phosphine oxide. The resin composition may contain one kind of photopolymerization initiator alone, or may contain two or more kinds of photopolymerization initiators in combination.
　光重合開始剤としては、硬化性の観点から、アシルホスフィンオキサイド化合物、芳香族ケトン化合物、及びオキシムエステル化合物からなる群より選択される少なくとも１種が好ましく、アシルホスフィンオキサイド化合物及び芳香族ケトン化合物からなる群より選択される少なくとも１種がより好ましく、アシルホスフィンオキサイド化合物がさらに好ましい。 As the photopolymerization initiator, at least one selected from the group consisting of an acylphosphine oxide compound, an aromatic ketone compound, and an oxime ester compound is preferable from the viewpoint of curability, and from the acylphosphine oxide compound and the aromatic ketone compound. At least one selected from the above group is more preferable, and an acylphosphine oxide compound is further preferable.
　樹脂組成物中の光重合開始剤の含有率は、樹脂組成物の全量に対して、例えば、０．１質量％～５質量％であることが好ましく、０．１質量％～３質量％であることがより好ましく、０．１質量％～１．５質量％であることがさらに好ましい。光重合開始剤の含有率が０．１質量％以上であると、樹脂組成物の感度が充分なものとなる傾向にあり、光重合開始剤の含有率が５質量％以下であると、樹脂組成物の色相への影響及び保存安定性の低下が抑えられる傾向にある。 The content of the photopolymerization initiator in the resin composition is preferably, for example, 0.1% by mass to 5% by mass, preferably 0.1% by mass to 3% by mass, based on the total amount of the resin composition. It is more preferably 0.1% by mass to 1.5% by mass. When the content of the photopolymerization initiator is 0.1% by mass or more, the sensitivity of the resin composition tends to be sufficient, and when the content of the photopolymerization initiator is 5% by mass or less, the resin The influence of the composition on the hue and the decrease in storage stability tend to be suppressed.
（光拡散材）
　光変換効率向上の観点から、樹脂組成物は、光拡散材をさらに含有していてもよい。光拡散材の具体例としては、酸化チタン、硫酸バリウム、酸化亜鉛、炭酸カルシウム等が挙げられる。これらの中でも、光散乱効率の観点からは光拡散材は酸化チタンであることが好ましい。酸化チタンはルチル型酸化チタンであってもアナターゼ型酸化チタンであってもよく、ルチル型酸化チタンであることが好ましい。 (Light diffuser)
From the viewpoint of improving the light conversion efficiency, the resin composition may further contain a light diffusing material. Specific examples of the light diffusing material include titanium oxide, barium sulfate, zinc oxide, calcium carbonate and the like. Among these, the light diffusing material is preferably titanium oxide from the viewpoint of light scattering efficiency. The titanium oxide may be rutile-type titanium oxide or anatase-type titanium oxide, and is preferably rutile-type titanium oxide.
　光拡散材の平均粒子径は、０．１μｍ～１μｍであることが好ましく、０．２μｍ～０．８μｍであることがより好ましく、０．２μｍ～０．５μｍであることがさらに好ましい。
　本開示において光拡散材の平均粒子径は、以下のようにして測定することができる。
　光拡散材が樹脂組成物に含まれている場合、抽出した光拡散材を、界面活性剤を含んだ精製水に分散させ、分散液を得る。この分散液を用いてレーザー回折式粒度分布測定装置（例えば、株式会社島津製作所、ＳＡＬＤ－３０００Ｊ）で測定される体積基準の粒度分布において、小径側からの積算が５０％となるときの値（メジアン径（Ｄ５０））を光拡散材の平均粒子径とする。樹脂組成物から光拡散材を抽出する方法としては、例えば、樹脂組成物を液状媒体で希釈し、遠心分離処理等により光拡散材を沈澱させて分収することで得ることができる。
　光拡散材を含む樹脂組成物を硬化して得られる硬化物中における光拡散材の平均粒子径は、走査型電子顕微鏡を用いた粒子の観察により、５０個の粒子について円相当径（長径と短径の幾何平均）を算出し、その算術平均値として求めることができる。 The average particle size of the light diffusing material is preferably 0.1 μm to 1 μm, more preferably 0.2 μm to 0.8 μm, and even more preferably 0.2 μm to 0.5 μm.
In the present disclosure, the average particle size of the light diffusing material can be measured as follows.
When the light diffusing material is contained in the resin composition, the extracted light diffusing material is dispersed in purified water containing a surfactant to obtain a dispersion liquid. In the volume-based particle size distribution measured by a laser diffraction type particle size distribution measuring device (for example, Shimadzu Corporation, SALD-3000J) using this dispersion, the value when the integration from the small diameter side is 50% (for example). The median diameter (D50)) is defined as the average particle size of the light diffusing material. As a method for extracting the light diffusing material from the resin composition, for example, the resin composition can be obtained by diluting the resin composition with a liquid medium, precipitating the light diffusing material by centrifugation or the like, and distributing the light diffusing material.
The average particle size of the light diffusing material in the cured product obtained by curing the resin composition containing the light diffusing material is the equivalent circle diameter (major axis) of 50 particles by observing the particles using a scanning electron microscope. The geometric mean of the minor axis) can be calculated and calculated as the arithmetic mean value.
　樹脂組成物中で光拡散材が凝集するのを抑制する観点から、光拡散材は、表面の少なくとも一部に有機物を含む有機物層を有することが好ましい。有機物層に含まれる有機物としては、有機シラン、オルガノシロキサン、フルオロシラン、有機ホスホネート、有機リン酸化合物、有機ホスフィネート、有機スルホン酸化合物、カルボン酸、カルボン酸エステル、カルボン酸の誘導体、アミド、炭化水素ワックス、ポリオレフィン、ポリオレフィンのコポリマー、ポリオール、ポリオールの誘導体、アルカノールアミン、アルカノールアミンの誘導体、有機分散剤等が挙げられる。
　有機物層に含まれる有機物は、ポリオール、有機シラン等を含むことが好ましく、ポリオール又は有機シランの少なくとも一方を含むことがより好ましい。
　有機シランの具体例としては、オクチルトリエトキシシラン、ノニルトリエトキシシラン、デシルトリエトキシシラン、ドデシルトリエトキシシラン、トリデシルトリエトキシシラン、テトラデシルトリエトキシシラン、ペンタデシルトリエトキシシラン、ヘキサデシルトリエトキシシラン、ヘプタデシルトリエトキシシラン、オクタデシルトリエトキシシラン等が挙げられる。
　オルガノシロキサンの具体例としては、トリメチルシリル基で終端されたポリジメチルシロキサン（ＰＤＭＳ）、ポリメチルヒドロシロキサン（ＰＭＨＳ）、ＰＭＨＳのオレフィンによる官能化（ヒドロシリル化による）により誘導されるポリシロキサン等が挙げられる。
　有機ホスホネートの具体例としては、例えば、ｎ－オクチルホスホン酸及びそのエステル、ｎ－デシルホスホン酸及びそのエステル、２－エチルヘキシルホスホン酸及びそのエステル並びにカンフィル（ｃａｍｐｈｙｌ）ホスホン酸及びそのエステルが挙げられる。
　有機リン酸化合物の具体例としては、有機酸性ホスフェート、有機ピロホスフェート、有機ポリホスフェート、有機メタホスフェート、これらの塩等が挙げられる。
　有機ホスフィネートの具体例としては、例えば、ｎ－ヘキシルホスフィン酸及びそのエステル、ｎ－オクチルホスフィン酸及びそのエステル、ジ－ｎ－ヘキシルホスフィン酸及びそのエステル並びにジ－ｎ－オクチルホスフィン酸及びそのエステルが挙げられる。
　有機スルホン酸化合物の具体例としては、ヘキシルスルホン酸、オクチルスルホン酸、２－エチルヘキシルスルホン酸等のアルキルスルホン酸、これらアルキルスルホン酸と、ナトリウム、カルシウム、マグネシウム、アルミニウム、チタン等の金属イオン、アンモニウムイオン、トリエタノールアミン等の有機アンモニウムイオンなどとの塩が挙げられる。
　カルボン酸の具体例としては、マレイン酸、マロン酸、フマル酸、安息香酸、フタル酸、ステアリン酸、オレイン酸、リノール酸等が挙げられる。
　カルボン酸エステルの具体例としては、上記カルボン酸と、エチレングリコール、プロピレングリコール、トリメチロールプロパン、ジエタノールアミン、トリエタノールアミン、グリセロール、ヘキサントリオール、エリトリトール、マンニトール、ソルビトール、ペンタエリトリトール、ビスフェノールＡ、ヒドロキノン、フロログルシノール等のヒドロキシ化合物との反応により生成するエステル及び部分エステルが挙げられる。
　アミドの具体例としては、ステアリン酸アミド、オレイン酸アミド、エルカ酸アミド等が挙げられる。
　ポリオレフィン及びそのコポリマーの具体例としては、ポリエチレン、ポリプロピレン、エチレンと、プロピレン、ブチレン、酢酸ビニル、アクリレート、アクリルアミド等から選択される１種又は２種以上の化合物との共重合体などが挙げられる。
　ポリオールの具体例としては、グリセロール、トリメチロールエタン、トリメチロールプロパン等が挙げられる。
　アルカノールアミンの具体例としては、ジエタノールアミン、トリエタノールアミン等が挙げられる。
　有機分散剤の具体例としては、クエン酸、ポリアクリル酸、ポリメタクリル酸、陰イオン性、陽イオン性、双性、非イオン性等の官能基をもつ高分子有機分散剤などが挙げられる。
　樹脂組成物中における光拡散材の凝集が抑制されると、硬化物中における光拡散材の分散性が向上する傾向にある。 From the viewpoint of suppressing the aggregation of the light diffusing material in the resin composition, the light diffusing material preferably has an organic substance layer containing an organic substance on at least a part of the surface thereof. The organic substances contained in the organic substance layer include organic silane, organosiloxane, fluorosilane, organic phosphonate, organic phosphoric acid compound, organic phosphinate, organic sulfonic acid compound, carboxylic acid, carboxylic acid ester, carboxylic acid derivative, amide, and hydrocarbon. Examples thereof include waxes, polyolefins, copolymers of polyolefins, polyols, derivatives of polyols, alkanolamines, derivatives of alkanolamines, organic dispersants and the like.
The organic substance contained in the organic substance layer preferably contains a polyol, an organic silane, or the like, and more preferably contains at least one of the polyol or the organic silane.
Specific examples of organic silanes include octyltriethoxysilane, nonyltriethoxysilane, decyltriethoxysilane, dodecyltriethoxysilane, tridecyltriethoxysilane, tetradecyltriethoxysilane, pentadecyltriethoxysilane, and hexadecyltriethoxysilane. Examples thereof include silane, heptadecyltriethoxysilane, and octadecyltriethoxysilane.
Specific examples of the organosiloxane include polydimethylsiloxane (PDMS) terminated with a trimethylsilyl group, polymethylhydrosiloxane (PMHS), polysiloxane induced by functionalization of PMHS with an olefin (by hydrosilylation), and the like. ..
Specific examples of organic phosphonates include n-octylphosphonic acid and its ester, n-decylphosphonic acid and its ester, 2-ethylhexylphosphonic acid and its ester, and camphyl phosphonic acid and its ester.
Specific examples of the organic phosphoric acid compound include organic acidic phosphate, organic pyrophosphate, organic polyphosphate, organic metaphosphate, salts thereof and the like.
Specific examples of the organic phosphinate include n-hexylphosphinic acid and its ester, n-octylphosphinic acid and its ester, di-n-hexylphosphinic acid and its ester, and di-n-octylphosphinic acid and its ester. Can be mentioned.
Specific examples of the organic sulfonic acid compound include alkyl sulfonic acids such as hexyl sulfonic acid, octyl sulfonic acid, and 2-ethylhexyl sulfonic acid, these alkyl sulfonic acids, metal ions such as sodium, calcium, magnesium, aluminum, and titanium, and ammonium. Examples thereof include salts with ions and organic ammonium ions such as triethanolamine.
Specific examples of the carboxylic acid include maleic acid, malonic acid, fumaric acid, benzoic acid, phthalic acid, stearic acid, oleic acid, linoleic acid and the like.
Specific examples of the carboxylic acid ester include the above carboxylic acid, ethylene glycol, propylene glycol, trimethylolpropane, diethanolamine, triethanolamine, glycerol, hexanetriol, erythritol, mannitol, sorbitol, pentaerythritol, bisphenol A, hydroquinone, and flo. Examples thereof include esters and partial esters produced by reaction with a hydroxy compound such as loglucinol.
Specific examples of the amide include stearic acid amide, oleic acid amide, and erucic acid amide.
Specific examples of the polyolefin and its copolymer include a copolymer of polyethylene, polypropylene, ethylene and one or more compounds selected from propylene, butylene, vinyl acetate, acrylate, acrylamide and the like.
Specific examples of the polyol include glycerol, trimethylolethane, trimethylolpropane and the like.
Specific examples of the alkanolamine include diethanolamine and triethanolamine.
Specific examples of the organic dispersant include high molecular weight organic dispersants having functional groups such as citric acid, polyacrylic acid, polymethacrylic acid, anionic, cationic, bipolar and nonionic.
When the aggregation of the light diffusing material in the resin composition is suppressed, the dispersibility of the light diffusing material in the cured product tends to be improved.
　光拡散材は、表面の少なくとも一部に金属酸化物を含む金属酸化物層を有していてもよい。金属酸化物層に含まれる金属酸化物としては、二酸化ケイ素、酸化アルミニウム、ジルコニア、ホスホリア（ｐｈｏｓｐｈｏｒｉａ）、ボリア（ｂｏｒｉａ）等が挙げられる。金属酸化物層は一層であっても二層以上であってもよい。光拡散材が二層の金属酸化物層を有する場合、二酸化ケイ素を含む第一金属酸化物層及び酸化アルミニウムを含む第二金属酸化物層を含むものであることが好ましい。
　光拡散材が金属酸化物層を有することで、硬化物中における光拡散材の分散性が向上する傾向にある。 The light diffusing material may have a metal oxide layer containing a metal oxide on at least a part of the surface thereof. Examples of the metal oxide contained in the metal oxide layer include silicon dioxide, aluminum oxide, zirconia, phosphoria, and boria. The metal oxide layer may be one layer or two or more layers. When the light diffusing material has two metal oxide layers, it preferably contains a first metal oxide layer containing silicon dioxide and a second metal oxide layer containing aluminum oxide.
When the light diffusing material has a metal oxide layer, the dispersibility of the light diffusing material in the cured product tends to be improved.
　光拡散材が有機物を含む有機物層と金属酸化物層とを有する場合、光拡散材の表面に、金属酸化物層及び有機物層が、金属酸化物層及び有機物層の順に設けられることが好ましい。
　光拡散材が有機物層と二層の金属酸化物層とを有するものである場合、光拡散材の表面に、二酸化ケイ素を含む第一金属酸化物層、酸化アルミニウムを含む第二金属酸化物層及び有機物層が、第一金属酸化物層、第二金属酸化物層及び有機物層の順に設けられる（有機物層が最外層となる）ことが好ましい。 When the light diffusing material has an organic material layer containing an organic substance and a metal oxide layer, it is preferable that the metal oxide layer and the organic material layer are provided on the surface of the light diffusing material in the order of the metal oxide layer and the organic material layer.
When the light diffusing material has an organic material layer and two metal oxide layers, a first metal oxide layer containing silicon dioxide and a second metal oxide layer containing aluminum oxide are formed on the surface of the light diffusing material. It is preferable that the organic material layer is provided in the order of the first metal oxide layer, the second metal oxide layer, and the organic material layer (the organic material layer is the outermost layer).
　樹脂組成物が光拡散材を含有する場合、これを硬化して形成される波長変換層における光拡散材の含有率は、波長変換層の全量に対して、例えば、０．１質量％～１．０質量％であることが好ましく、０．２質量％～１．０質量％であることがより好ましく、０．３質量％～１．０質量％であることがさらに好ましい。 When the resin composition contains a light diffusing material, the content of the light diffusing material in the wavelength conversion layer formed by curing the light diffusing material is, for example, 0.1% by mass to 1% by mass with respect to the total amount of the wavelength conversion layer. It is preferably 0.0% by mass, more preferably 0.2% by mass to 1.0% by mass, and even more preferably 0.3% by mass to 1.0% by mass.
（液状媒体）
　樹脂組成物は、液状媒体をさらに含有していてもよい。液状媒体とは、室温（２５℃）において液体の状態の媒体をいう。 (Liquid medium)
The resin composition may further contain a liquid medium. The liquid medium means a medium in a liquid state at room temperature (25 ° C.).
　液状媒体の具体例としては、アセトン、メチルエチルケトン、メチル－ｎ－プロピルケトン、メチルイソプロピルケトン、メチル－ｎ－ブチルケトン、メチルイソブチルケトン、メチル－ｎ－ペンチルケトン、メチル－ｎ－ヘキシルケトン、ジエチルケトン、ジプロピルケトン、ジイソブチルケトン、トリメチルノナノン、シクロヘキサノン、シクロペンタノン、メチルシクロヘキサノン、２，４－ペンタンジオン、アセトニルアセトン等のケトン溶剤；ジエチルエーテル、メチルエチルエーテル、メチル－ｎ－プロピルエーテル、ジイソプロピルエーテル、テトラヒドロフラン、メチルテトラヒドロフラン、ジオキサン、ジメチルジオキサン、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールジ－ｎ－プロピルエーテル、エチレングリコールジ－ｎ－ブチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールメチルエチルエーテル、ジエチレングリコールメチル－ｎ－プロピルエーテル、ジエチレングリコールメチル－ｎ－ブチルエーテル、ジエチレングリコールジ－ｎ－プロピルエーテル、ジエチレングリコールジ－ｎ－ブチルエーテル、ジエチレングリコールメチル－ｎ－ヘキシルエーテル、トリエチレングリコールジメチルエーテル、トリエチレングリコールジエチルエーテル、トリエチレングリコールメチルエチルエーテル、トリエチレングリコールメチル－ｎ－ブチルエーテル、トリエチレングリコールジ－ｎ－ブチルエーテル、トリエチレングリコールメチル－ｎ－ヘキシルエーテル、テトラエチレングリコールジメチルエーテル、テトラエチレングリコールジエチルエーテル、テトラエチレングリコールメチルエチルエーテル、テトラエチレングリコールメチル－ｎ－ブチルエーテル、テトラエチレングリコールジ－ｎ－ブチルエーテル、テトラエチレングリコールメチル－ｎ－ヘキシルエーテル、プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、プロピレングリコールジ－ｎ－プロピルエーテル、プロピレングリコールジ－ｎ－ブチルエーテル、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールジエチルエーテル、ジプロピレングリコールメチルエチルエーテル、ジプロピレングリコールメチル－ｎ－ブチルエーテル、ジプロピレングリコールジ－ｎ－プロピルエーテル、ジプロピレングリコールジ－ｎ－ブチルエーテル、ジプロピレングリコールメチル－ｎ－ヘキシルエーテル、トリプロピレングリコールジメチルエーテル、トリプロピレングリコールジエチルエーテル、トリプロピレングリコールメチルエチルエーテル、トリプロピレングリコールメチル－ｎ－ブチルエーテル、トリプロピレングリコールジ－ｎ－ブチルエーテル、トリプロピレングリコールメチル－ｎ－ヘキシルエーテル、テトラプロピレングリコールジメチルエーテル、テトラプロピレングリコールジエチルエーテル、テトラプロピレングリコールメチルエチルエーテル、テトラプロピレングリコールメチル－ｎ－ブチルエーテル、テトラプロピレングリコールジ－ｎ－ブチルエーテル、テトラプロピレングリコールメチル－ｎ－ヘキシルエーテル等のエーテル溶剤；プロピレンカーボネート、エチレンカーボネート、ジエチルカーボネート等のカーボネート溶剤；酢酸メチル、酢酸エチル、酢酸ｎ－プロピル、酢酸イソプロピル、酢酸ｎ－ブチル、酢酸イソブチル、酢酸ｓｅｃ－ブチル、酢酸ｎ－ペンチル、酢酸ｓｅｃ－ペンチル、酢酸３－メトキシブチル、酢酸メチルペンチル、酢酸２－エチルブチル、酢酸２－エチルヘキシル、酢酸２－（２－ブトキシエトキシ）エチル、酢酸ベンジル、酢酸シクロヘキシル、酢酸メチルシクロヘキシル、酢酸ノニル、アセト酢酸メチル、アセト酢酸エチル、酢酸ジエチレングリコールメチルエーテル、酢酸ジエチレングリコールモノエチルエーテル、酢酸ジプロピレングリコールメチルエーテル、酢酸ジプロピレングリコールエチルエーテル、ジ酢酸グリコール、酢酸メトキシトリエチレングリコール、プロピオン酸エチル、プロピオン酸ｎ－ブチル、プロピオン酸イソアミル、シュウ酸ジエチル、シュウ酸ジ－ｎ－ブチル、乳酸メチル、乳酸エチル、乳酸ｎ－ブチル、乳酸ｎ－アミル、エチレングリコールメチルエーテルプロピオネート、エチレングリコールエチルエーテルプロピオネート、エチレングリコールメチルエーテルアセテート、エチレングリコールエチルエーテルアセテート、プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート、γ－ブチロラクトン、γ－バレロラクトン等のエステル溶剤；アセトニトリル、Ｎ－メチルピロリジノン、Ｎ－エチルピロリジノン、Ｎ－プロピルピロリジノン、Ｎ－ブチルピロリジノン、Ｎ－ヘキシルピロリジノン、Ｎ－シクロヘキシルピロリジノン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、ジメチルスルホキシド等の非プロトン性極性溶剤；メタノール、エタノール、ｎ－プロパノール、イソプロパノール、ｎ－ブタノール、イソブタノール、ｓｅｃ－ブタノール、ｔ－ブタノール、ｎ－ペンタノール、イソペンタノール、２－メチルブタノール、ｓｅｃ－ペンタノール、ｔ－ペンタノール、３－メトキシブタノール、ｎ－ヘキサノール、２－メチルペンタノール、ｓｅｃ－ヘキサノール、２－エチルブタノール、ｓｅｃ－ヘプタノール、ｎ－オクタノール、２－エチルヘキサノール、ｓｅｃ－オクタノール、ｎ－ノニルアルコール、ｎ－デカノール、ｓｅｃ－ウンデシルアルコール、トリメチルノニルアルコール、ｓｅｃ－テトラデシルアルコール、ｓｅｃ－ヘプタデシルアルコール、シクロヘキサノール、メチルシクロヘキサノール、ベンジルアルコール、エチレングリコール、１，２－プロピレングリコール、１，３－ブチレングリコール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、トリプロピレングリコール等のアルコール溶剤；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノフェニルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノ－ｎ－ブチルエーテル、ジエチレングリコールモノ－ｎ－ヘキシルエーテル、トリエチレングリコールモノエチルエーテル、テトラエチレングリコールモノ－ｎ－ブチルエーテル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、トリプロピレングリコールモノメチルエーテル等のグリコールモノエーテル溶剤；テルピネン、テルピネオール、ミルセン、アロオシメン、リモネン、ジペンテン、ピネン、カルボン、オシメン、フェランドレン等のテルペン溶剤；ジメチルシリコーンオイル、メチルフェニルシリコーンオイル、メチルハイドロジェンシリコーンオイル等のストレートシリコーンオイル；アミノ変性シリコーンオイル、エポキシ変性シリコーンオイル、カルボキシ変性シリコーンオイル、カルビノール変性シリコーンオイル、メルカプト変性シリコーンオイル、異種官能基変性シリコーンオイル、ポリエーテル変性シリコーンオイル、メチルスチリル変性シリコーンオイル、親水性特殊変性シリコーンオイル、高級アルコキシ変性シリコーンオイル、高級脂肪酸変性シリコーンオイル、フッ素変性シリコーンオイル等の変性シリコーンオイル；ブタン酸、ペンタン酸、ヘキサン酸、ヘプタン酸、オクタン酸、ノナン酸、デカン酸、ウンデカン酸、ドデカン酸、トリデカン酸、テトラデカン酸、ペンタデカン酸、ヘキサデカン酸、ヘプタデカン酸、オクタデカン酸、ノナデカン酸、イコサン酸、エイコセン酸等の炭素数４以上の飽和脂肪族モノカルボン酸；オレイン酸、エライジン酸、リノール酸、パルミトレイン酸等の炭素数８以上の不飽和脂肪族モノカルボン酸などが挙げられる。樹脂組成物が液状媒体を含有する場合、樹脂組成物は、１種類の液状媒体を単独で含有していてもよく、２種類以上の液状媒体を組み合わせて含有していてもよい。 Specific examples of the liquid medium include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl-n-pentyl ketone, methyl-n-hexyl ketone, diethyl ketone, and the like. Ketone solvents such as dipropyl ketone, diisobutyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentandione, acetonylacetone; diethyl ether, methyl ethyl ether, methyl-n-propyl ether, diisopropyl Ether, tetrahydrofuran, methyl tetrahydrofuran, dioxane, dimethyl dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di-n-propyl ether, ethylene glycol di-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, Diethylene glycol methyl-n-propyl ether, diethylene glycol methyl-n-butyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, diethylene glycol methyl-n-hexyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tri Ethylene glycol methyl ethyl ether, triethylene glycol methyl-n-butyl ether, triethylene glycol di-n-butyl ether, triethylene glycol methyl-n-hexyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol methyl ethyl Ether, tetraethylene glycol methyl-n-butyl ether, tetraethylene glycol di-n-butyl ether, tetraethylene glycol methyl-n-hexyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n-propyl ether, propylene glycol Di-n-butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol methyl-n-butyl ether, dipropi Lenglycol di-n-propyl ether, dipropylene glycol di-n-butyl ether, dipropylene glycol methyl-n-hexyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol methyl ethyl ether, tripropylene glycol methyl -N-butyl ether, tripropylene glycol di-n-butyl ether, tripropylene glycol methyl-n-hexyl ether, tetrapropylene glycol dimethyl ether, tetrapropylene glycol diethyl ether, tetrapropylene glycol methyl ethyl ether, tetrapropylene glycol methyl-n-butyl ether , Tetrapropylene glycol di-n-butyl ether, tetrapropylene glycol methyl-n-hexyl ether and other ether solvents; propylene carbonate, ethylene carbonate, diethyl carbonate and other carbonate solvents; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate , N-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, 2- (2- (2-) Butoxyethoxy) ethyl, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, nonyl acetate, methyl acetoacetate, ethyl acetoacetate, diethylene glycol methyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl acetate ether , Glycol diacetate, methoxytriethylene glycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n lactate -Amil, ethylene glycol methyl ether propionate, ethylene glycol ethyl ether propionate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, γ -Ester solvents such as butyrolactone and γ-valerolactone; acetonitrile, N- Aprotonic polarities such as methylpyrrolidinone, N-ethylpyrrolidinone, N-propylpyrrolidinone, N-butylpyrrolidinone, N-hexylpyrrolidinone, N-cyclohexylpyrrolidinone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, etc. Solvents: methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, t-pentanol , 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, n-decanol , Se-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, cyclohexanol, methylcyclohexanol, benzyl alcohol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, Alcohol solvents such as diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether. , Diethylene glycol mono-n-hexyl ether, triethylene glycol monoethyl ether, tetraethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, etc. Glycol monoether solvent; terpene solvent such as terpinene, terpineol, milsen, aloosimene, limonene, dipentene, pinene, carboxylic, ossimen, ferlandrene; straight silicone oil such as dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil; Amino-modified silicone oil, epoxy-modified silicone oil, cal Boxy-modified silicone oil, carbinol-modified silicone oil, mercapto-modified silicone oil, heterologous functional group-modified silicone oil, polyether-modified silicone oil, methylstyryl-modified silicone oil, hydrophilic special-modified silicone oil, higher alkoxy-modified silicone oil, higher fatty acids Modified silicone oils such as modified silicone oils, fluorine-modified silicone oils; butanoic acid, pentanoic acid, hexanoic acid, heptanic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, Saturated aliphatic monocarboxylic acids with 4 or more carbon atoms such as hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanic acid, icosanoic acid, and eicosenoic acid; Examples include saturated aliphatic monocarboxylic acids. When the resin composition contains a liquid medium, the resin composition may contain one kind of liquid medium alone or a combination of two or more kinds of liquid media.
　樹脂組成物が液状媒体を含有する場合、樹脂組成物中の液状媒体の含有率は、樹脂組成物の全量に対して、例えば、１質量％～１０質量％であることが好ましく、４質量％～１０質量％であることがより好ましく、４質量％～７質量％であることがさらに好ましい。 When the resin composition contains a liquid medium, the content of the liquid medium in the resin composition is preferably, for example, 1% by mass to 10% by mass, and 4% by mass, based on the total amount of the resin composition. It is more preferably about 10% by mass, and even more preferably 4% by mass to 7% by mass.
（その他の成分）
　樹脂組成物は、上述した成分以外の成分をさらに含有していてもよい。例えば、樹脂組成物は、重合禁止剤、シランカップリング剤、界面活性剤、密着付与剤、酸化防止剤、酢酸等のカルボン酸などの成分をさらに含有していてもよい。各成分は、１種を単独で用いても２種以上を併用してもよい。 (Other ingredients)
The resin composition may further contain components other than the above-mentioned components. For example, the resin composition may further contain components such as a polymerization inhibitor, a silane coupling agent, a surfactant, an adhesion imparting agent, an antioxidant, and a carboxylic acid such as acetic acid. Each component may be used alone or in combination of two or more.
（樹脂組成物の調製方法）
　樹脂組成物は、蛍光体、重合性化合物、光重合開始剤、及び必要に応じてその他の成分を常法により混合することで調製することができる。 (Method for preparing resin composition)
The resin composition can be prepared by mixing a phosphor, a polymerizable compound, a photopolymerization initiator, and if necessary, other components by a conventional method.
　波長変換層は、１種類の樹脂組成物を硬化したものであってもよく、２種類以上の樹脂組成物を硬化したものであってもよい。例えば、波長変換部材がフィルム状である場合、波長変換層は、第１の蛍光体を含有する樹脂組成物を硬化した第１の硬化物層と、第１の蛍光体とは発光特性が異なる第２の蛍光体を含有する樹脂組成物を硬化した第２の硬化物層とが積層されたものであってもよい。 The wavelength conversion layer may be one obtained by curing one kind of resin composition, or may be one obtained by curing two or more kinds of resin compositions. For example, when the wavelength conversion member is in the form of a film, the wavelength conversion layer has different light emitting characteristics from the first cured product layer obtained by curing the resin composition containing the first phosphor and the first phosphor. A resin composition containing a second phosphor may be laminated with a second cured product layer obtained by curing the resin composition.
　波長変換層の平均厚みは特に制限されず、例えば、５０μｍ～２００μｍであることが好ましく、５０μｍ～１５０μｍであることがより好ましく、７０μｍ～１２０μｍであることがさらに好ましい。波長変換層の平均厚みが５０μｍ以上であると、波長変換効率がより向上する傾向にあり、波長変換層の平均厚みが２００μｍ以下であると、後述するバックライトユニットに波長変換部材を適用した場合に、バックライトユニットをより薄型化できる傾向にある。波長変換層の平均厚みは、例えば、マイクロメータを用いて測定した任意の３箇所の厚みの算術平均値として求められる。 The average thickness of the wavelength conversion layer is not particularly limited, and is preferably, for example, 50 μm to 200 μm, more preferably 50 μm to 150 μm, and even more preferably 70 μm to 120 μm. When the average thickness of the wavelength conversion layer is 50 μm or more, the wavelength conversion efficiency tends to be further improved, and when the average thickness of the wavelength conversion layer is 200 μm or less, when the wavelength conversion member is applied to the backlight unit described later. In addition, there is a tendency that the backlight unit can be made thinner. The average thickness of the wavelength conversion layer is obtained as, for example, an arithmetic mean value of the thicknesses of any three points measured using a micrometer.
　波長変換層は、密着性をより向上させる観点から、動的粘弾性測定により周波数１０Ｈｚかつ温度２５℃の条件で測定した損失正接（ｔａｎδ）が０．４～１．５であることが好ましく、０．４～１．２であることがより好ましく、０．４～０．６であることがさらに好ましい。波長変換層の損失正接（ｔａｎδ）は、動的粘弾性測定装置（例えば、Ｒｈｅｏｍｅｔｒｉｃ　Ｓｃｉｅｎｔｉｆｉｃ社、Ｓｏｌｉｄ　Ａｎａｌｙｚｅｒ　ＲＳＡ－ＩＩＩ）を用いて測定することができる。 From the viewpoint of further improving the adhesion, the wavelength conversion layer preferably has a loss tangent (tan δ) of 0.4 to 1.5 measured under the conditions of a frequency of 10 Hz and a temperature of 25 ° C. by dynamic viscoelasticity measurement. It is more preferably 0.4 to 1.2, and even more preferably 0.4 to 0.6. The loss tangent (tan δ) of the wavelength conversion layer can be measured using a dynamic viscoelasticity measuring device (for example, Rheometric Scientific, Solid Analyzer RSA-III).
　波長変換層は、密着性、耐熱性、及び耐湿熱性をより向上させる観点から、ガラス転移温度（Ｔｇ）が８５℃以上であることが好ましく、８５℃～１６０℃であることがより好ましく、９０℃～１２０℃であることがさらに好ましい。波長変換層のガラス転移温度（Ｔｇ）は、動的粘弾性測定装置（例えば、Ｒｈｅｏｍｅｔｒｉｃ　Ｓｃｉｅｎｔｉｆｉｃ社、Ｓｏｌｉｄ　Ａｎａｌｙｚｅｒ　ＲＳＡ－ＩＩＩ）を用いて、周波数１０Ｈｚの条件で測定することができる。 The wavelength conversion layer preferably has a glass transition temperature (Tg) of 85 ° C. or higher, more preferably 85 ° C. to 160 ° C., and 90 ° C., from the viewpoint of further improving adhesion, heat resistance, and moist heat resistance. It is more preferably ° C. to 120 ° C. The glass transition temperature (Tg) of the wavelength conversion layer can be measured under the condition of a frequency of 10 Hz using a dynamic viscoelasticity measuring device (for example, Rheometric Scientific, Solid Analyzer RSA-III).
　また、波長変換層は、密着性、耐熱性、及び耐湿熱性をより向上させる観点から、周波数１０Ｈｚかつ温度２５℃の条件で測定した貯蔵弾性率が１×１０７Ｐａ～１×１０１０Ｐａであることが好ましく、５×１０７Ｐａ～１×１０１０Ｐａであることがより好ましく、５×１０７Ｐａ～５×１０９Ｐａであることがさらに好ましい。樹脂硬化物の貯蔵弾性率は、動的粘弾性測定装置（例えば、Ｒｈｅｏｍｅｔｒｉｃ　Ｓｃｉｅｎｔｉｆｉｃ社、Ｓｏｌｉｄ　Ａｎａｌｙｚｅｒ　ＲＳＡ－ＩＩＩ）を用いて測定することができる。 In addition, the wavelength conversion layer has a storage elastic modulus of 1 × 10 7 Pa to 1 × 10 10 Pa measured under the conditions of a frequency of 10 Hz and a temperature of 25 ° C. from the viewpoint of further improving adhesion, heat resistance, and moisture heat resistance. It is preferably 5 × 10 7 Pa to 1 × 10 10 Pa, more preferably 5 × 10 7 Pa to 5 × 10 9 Pa. The storage elastic modulus of the cured resin product can be measured using a dynamic viscoelasticity measuring device (for example, Rheometric Scientific, Solid Analyzer RSA-III).
　波長変換層は、例えば、樹脂組成物の塗膜、成形体等を形成し、必要に応じて乾燥処理を行った後、紫外線等の活性エネルギー線を照射することにより得ることができる。活性エネルギー線の波長及び照射量は、樹脂組成物の組成に応じて適宜設定することができる。一態様では、２８０ｎｍ～４００ｎｍの波長の紫外線を１００ｍＪ／ｃｍ２～５０００ｍＪ／ｃｍ２の照射量で照射する。紫外線源としては、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、カーボンアーク灯、メタルハライドランプ、キセノンランプ、ケミカルランプ、ブラックライトランプ、マイクロウェーブ励起水銀灯等が挙げられる。 The wavelength conversion layer can be obtained, for example, by forming a coating film, a molded product, or the like of a resin composition, performing a drying treatment as necessary, and then irradiating with active energy rays such as ultraviolet rays. The wavelength and irradiation amount of the active energy rays can be appropriately set according to the composition of the resin composition. In one aspect, it is irradiated with ultraviolet rays having a wavelength of 280 nm ~ 400 nm at an irradiation amount of 100mJ / cm 2 ~ 5000mJ / cm 2. Examples of the ultraviolet source include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, and the like.
　波長変換部材の概略構成の一例を図１に示す。但し、本開示の波長変換部材は図１の構成に限定されるものではない。 FIG. 1 shows an example of the schematic configuration of the wavelength conversion member. However, the wavelength conversion member of the present disclosure is not limited to the configuration shown in FIG.
　図１に示す波長変換部材１０は、フィルム状の硬化物である波長変換層１１と、波長変換層１１の両面に設けられたフィルム状の被覆材１２Ａ及び１２Ｂと、を有する。被覆材１２Ａ及び被覆材１２Ｂの種類及び平均厚みは、それぞれ同一であっても異なっていてもよい。被覆材１２Ａ及び１２Ｂは粗面化されていてもよい。 The wavelength conversion member 10 shown in FIG. 1 has a wavelength conversion layer 11 which is a film-like cured product, and film- like coating materials 12A and 12B provided on both sides of the wavelength conversion layer 11. The types and average thicknesses of the covering material 12A and the covering material 12B may be the same or different. The covering materials 12A and 12B may be roughened.
　図１に示す構成の波長変換部材は、例えば、以下のような製造方法により製造することができる。 The wavelength conversion member having the configuration shown in FIG. 1 can be manufactured by, for example, the following manufacturing method.
　まず、連続搬送されるフィルム状の被覆材（以下、「第１の被覆材」ともいう。）の表面に波長変換層形成用の樹脂組成物を付与し、塗膜を形成する。樹脂組成物の付与方法は特に制限されず、ダイコーティング法、カーテンコーティング法、エクストルージョンコーティング法、ロッドコーティング法、ロールコーティング法等が挙げられる。 First, a resin composition for forming a wavelength conversion layer is applied to the surface of a film-like coating material (hereinafter, also referred to as "first coating material") that is continuously conveyed to form a coating film. The method for applying the resin composition is not particularly limited, and examples thereof include a die coating method, a curtain coating method, an extrusion coating method, a rod coating method, and a roll coating method.
　次いで、樹脂組成物の塗膜の上に、連続搬送されるフィルム状の被覆材（以下、「第２の被覆材」ともいう。）を貼り合わせる。 Next, a film-like coating material (hereinafter, also referred to as "second coating material") that is continuously conveyed is attached onto the coating film of the resin composition.
　次いで、第１の被覆材及び第２の被覆材のうち活性エネルギー線を透過可能な被覆材側から活性エネルギー線を照射することにより、塗膜を硬化し、硬化物層を形成する。その後、規定のサイズに切り出すことにより、図１に示す構成の波長変換部材を得ることができる。 Next, the coating film is cured and a cured product layer is formed by irradiating the active energy rays from the side of the first coating material and the second coating material that can transmit the active energy rays. Then, by cutting out to a specified size, a wavelength conversion member having the configuration shown in FIG. 1 can be obtained.
　なお、第１の被覆材及び第２の被覆材のいずれも活性エネルギー線を透過可能でない場合には、第２の被覆材を貼り合わせる前に塗膜に活性エネルギー線を照射して硬化物層を形成し、その後に第２の被覆材を貼り合わせてもよい。 If neither the first coating material nor the second coating material can transmit the active energy rays, the coating film is irradiated with the active energy rays before the second coating material is bonded to form a cured product layer. May be formed, and then a second covering material may be attached.
≪バックライトユニット≫
　本開示のバックライトユニットは、光源と、本開示の波長変換部材と、を有する。 ≪Backlight unit≫
The backlight unit of the present disclosure includes a light source and a wavelength conversion member of the present disclosure.
　バックライトユニットとしては、色再現性を向上させる観点から、多波長光源化されたものが好ましい。好ましい一態様としては、４３０ｎｍ～４８０ｎｍの波長域に発光中心波長を有し、半値幅が１００ｎｍ以下である発光強度ピークを有する青色光と、５２０ｎｍ～５６０ｎｍの波長域に発光中心波長を有し、半値幅が１００ｎｍ以下である発光強度ピークを有する緑色光と、６００ｎｍ～６８０ｎｍの波長域に発光中心波長を有し、半値幅が１００ｎｍ以下である発光強度ピークを有する赤色光と、を発光するバックライトユニットを挙げることができる。なお、発光強度ピークの半値幅とは、ピーク高さの１／２の高さにおけるピーク幅を意味する。 The backlight unit is preferably a multi-wavelength light source from the viewpoint of improving color reproducibility. In a preferred embodiment, blue light having an emission center wavelength in the wavelength range of 430 nm to 480 nm and having an emission intensity peak having a half-value width of 100 nm or less, and emission center wavelength in the wavelength range of 520 nm to 560 nm. A back that emits green light having an emission intensity peak having a half-value width of 100 nm or less and red light having an emission center wavelength in the wavelength range of 600 nm to 680 nm and having an emission intensity peak having a half-value width of 100 nm or less. The light unit can be mentioned. The half-value width of the emission intensity peak means the peak width at a height of 1/2 of the peak height.
　色再現性をより向上させる観点から、バックライトユニットが発光する青色光の発光中心波長は、４４０ｎｍ～４７５ｎｍの範囲であることが好ましい。同様の観点から、バックライトユニットが発光する緑色光の発光中心波長は、５２０ｎｍ～５４５ｎｍの範囲であることが好ましい。また、同様の観点から、バックライトユニットが発光する赤色光の発光中心波長は、６１０ｎｍ～６４０ｎｍの範囲であることが好ましい。 From the viewpoint of further improving the color reproducibility, the emission center wavelength of the blue light emitted by the backlight unit is preferably in the range of 440 nm to 475 nm. From the same viewpoint, the emission center wavelength of the green light emitted by the backlight unit is preferably in the range of 520 nm to 545 nm. From the same viewpoint, the emission center wavelength of the red light emitted by the backlight unit is preferably in the range of 610 nm to 640 nm.
　また、色再現性をより向上させる観点から、バックライトユニットが発光する青色光、緑色光、及び赤色光の各発光強度ピークの半値幅は、いずれも８０ｎｍ以下であることが好ましく、５０ｎｍ以下であることがより好ましく、４０ｎｍ以下であることがさらに好ましく、３０ｎｍ以下であることが特に好ましく、２５ｎｍ以下であることが極めて好ましい。 Further, from the viewpoint of further improving the color reproducibility, the half-value width of each emission intensity peak of the blue light, green light, and red light emitted by the backlight unit is preferably 80 nm or less, preferably 50 nm or less. It is more preferably 40 nm or less, particularly preferably 30 nm or less, and extremely preferably 25 nm or less.
　バックライトユニットの光源としては、例えば、４３０ｎｍ～４８０ｎｍの波長域に発光中心波長を有する青色光を発光する光源を用いることができる。光源としては、例えば、ＬＥＤ（Ｌｉｇｈｔ　Ｅｍｉｔｔｉｎｇ　Ｄｉｏｄｅ）及びレーザーが挙げられる。青色光を発光する光源を用いる場合、波長変換部材は、少なくとも、赤色光を発光する量子ドット蛍光体Ｒ及び緑色光を発光する量子ドット蛍光体Ｇを含むことが好ましい。これにより、波長変換部材から発光される赤色光及び緑色光と、波長変換部材を透過した青色光とにより、白色光を得ることができる。 As the light source of the backlight unit, for example, a light source that emits blue light having a emission center wavelength in the wavelength range of 430 nm to 480 nm can be used. Examples of the light source include an LED (Light Emitting Diode) and a laser. When a light source that emits blue light is used, the wavelength conversion member preferably includes at least a quantum dot phosphor R that emits red light and a quantum dot phosphor G that emits green light. As a result, white light can be obtained from the red light and green light emitted from the wavelength conversion member and the blue light transmitted through the wavelength conversion member.
　また、バックライトユニットの光源としては、例えば、３００ｎｍ～４３０ｎｍの波長域に発光中心波長を有する紫外光を発光する光源を用いることもできる。光源としては、例えば、ＬＥＤ及びレーザーが挙げられる。紫外光を発光する光源を用いる場合、波長変換部材は、量子ドット蛍光体Ｒ及び量子ドット蛍光体Ｇとともに、励起光により励起され青色光を発光する量子ドット蛍光体Ｂを含むことが好ましい。これにより、波長変換部材から発光される赤色光、緑色光、及び青色光により、白色光を得ることができる。 Further, as the light source of the backlight unit, for example, a light source that emits ultraviolet light having a emission center wavelength in the wavelength range of 300 nm to 430 nm can be used. Examples of the light source include LEDs and lasers. When a light source that emits ultraviolet light is used, the wavelength conversion member preferably includes a quantum dot phosphor B that is excited by excitation light and emits blue light, together with a quantum dot phosphor R and a quantum dot phosphor G. As a result, white light can be obtained from the red light, green light, and blue light emitted from the wavelength conversion member.
　本開示のバックライトユニットは、エッジライト方式であっても直下型方式であってもよい。 The backlight unit of the present disclosure may be an edge light type or a direct type.
　エッジライト方式のバックライトユニットの概略構成の一例を図２に示す。 Fig. 2 shows an example of the schematic configuration of the edge light type backlight unit.
　図２に示すバックライトユニット２０は、青色光ＬＢを出射する光源２１と、光源２１から出射された青色光ＬＢを導光して出射させる導光板２２と、導光板２２と対向配置される波長変換部材１０と、波長変換部材１０を介して導光板２２と対向配置される再帰反射性部材２３と、導光板２２を介して波長変換部材１０と対向配置される反射板２４とを備える。波長変換部材１０は、青色光ＬＢの一部を励起光として赤色光ＬＲ及び緑色光ＬＧを発光し、赤色光ＬＲ及び緑色光ＬＧと、励起光とならなかった青色光ＬＢとを出射する。この赤色光ＬＲ、緑色光ＬＧ、及び青色光ＬＢにより、再帰反射性部材２３から白色光ＬＷが出射される。 The backlight unit 20 shown in FIG. 2 includes a light source 21 for emitting the blue light L B, a light guide plate 22 to be emitted guiding the blue light L B emitted from the light source 21, the light guide plate 22 and disposed to face The wavelength conversion member 10 is provided with a retroreflective member 23 arranged to face the light source plate 22 via the wavelength conversion member 10, and a reflection plate 24 arranged to face the wavelength conversion member 10 via the light guide plate 22. .. Wavelength conversion member 10 emits the red light L R and the green light L G part of the blue light L B as the excitation light, the red light L and R and the green light L G, the blue light was not the excitation light L B is emitted. The red light L R, the green light L G, and the blue light L B, the white light L W is emitted from the retroreflective member 23.
≪画像表示装置≫
　本開示の画像表示装置は、上述した本開示のバックライトユニットを備える。画像表示装置としては特に制限されず、例えば、液晶表示装置が挙げられる。 ≪Image display device≫
The image display device of the present disclosure includes the backlight unit of the present disclosure described above. The image display device is not particularly limited, and examples thereof include a liquid crystal display device.
　液晶表示装置の概略構成の一例を図３に示す。 FIG. 3 shows an example of the schematic configuration of the liquid crystal display device.
　図３に示す液晶表示装置３０は、バックライトユニット２０と、バックライトユニット２０と対向配置される液晶セルユニット３１とを備える。液晶セルユニット３１は、液晶セル３２が偏光板３３Ａと偏光板３３Ｂとの間に配置された構成とされる。 The liquid crystal display device 30 shown in FIG. 3 includes a backlight unit 20 and a liquid crystal cell unit 31 arranged to face the backlight unit 20. The liquid crystal cell unit 31 has a configuration in which the liquid crystal cell 32 is arranged between the polarizing plate 33A and the polarizing plate 33B.
　液晶セル３２の駆動方式は特に制限されず、ＴＮ（Ｔｗｉｓｔｅｄ　Ｎｅｍａｔｉｃ）方式、ＳＴＮ（Ｓｕｐｅｒ　Ｔｗｉｓｔｅｄ　Ｎｅｍａｔｉｃ）方式、ＶＡ（Ｖｅｒｔｉｃａｌ　Ａｌｉｇｎｍｅｎｔ）方式、ＩＰＳ（Ｉｎ－Ｐｌａｎｅ－Ｓｗｉｔｃｈｉｎｇ）方式、ＯＣＢ（Ｏｐｔｉｃａｌｌｙ　Ｃｏｍｐｅｎｓａｔｅｄ　Ｂｉｒｅｆｒｉｎｇｅｎｃｅ）方式等が挙げられる。 The drive method of the liquid crystal cell 32 is not particularly limited, and is a TN (Twisted Nematic) method, an STN (Super Twisted Nematic) method, a VA (Vertical Birefringence) method, an IPS (In-Plane-Switching) method, an OCB (Optical Birefringence) method. The method and the like can be mentioned.
　次に本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Next, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
＜実施例及び比較例＞
（硬化性組成物の調製）
　表１に示す各成分を同表に示す配合量（単位：質量部）で混合することにより、実施例及び比較例の硬化性組成物をそれぞれ調製した。 <Examples and Comparative Examples>
(Preparation of curable composition)
The curable compositions of Examples and Comparative Examples were prepared by mixing each component shown in Table 1 in the blending amount (unit: parts by mass) shown in the same table.
　なお、（メタ）アクリル化合物としては、トリシクロデカンジメタノールジアクリレート（新中村化学工業株式会社、Ａ－ＤＣＰ）及びエトキシ化ビスフェノールＡジアクリレート（新中村化学工業株式会社、ＡＢＥ－３００；アルキレンオキシ基を含有する化合物）を用いた。 Examples of the (meth) acrylic compound include tricyclodecanedimethanol diacrylate (Shin-Nakamura Chemical Industry Co., Ltd., A-DCP) and ethoxylated bisphenol A diacrylate (Shin-Nakamura Chemical Industry Co., Ltd., ABE-300; alkyleneoxy). A group-containing compound) was used.
　チオール化合物として、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）（ＳＣ有機化学株式会社、ＰＥＭＰ）を用いた。 As the thiol compound, pentaerythritol tetrakis (3-mercaptopropionate) (SC Organic Chemistry Co., Ltd., PEMP) was used.
　光重合開始剤としては、２，４，６－トリメチルベンゾイル－ジフェニル－ホスフィンオキサイド（ＢＡＳＦ社、ＩＲＧＡＣＵＲＥ　ＴＰＯ）を用いた。 As the photopolymerization initiator, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (BASF, IRGACURE TPO) was used.
　量子ドット蛍光体分散液としては、ＣｄＳｅ／ＺｎＳ（コア／シェル）分散液（Ｎａｎｏｓｙｓ社、Ｇｅｎ３．５　ＱＤ　Ｃｏｎｃｅｎｔｒａｔｅ）を用いた。このＣｄＳｅ／ＺｎＳ（コア／シェル）分散液の分散媒体としては、イソボルニルアクリレート（ＩＢＯＡ）を使用した。ＣｄＳｅ／ＺｎＳ（コア／シェル）分散液中に、イソボルニルアクリレートが８６質量％以上含有されている。 As the quantum dot phosphor dispersion liquid, a CdSe / ZnS (core / shell) dispersion liquid (Nanosys, Gen3.5 QD Concentrate) was used. Isobornyl acrylate (IBOA) was used as the dispersion medium for the CdSe / ZnS (core / shell) dispersion. The CdSe / ZnS (core / shell) dispersion contains 86% by mass or more of isobornyl acrylate.
　カルボン酸として、酢酸を用いた。 Acetic acid was used as the carboxylic acid.
　光拡散材として、酸化チタン（Ｃｈｅｍｏｕｒｓ社、タイピュア　Ｒ－７０６、粒子径０．３６μｍ）を用いた。酸化チタンの表面には、酸化ケイ素を含む第一金属酸化物層、酸化アルミニウムを含む第二金属酸化物層及びポリオール化合物を含む有機物層が、第一金属酸化物層、第二金属酸化物層及び有機物層の順に設けられている。 Titanium oxide (The Chemours Company, Typure R-706, particle size 0.36 μm) was used as the light diffusing material. On the surface of titanium oxide, a first metal oxide layer containing silicon oxide, a second metal oxide layer containing aluminum oxide, and an organic substance layer containing a polyol compound are formed as a first metal oxide layer and a second metal oxide layer. And the organic layer are provided in this order.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
（波長変換部材の製造）
　以下の３種の異なるバリアフィルムのいずれかに、上記で得られた各硬化性組成物を７０μｍ～９０μｍの厚みで塗布して塗膜を形成した。用いられた硬化性組成物及び波長変換層の厚み、並びにバリアフィルムの種類を表２に示す。
バリアフィルム１：平均厚み７５μｍのバリアフィルム（ＰＥＴフィルムの片側にバリア成分を蒸着したもの）
バリアフィルム２：平均厚み２５μｍのバリアフィルム（ＰＥＴフィルムの片側にバリア成分をスパッタしたもの）
バリアフィルム３：平均厚み１０３μｍのバリアフィルム（ＰＥＴフィルムの片側にバリア成分を塗布したもの）
　この塗膜上に、上記塗膜が形成されたバリアフィルムと同じバリアフィルムを貼り合わせ、紫外線照射装置（アイグラフィックス株式会社）を用いて紫外線を照射（照射量：１０００ｍＪ／ｃｍ２）することにより、樹脂硬化物を含む波長変換層の両面に被覆材が配置された波長変換部材をそれぞれ得た。 (Manufacturing of wavelength conversion member)
Each of the curable compositions obtained above was applied to any of the following three different barrier films to a thickness of 70 μm to 90 μm to form a coating film. Table 2 shows the curable composition used, the thickness of the wavelength conversion layer, and the type of barrier film.
Barrier film 1: Barrier film with an average thickness of 75 μm (a PET film with a barrier component deposited on one side)
Barrier film 2: Barrier film with an average thickness of 25 μm (a PET film sputtered with a barrier component on one side)
Barrier film 3: Barrier film with an average thickness of 103 μm (a PET film coated on one side with a barrier component)
The same barrier film as the barrier film on which the coating film is formed is attached onto this coating film, and ultraviolet rays are irradiated using an ultraviolet irradiation device (Igraphics Co., Ltd.) (irradiation amount: 1000 mJ / cm 2 ). As a result, wavelength conversion members in which coating materials were arranged on both sides of the wavelength conversion layer containing the cured resin product were obtained.
（熱膨張係数）
　上記で得られた波長変換部材を幅４ｍｍ、長さ３０ｍｍの寸法に裁断して評価用硬化物を得た。そして、熱機械分析（ＴＭＡ）装置（ＴＡインスツルメンツ社製、商品名：Ｑ４００）を用いて引張法で熱機械分析を行った。熱機械分析は、前記装置に評価用硬化物をＭＤ方向に装着後、荷重０．０５Ｎ、昇温速度１０℃／分の条件で連続して２回行い、２回目の分析における３０℃から５０℃及び１２０℃から１４０℃の平均熱膨張率を算出し、これを熱膨張係数の値とした。
　また、バリアフィルムについても熱機械分析（ＴＭＡ）装置を用いて同様に熱膨張係数を測定した。 (Coefficient of thermal expansion)
The wavelength conversion member obtained above was cut into dimensions having a width of 4 mm and a length of 30 mm to obtain a cured product for evaluation. Then, thermomechanical analysis was performed by a tensile method using a thermomechanical analysis (TMA) device (manufactured by TA Instruments, trade name: Q400). The thermomechanical analysis is performed twice in succession under the conditions of a load of 0.05 N and a heating rate of 10 ° C./min after mounting the cured product for evaluation in the device in the MD direction, and the thermomechanical analysis is performed from 30 ° C. to 50 in the second analysis. The average coefficient of thermal expansion from ° C. and 120 ° C. to 140 ° C. was calculated and used as the value of the coefficient of thermal expansion.
The coefficient of thermal expansion of the barrier film was similarly measured using a thermomechanical analysis (TMA) device.
（ガラス転移温度、貯蔵弾性率、及び損失正接（ｔａｎδ））
　上記で得られた各波長変換部材を幅５ｍｍ、長さ４０ｍｍの寸法に裁断して評価用硬化物を得た。そして、動的粘弾性測定装置（Ｒｈｅｏｍｅｔｒｉｃ　Ｓｃｉｅｎｔｉｆｉｃ社、Ｓｏｌｉｄ　Ａｎａｌｙｚｅｒ　ＲＳＡ－ＩＩＩ）を用いて、「引張モード、チャック間距離：２５ｍｍ、周波数：１０Ｈｚ、測定温度範囲：－２０℃～１８０℃、昇温速度：１０℃／分」の条件で、評価用硬化物の貯蔵弾性率（Ｅ’）、及び損失弾性率（Ｅ’’）を測定し、その比から損失正接（ｔａｎδ）を求めた。損失正接（ｔａｎδ）のピークトップ部分の温度からガラス転移温度（Ｔｇ）を求めた。
　また、バリアフィルムのガラス転移温度についても同様に測定した。 (Glass transition temperature, storage modulus, and loss tangent (tan δ))
Each wavelength conversion member obtained above was cut into dimensions having a width of 5 mm and a length of 40 mm to obtain a cured product for evaluation. Then, using a dynamic elastic modulus measuring device (Rheometric Scientific, Solid Analyzer RSA-III), "tensile mode, interchuck distance: 25 mm, frequency: 10 Hz, measurement temperature range: -20 ° C to 180 ° C, temperature rise. The storage elastic modulus (E') and the loss elastic modulus (E'') of the cured product for evaluation were measured under the condition of "velocity: 10 ° C./min", and the loss tangent (tan δ) was determined from the ratio. The glass transition temperature (Tg) was determined from the temperature of the peak top portion of the loss tangent (tan δ).
The glass transition temperature of the barrier film was also measured in the same manner.
（特定値）
　上記で得られた各波長変換部材を幅２０ｍｍ、長さ２０ｃｍの寸法に裁断して評価用の波長変換部材を得た。高さが１０ｃｍ以上ある台に、加工した波長変換部材の一方の端が台から外側に１０ｃｍはみ出すように固定し、はみ出させた波長変換部材の先端が台の水平面に対して何ｍｍ下方にあるか測定した。測定された特定値を表２に示す。 (Specific value)
Each wavelength conversion member obtained above was cut into dimensions having a width of 20 mm and a length of 20 cm to obtain a wavelength conversion member for evaluation. One end of the processed wavelength conversion member is fixed to a table having a height of 10 cm or more so as to protrude 10 cm from the table, and the tip of the protruding wavelength conversion member is several mm below the horizontal plane of the table. Was measured. The measured specific values are shown in Table 2.
〔評価〕
（カール量）
　上記で得られた各波長変換部材を直径６インチの巻き芯に巻き付けて２５℃で１０００時間静置した後、１４７０ｍｍ×８５０ｍｍの矩形に打ち抜き加工し、これを５０枚重ねてガラス板に挟み、４５℃で２４時間、６０℃で４時間、６０℃で１０時間、又は８５℃で４時間静置して評価用の波長変換部材を得た。カール量（反り量）は、打ち抜き加工された波長変換部材の端部６点にて測定したときの最大値とする。結果を表２に示す。 〔evaluation〕
(Curl amount)
Each wavelength conversion member obtained above was wound around a winding core having a diameter of 6 inches, allowed to stand at 25 ° C. for 1000 hours, punched into a rectangle of 1470 mm × 850 mm, and 50 sheets were stacked and sandwiched between glass plates. A wavelength conversion member for evaluation was obtained by allowing to stand at 45 ° C. for 24 hours, 60 ° C. for 4 hours, 60 ° C. for 10 hours, or 85 ° C. for 4 hours. The curl amount (warp amount) is the maximum value measured at 6 points at the ends of the punched wavelength conversion member. The results are shown in Table 2.
（光学特性）
　上記で得られた各波長変換部材を直径６インチの巻き芯に巻き付けて２５℃で１０００時間静置した後、１４７０ｍｍ×８５０ｍｍの矩形に打ち抜き加工し、分光放射計（ＰＨＯＴＯ ＲＥＳＥＡＲＣＨ社、ＰＲ－６５５）を用いて輝度を測定した。
　輝度を測定した後、打ち抜き加工した各波長変換部材を５０枚重ねてガラス板に挟み、４５℃で２４時間、６０℃で４時間、６０℃で１０時間、又は８５℃で４時間静置し、分光放射計（ＰＨＯＴＯ ＲＥＳＥＡＲＣＨ社、ＰＲ－６５５）を用いて輝度を再度測定し、１回目と２回目の測定で得られた輝度、及びＷｈｉｔｅ　Ｐｏｉｎｔの差分を評価した。結果を表２に示す。表２において、Ｗｈｉｔｅ　ｐｏｉｎｔｅの差分が±０．００１以内、かつ輝度の低下が３％以下であった場合にＡと表示し、これ以外の場合にＢと表示する。　 (optical properties)
Each wavelength conversion member obtained above is wound around a winding core having a diameter of 6 inches, allowed to stand at 25 ° C. for 1000 hours, punched into a rectangle of 1470 mm × 850 mm, and a spectroradiometer (PHOTO RESEARCH, PR-655). ) Was used to measure the brightness.
After measuring the brightness, 50 punched wavelength conversion members were stacked and sandwiched between glass plates, and allowed to stand at 45 ° C. for 24 hours, 60 ° C. for 4 hours, 60 ° C. for 10 hours, or 85 ° C. for 4 hours. , The brightness was measured again using a spectroradiometer (PHOTO RESEARCH, PR-655), and the difference between the brightness obtained in the first and second measurements and the white point was evaluated. The results are shown in Table 2. In Table 2, when the difference between the White points is within ± 0.001 and the decrease in brightness is 3% or less, A is displayed, and in other cases, B is displayed.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２から分かるように、実施例においては、４５℃で２４時間、６０℃で４時間、及び６０℃で１０時間のいずれの条件でもカール量が抑制されており、且つ光学特性の変化も抑制されていた。なお、８５℃で４時間の条件では、実施例及び比較例においてカール量が少なかったが、光学特性の変化が観察された。 As can be seen from Table 2, in the examples, the curl amount was suppressed under any of the conditions of 45 ° C. for 24 hours, 60 ° C. for 4 hours, and 60 ° C. for 10 hours, and the change in optical characteristics was also suppressed. It had been. Under the condition of 85 ° C. for 4 hours, the amount of curl was small in Examples and Comparative Examples, but a change in optical characteristics was observed.
　本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に援用されて取り込まれる。 All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Incorporated herein by reference.
　１０…波長変換部材
　１１…波長変換層
　１２Ａ…被覆材
　１２Ｂ…被覆材
　２０…バックライトユニット
　２１…光源
　２２…導光板　
　２３…再帰反射性部材
　２４…反射板
　３０…液晶表示装置
　３１…液晶セルユニット
　３２…液晶セル
　３３Ａ…偏光板
　３３Ｂ…偏光板
　ＬＢ…青色光
　ＬＲ…赤色光
　ＬＧ…緑色光
　ＬＷ…白色光 10 ... Wavelength conversion member 11 ... Wavelength conversion layer 12A ... Coating material 12B ... Coating material 20 ... Backlight unit 21 ... Light source 22 ... Light guide plate
23 ... retroreflective member 24 ... reflector 30 ... liquid crystal display device 31 ... liquid crystal cell unit 32 ... liquid crystal cell 33A ... polarizing plate 33B ... polarizing plate L B ... blue light L R ... red light L G ... green light L W ... White light

Claims (11)

  1. 　蛍光体を含む波長変換層を有し、熱機械分析装置で荷重０．０５Ｎ、昇温速度１０℃／分の条件で測定したときのガラス転移温度以下での熱膨張係数が３０ｐｐｍ／℃以上であるか、ガラス転移温度以上での熱膨張係数が０ｐｐｍ／℃以下であるか、又はこれらの両方を満たす、波長変換部材。 It has a wavelength conversion layer containing a phosphor, and has a coefficient of thermal expansion of 30 ppm / ° C or higher below the glass transition temperature when measured with a thermomechanical analyzer under the conditions of a load of 0.05 N and a heating rate of 10 ° C / min. A wavelength conversion member having a coefficient of thermal expansion above the glass transition temperature of 0 ppm / ° C. or less, or satisfying both of these.
  2. 　前記波長変換部材が、前記波長変換層の一方の面側又は両方の面側に配置される被覆材を含み、熱機械分析装置で荷重０．０５Ｎ、昇温速度１０℃／分の条件で測定したときの前記被覆材のガラス転移温度以上での熱膨張係数が０ｐｐｍ／℃以下である請求項１に記載の波長変換部材。 The wavelength conversion member includes a coating material arranged on one surface side or both surface sides of the wavelength conversion layer, and is measured by a thermomechanical analyzer under the conditions of a load of 0.05 N and a heating rate of 10 ° C./min. The wavelength conversion member according to claim 1, wherein the thermal expansion coefficient of the coating material at the glass transition temperature or higher is 0 ppm / ° C. or lower.
  3. 　前記波長変換部材が被覆材を含み、前記波長変換部材のガラス転移温度以下での熱膨張係数から、熱機械分析装置で荷重０．０５Ｎ、昇温速度１０℃／分の条件で測定したときの前記被覆材のガラス転移温度以下での熱膨張係数を引いた値が１０ｐｐｍ／℃以上である、請求項１又は請求項２に記載の波長変換部材。 When the wavelength conversion member contains a coating material and is measured from the coefficient of thermal expansion of the wavelength conversion member below the glass transition temperature under the conditions of a load of 0.05 N and a temperature rise rate of 10 ° C./min with a thermomechanical analyzer. The wavelength conversion member according to claim 1 or 2, wherein the value obtained by subtracting the coefficient of thermal expansion below the glass transition temperature of the coating material is 10 ppm / ° C. or higher.
  4. 　動的粘弾性測定装置で周波数１０Ｈｚかつ温度３０℃の条件で測定したときの貯蔵弾性率が３．７ＧＰａ以下である、請求項１～請求項３のいずれか１項に記載の波長変換部材。 The wavelength conversion member according to any one of claims 1 to 3, wherein the storage elastic modulus when measured with a dynamic viscoelasticity measuring device under the conditions of a frequency of 10 Hz and a temperature of 30 ° C. is 3.7 GPa or less.
  5. 　以下の方法により測定される値が６．０ｍｍ以上である、請求項１～請求項４のいずれか１項に記載の波長変換部材：
    　試験台上に、幅２０ｍｍの矩形に加工された前記波長変換部材を、前記試験台から外側に、長さ１０ｃｍ突出するように配置し、自重で下垂した前記波長変換部材の先端部の高さと、前記試験台の基準面の高さと、の距離を測定する。     The wavelength conversion member according to any one of claims 1 to 4, wherein the value measured by the following method is 6.0 mm or more.
    The wavelength conversion member processed into a rectangle having a width of 20 mm is arranged on the test table so as to project outward by 10 cm in length from the test table, and the height of the tip portion of the wavelength conversion member that hangs down by its own weight. , Measure the distance from the height of the reference plane of the test stand.
  6. 　前記蛍光体が量子ドット蛍光体を含む、請求項１～請求項５のいずれか１項に記載の波長変換部材。 The wavelength conversion member according to any one of claims 1 to 5, wherein the phosphor includes a quantum dot phosphor.
  7. 　前記量子ドット蛍光体がＣｄ及びＩｎの少なくとも一方を含む、請求項６に記載の波長変換部材。 The wavelength conversion member according to claim 6, wherein the quantum dot phosphor contains at least one of Cd and In.
  8. 　前記波長変換層が、
    　前記蛍光体と、
    　チオール化合物と、
    　（メタ）アクリル化合物及び（メタ）アリル化合物からなる群より選択される少なくとも１種と、
    　光重合開始剤と、
    を含有する樹脂組成物の硬化物を含む、請求項１～請求項７のいずれか１項に記載の波長変換部材。     The wavelength conversion layer
    With the phosphor
    With thiol compounds
    At least one selected from the group consisting of (meth) acrylic compounds and (meth) allyl compounds, and
    Photopolymerization initiator and
    The wavelength conversion member according to any one of claims 1 to 7, which comprises a cured product of a resin composition containing.
  9. 　ロール状に形成されている、請求項１～請求項８のいずれか１項に記載の波長変換部材。 The wavelength conversion member according to any one of claims 1 to 8, which is formed in a roll shape.
  10. 　請求項１～請求項８のいずれか１項に記載の波長変換部材と、光源と、を備えるバックライトユニット。 A backlight unit including the wavelength conversion member according to any one of claims 1 to 8 and a light source.
  11. 　請求項１０に記載のバックライトユニットを備える画像表示装置。 An image display device including the backlight unit according to claim 10.
PCT/JP2020/003220 2020-01-29 2020-01-29 Wavelength conversion member, backlight unit, and image display device WO2021152737A1 (en)

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