WO2018047758A1 - 波長変換シート、積層体および発光装置、並びに、波長変換シートの製造方法 - Google Patents

波長変換シート、積層体および発光装置、並びに、波長変換シートの製造方法 Download PDF

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Publication number
WO2018047758A1
WO2018047758A1 PCT/JP2017/031730 JP2017031730W WO2018047758A1 WO 2018047758 A1 WO2018047758 A1 WO 2018047758A1 JP 2017031730 W JP2017031730 W JP 2017031730W WO 2018047758 A1 WO2018047758 A1 WO 2018047758A1
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Prior art keywords
wavelength conversion
silicone resin
conversion sheet
formula
structural unit
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PCT/JP2017/031730
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English (en)
French (fr)
Japanese (ja)
Inventor
建太朗 増井
篤典 土居
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Priority to EP17848698.1A priority Critical patent/EP3511611A4/en
Priority to CN201780054505.8A priority patent/CN109690367A/zh
Priority to KR1020197009938A priority patent/KR20190041020A/ko
Priority to US16/330,427 priority patent/US20210284903A1/en
Publication of WO2018047758A1 publication Critical patent/WO2018047758A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7774—Aluminates
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • F21V7/00—Reflectors for light sources
    • F21V7/04—Optical design
    • 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
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/0001—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
    • G02B6/0005—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being of the fibre type
    • G02B6/0008—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being of the fibre type the light being emitted at the end of the fibre
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/851—Wavelength conversion means
    • H10H20/8511—Wavelength conversion means characterised by their material, e.g. binder
    • H10H20/8512—Wavelength conversion materials

Definitions

  • the present invention relates to a wavelength conversion sheet, a laminate, a light emitting device, and a method for manufacturing the wavelength conversion sheet.
  • Semiconductor lasers (LD, Laser Diode) can maintain high conversion efficiency even in a high current density region.
  • the semiconductor laser can be downsized by separating the light emitting portion and the excitation portion. Therefore, it is expected that a semiconductor laser is used for the lighting device.
  • the emission spectrum of a semiconductor laser depends on the semiconductor material that is the material for forming the semiconductor laser.
  • a semiconductor laser emits all three colors of RGB (the former method), an LD element and a wavelength conversion material are placed, and the wavelength conversion material is irradiated with light emitted from the LD element to convert the emission wavelength.
  • a method of obtaining white light (the latter method) is adopted. Since the latter method is suitable for downsizing of the apparatus, development for applications such as projectors is being studied.
  • the emission spectrum of a light emitting diode also depends on the semiconductor material that is the material for forming the light emitting diode.
  • LED Light Emitting Diode
  • a light-emitting device that obtains white light using a light-emitting diode a light-emitting device in which a sheet containing phosphor as a wavelength conversion material (hereinafter referred to as “phosphor sheet”) is disposed on a light-emitting surface of an LED element is known. (For example, see Patent Document 1).
  • the phosphor sheet described in Patent Document 1 has insufficient heat resistance. Specifically, when the phosphor sheet described in Patent Document 1 is applied to a phosphor sheet of a semiconductor light emitting device using a high-power LD element, the phosphor sheet generates heat due to high-energy light irradiation. In some cases, the resin contained deteriorates and cracks, coloring, wrinkles, etc. occur in the phosphor sheet. For this reason, a wavelength conversion sheet having excellent heat resistance has been demanded.
  • This invention is made
  • the present invention provides the following [1] to [11].
  • a condensed silicone resin cured product and a wavelength conversion material The storage elastic modulus at 25 ° C. is 2 GPa or more and 10 GPa or less, The wavelength conversion sheet whose storage elastic modulus in 150 degreeC is 0.1 GPa or more and 5 GPa or less.
  • the content of the condensed silicone resin cured product is 5% by mass or more and 80% by mass or less based on the total content of the condensed silicone resin cured product and the wavelength conversion material.
  • R 1 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.
  • the cured silicone resin cured product comprises a structural unit represented by the following formula (A1), a structural unit represented by the following formula (A1 ′), and a structural unit represented by the following formula (A2).
  • Sheet. [In Formula (A1), Formula (A1 ′) and Formula (A2), R 1 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.
  • R 2 represents an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group.
  • a plurality of R 1 and R 2 may be the same or different.
  • the content of the structural unit represented by the formula (A3) contained in the condensed silicone resin cured product is based on the total content of all the structural units contained in the condensed silicone resin cured product.
  • a second molded body after the first heating step is cured by leaving it in an atmosphere heated from 120 ° C. to 150 ° C. so as to satisfy the requirement of 1.01 ⁇ C / B ⁇ 1.30.
  • a manufacturing method of a wavelength conversion sheet including a heating process.
  • D represents the mass of the molded body before the first heating step.
  • E represents the mass of the molded body after the first heating step.
  • B represents the content of the structural unit represented by the formula (A3) with respect to the total content of all the structural units contained in the molded body after the first heating step.
  • C represents the content of the structural unit represented by the formula (A3) with respect to the total content of all the structural units contained in the molded body after the second heating step.
  • the present invention it is possible to provide a wavelength conversion sheet having excellent heat resistance, a laminate including the wavelength conversion sheet, a light emitting device, and a method for manufacturing the wavelength conversion sheet.
  • the structural unit contained in the condensed silicone resin cured product is preferably contained in the condensed silicone resin cured product as a repeating unit.
  • the wavelength conversion sheet of the present embodiment includes a condensed silicone resin cured product and a wavelength conversion material.
  • the condensation type silicone resin used for the production of the wavelength conversion sheet of the present embodiment is a resin mixed with the wavelength conversion material, and can be formed into a sheet.
  • the condensed silicone resin cured product contained in the wavelength conversion sheet of the present embodiment is a resin having excellent heat resistance because it is less likely to cause wrinkles and cracks even when exposed to high temperatures.
  • Condensed silicone resin cured product A condensed silicone resin is used as a raw material for the condensed silicone resin cured product contained in the wavelength conversion sheet of the present embodiment. That is, the “condensed silicone resin cured product” is a cured product cured by a condensation reaction of the condensed silicone resin and does not have fluidity.
  • the condensation-type silicone resin is a resin that undergoes polycondensation by causing a dealcoholization reaction or a dehydration reaction between a hydroxyl group bonded to a silicon atom and an alkoxy group or hydroxyl group bonded to another silicon atom.
  • the specific gravity of the condensed silicone resin cured product contained in the wavelength conversion sheet of this embodiment is preferably 1.20 to 1.35.
  • the condensed silicone resin cured product contained in the wavelength conversion sheet of the present embodiment preferably includes a structural unit represented by the following formula (A3).
  • the condensed silicone resin cured product contained in the wavelength conversion sheet of the present embodiment includes a structural unit represented by the following formula (A1), a structural unit represented by the following formula (A1 ′), and the following formula (A2).
  • R 2 represents an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group. A plurality of R 1 and R 2 may be the same or different. ]
  • the condensed silicone resin cured product contained in the wavelength conversion sheet of the present embodiment includes a structural unit represented by the formula (A3), a structural unit represented by the formula (A1), and a structure represented by the formula (A1 ′). It is preferable that all of the unit and the structural unit represented by the formula (A2) are included.
  • a structural unit including a silicon atom bonded to three oxygen atoms is referred to as a “T body”.
  • a structural unit containing a silicon atom in which all of the three oxygen atoms are bonded to another silicon atom is referred to as a “T3 body”.
  • a structural unit containing a silicon atom in which two of the three oxygen atoms are bonded to another silicon atom is referred to as a “T2 body”.
  • a structural unit including a silicon atom in which one of the three oxygen atoms is bonded to another silicon atom is referred to as a “T1 body”. That is, “T body” means “T1 body”, “T2 body”, and “T3 body”.
  • a structural unit containing a silicon atom bonded to two oxygen atoms is referred to as “D-form”.
  • a structural unit containing a silicon atom bonded to one oxygen atom is referred to as an “M body”.
  • a structural unit containing a silicon atom bonded to four oxygen atoms is referred to as a “Q body”.
  • the structural unit represented by the formula (A3) includes three oxygen atoms bonded to other silicon atoms and a silicon atom bonded to R 1 . Since R 1 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, the structural unit represented by the formula (A3) is a T3 isomer.
  • the structural unit represented by the formula (A2) includes two oxygen atoms bonded to other silicon atoms, a silicon atom bonded to R 1 and R 2 . Since R 2 is an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group, the structural unit represented by the formula (A2) is a T2 isomer.
  • the structural unit represented by the formula (A1) includes one oxygen atom bonded to another silicon atom, a silicon atom bonded to R 1 and two R 2 atoms. Since R 1 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R 2 is an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group, the structural unit represented by the formula (A1) Is T1 body.
  • the structural unit represented by the formula (A1 ′) includes a silicon atom bonded to R 1 and two R 2, and the silicon atom is bonded to a silicon atom in another structural unit. It is bonded to an atom. Since R 1 is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R 2 is an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group, the structure represented by the formula (A1 ′) The unit is T1 body.
  • the structural unit represented by the formula (A1) and the structural unit represented by the formula (A1 ′) constitute an end of the organopolysiloxane chain contained in the condensed silicone resin cured product.
  • the structural unit represented by the formula (A3) constitutes a branched structure of an organopolysiloxane chain included in the condensed silicone resin cured product. That is, the structural unit represented by the formula (A3) forms a part of the network structure or the ring structure of the condensed silicone resin cured product.
  • T3 silicon atom A silicon atom contained in the T2 body is referred to as “T2 silicon atom”.
  • T1 silicon atom The silicon atom contained in the T1 body is referred to as “T1 silicon atom”.
  • the total content of the units and the structural unit represented by the formula (A2) is preferably 50 mol% or more, based on the total content of all the structural units contained in the condensed silicone resin cured product, 60 mol % Or more, more preferably 70 mol% or more, particularly preferably 80 mol% or more, and particularly preferably 90 mol% or more.
  • the total content of T1, T2, and T3 is the total content of all structural units contained in the condensed silicone resin cured product.
  • the amount is preferably 50 mol% or more, more preferably 60 mol% or more, further preferably 70 mol% or more, particularly preferably 80 mol% or more, and 90 mol%, based on the amount. It is even more preferable that it is at least%.
  • the total content of T1 silicon atoms, T2 silicon atoms, and T3 silicon atoms is the total silicon included in the condensed silicone resin cured product. It is preferably 50 mol% or more, more preferably 60 mol% or more, further preferably 70 mol% or more, and particularly preferably 80 mol% or more with respect to the total content of atoms. More preferably, it is 90 mol% or more.
  • the content of the structural unit represented by the formula (A3) is the total content of all structural units contained in the condensed silicone resin cured product.
  • it is preferably 50 mol% or more, more preferably 55 mol% or more, further preferably 60 mol% or more, particularly preferably 65 mol% or more, and 70 mol% or more. It is particularly preferred that
  • the content of the T3 body is 50 mol relative to the total content of all structural units contained in the condensed silicone resin cured product. %, More preferably 55 mol% or more, still more preferably 60 mol% or more, particularly preferably 65 mol% or more, and particularly preferably 70 mol% or more. Is preferable.
  • the content of T3 silicon atoms is relative to the total content of all silicon atoms contained in the condensed silicone resin cured product. It is preferably 50 mol% or more, more preferably 55 mol% or more, still more preferably 60 mol% or more, particularly preferably 65 mol% or more, and 70 mol% or more. Is even more preferred.
  • the content of the structural unit represented by the formula (A3) is within this range, the room temperature (25 ° C.) of the obtained wavelength conversion sheet. And the storage elastic modulus at a high temperature (150 ° C.) can be controlled within a desired range.
  • the content of D-form is 30 mol% or less with respect to the total content of all structural units contained in the condensed silicone resin cured product. It is preferably 20 mol% or less, more preferably 10 mol% or less, particularly preferably 5 mol% or less, and particularly preferably 4 mol% or less.
  • the content of the T3 silicon atom contained in the condensed silicone resin cured product is the total area of signals of all silicon atoms obtained in the solid 29 Si-NMR measurement, and excludes the area of signals attributed as T3 silicon atoms. Can be obtained.
  • the content of silicon atoms other than T3 silicon atoms can be determined in the same manner.
  • the alkyl group having 1 to 10 carbon atoms represented by R 1 may be a linear alkyl group, a branched alkyl group, or an alkyl group having a cyclic structure. Good. Among these, a linear or branched alkyl group is preferable, a linear alkyl group is more preferable, and a methyl group is further preferable.
  • one or more hydrogen atoms constituting the alkyl group may be substituted with another functional group.
  • substituent of the alkyl group include aryl groups having 6 to 10 carbon atoms such as a phenyl group and a naphthyl group, and a phenyl group is preferable.
  • Examples of the alkyl group having 1 to 10 carbon atoms represented by R 1 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, and an n-pentyl group. And an unsubstituted alkyl group such as a neopentyl group, a hexyl group, an octyl group, a nonyl group and a decyl group, and an aralkyl group such as a phenylmethyl group, a phenylethyl group and a phenylpropyl group.
  • a methyl group, an ethyl group, an n-propyl group, an isopropyl group or an n-butyl group is preferable, a methyl group, an ethyl group or an isopropyl group is more preferable, and a methyl group is still more preferable.
  • one or more hydrogen atoms constituting the aryl group may be substituted with another functional group.
  • substituent for the aryl group include alkyl groups having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group.
  • Examples of the aryl group having 6 to 10 carbon atoms represented by R 1 include an unsubstituted aryl group such as a phenyl group and a naphthyl group, and an alkylaryl group such as a methylphenyl group, an ethylphenyl group, and a propylphenyl group. Can be mentioned. Among these, a phenyl group is preferable.
  • R 1 is preferably an alkyl group, and a methyl group is preferable from the viewpoint of heat resistance.
  • the C 1-4 alkoxy group represented by R 2 may be a linear alkoxy group, a branched alkoxy group, or an alkoxy group having a cyclic structure. Good. Among these, a linear or branched alkoxy group is preferable, and a linear alkoxy group is more preferable.
  • Examples of the alkoxy group having 1 to 4 carbon atoms represented by R 2 include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, or a tert-butoxy group. From the viewpoint of balancing the stability and curability of the silicone resin composition of the present embodiment in a balanced manner, a methoxy group, an ethoxy group, or an isopropoxy group is preferable.
  • R 2 is preferably a methoxy group or a hydroxyl group.
  • the condensation type silicone resin cured product contained in the wavelength conversion sheet of the present embodiment includes the repeating unit represented by the above formula (A1), the above formula (A1 ′), the above formula (A2), and the above formula (A3).
  • R 1 is a methyl group and R 2 is independently an alkoxy group having 1 to 3 carbon atoms or a hydroxyl group.
  • the condensed silicone resin cured product contained in the wavelength conversion sheet of the present embodiment is represented by the following formula (C1), formula (C1 ′), formula (C2), formula (C3), or formula (C4).
  • a structural unit may be further included.
  • R 7 represents an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group. A plurality of R 7 may be the same or different.
  • a structural unit including a silicon atom bonded to four oxygen atoms is referred to as a “Q body”.
  • a structural unit containing a silicon atom in which one of the four oxygen atoms is bonded to another silicon atom is referred to as “Q1 body”.
  • the structural unit represented by the formula (C1) and the structural unit represented by the formula (C1 ′) are “Q1 bodies”.
  • a structural unit containing a silicon atom in which two of the four oxygen atoms are bonded to another silicon atom is referred to as “Q2 body”.
  • the structural unit represented by the formula (C2) is “Q2 body”.
  • a structural unit including a silicon atom in which three oxygen atoms among the four oxygen atoms are bonded to other silicon atoms is referred to as “Q3 body”.
  • the structural unit represented by the formula (C3) is “Q3 body”.
  • a structural unit containing a silicon atom in which all of the four oxygen atoms are bonded to another silicon atom is referred to as “Q4 body”.
  • the structural unit represented by the formula (C4) is “Q4 body”.
  • Q body means Q1, Q2, Q3 and Q4 bodies.
  • the content of the condensed silicone resin cured product is 5% by mass or more and 80% by mass or less with respect to the total content of the condensed silicone resin cured product and the wavelength conversion material. Is preferably 10% to 70% by mass, more preferably 15% to 60% by mass, and particularly preferably 20% to 50% by mass.
  • the conversion efficiency of the wavelength conversion sheet can be increased, and the storage elastic modulus at room temperature (25 ° C.) of the wavelength conversion sheet. And the storage elastic modulus at a high temperature (150 ° C.) can be controlled within a desired range.
  • the content of the condensed silicone resin cured product in the wavelength conversion sheet of the present embodiment is calculated by a value calculated from the charged amount of the condensation silicone resin, the wavelength conversion material and other raw materials, or by elemental analysis of the wavelength conversion sheet. be able to.
  • Examples of the wavelength conversion material included in the wavelength conversion sheet of the present embodiment include phosphors and quantum dots.
  • Examples of the phosphor include a red phosphor that emits fluorescence in the wavelength range of 570 nm to 700 nm, a green phosphor that emits fluorescence in the range of 490 nm to 570 nm, and a blue phosphor that emits fluorescence in the range of 420 nm to 480 nm. . Only one type of phosphor may be used alone, or two or more types may be used in combination.
  • red phosphor examples include europium-activated alkaline earth silicon nitride phosphors composed of fractured particles having a red fracture surface and represented by (Mg, Ca, Sr, Ba) 2 Si 5 N 8 : Eu.
  • a europium-activated rare earth oxychalcogenide phosphor composed of grown particles having a substantially spherical shape as a regular crystal growth shape and represented by (Y, La, Gd, Lu) 2 O 2 S: Eu;
  • red phosphors include fluorescence containing oxynitride and / or oxysulfide containing at least one element selected from the group consisting of Ti, Zr, Hf, Nb, Ta, W and Mo, or both. And phosphors containing an oxynitride having an alpha sialon structure in which a part or all of the Al element is substituted with a Ga element.
  • red phosphors include Eu-activated oxysulfide phosphors such as (La, Y) 2 O 2 S: Eu; Eu such as Y (V, P) O 4 : Eu, Y 2 O 3 : Eu Activated oxide phosphor; (Ba, Sr, Ca, Mg) 2 SiO 4 : Eu, Mn, (Ba, Mg) 2 SiO 4 : Eu, Mn activated silicate phosphor such as Eu, Mn; (Ca Sr) Eu: Eu-activated sulfide phosphors such as Eu; YAlO 3 : Eu-activated aluminate phosphors such as Eu; LiY 9 (SiO 4 ) 6 O 2 : Eu, Ca 2 Y 8 (SiO 4 ) 6 O 2 : Eu, (Sr, Ba, Ca) 3 SiO 5 : Eu, Sr 2 BaSiO 5 : Eu-activated silicate phosphor such as Eu; (Y, Gd) 3 Al 5
  • Eu, Ce-activated nitride phosphors such as (Ca, Sr, Ba, Mg) 10 (PO 4 ) 6 (F, Cl, Br, OH): Eu, Mn-activated halophosphoric acid such as Eu, Mn Salt phosphor; ((Y, Lu, Gd, Tb) 1-x Sc x Ce y ) 2 (Ca, Mg) 1-r (Mg, Zn) 2+ r Si z-q Ge q O 12 + ⁇ , etc.
  • Examples include silicate phosphors.
  • red phosphors include red organic phosphors composed of rare earth element ion complexes having an anion such as ⁇ -diketonate, ⁇ -diketone, aromatic carboxylic acid and Bronsted acid as ligands, and perylene pigments (for example, Dibenzo ⁇ [f, f ′]-4,4 ′, 7,7′-tetraphenyl ⁇ diindeno [1,2,3-cd: 1 ′, 2 ′, 3′-lm] perylene), anthraquinone pigment, Lake pigments, azo pigments, quinacridone pigments, anthracene pigments, isoindoline pigments, isoindolinone pigments, phthalocyanine pigments, triphenylmethane basic dyes, indanthrone pigments, indophenol pigments, Examples thereof include cyanine pigments and dioxazine pigments.
  • perylene pigments for example, Dibenzo ⁇ [f, f
  • a red phosphor having a peak wavelength of fluorescence emission of 580 nm or more, preferably 590 nm or more and a peak wavelength of fluorescence emission of 620 nm or less, preferably 610 nm or less is suitable as an orange phosphor.
  • orange phosphors include (Sr, Ba) 3 SiO 5 : Eu, (Sr, Mg) 3 PO 4 ) 2 : Sn 2+ , and SrCaAlSiN 3 : Eu.
  • yellow phosphors include oxide-based, nitride-based, oxynitride-based, sulfide-based, and oxysulfide-based phosphors.
  • RE 3 M 5 O 12 Ce (where RE represents at least one element selected from the group consisting of Y, Tb, Gd, Lu and Sm, and M represents Al, Ga and Represents at least one element selected from the group consisting of Sc), M 2 3 M 3 2 M 4 3 O 12 : Ce (where M 2 represents a divalent metal element, and M 3 represents trivalent).
  • M 4 represents a tetravalent metal element garnet phosphor having a garnet structure represented by like; AE 2 M 5 O 4: Eu ( here, AE is, Ba, Sr , And at least one element selected from the group consisting of Ca, Mg and Zn, and M 5 represents at least one element selected from the group consisting of Si and Ge.
  • Oxynitride-based phosphor obtained by substituting a part of oxygen atoms are formed elemental nitrogen atom; AEAlSiN 3: Ce (here, AE is at least 1 selected from the group consisting of Ba, Sr, Ca, Mg and Zn And phosphors activated with Ce such as a nitride-based phosphor having a CaAlSiN 3 structure.
  • yellow phosphors include sulfide phosphors such as CaGa 2 S 4 : Eu (Ca, Sr) Ga 2 S 4 : Eu, (Ca, Sr) (Ga, Al) 2 S 4 : Eu; Examples include phosphors activated with Eu such as oxynitride phosphors having a SiAlON structure such as x (Si, Al) 12 (O, N) 16 : Eu.
  • Green phosphor for example, a europium-activated alkaline earth silicon oxynitride fluorescent material composed of fractured particles having a fracture surface and represented by (Mg, Ca, Sr, Ba) Si 2 O 2 N 2 : Eu Body: Europium-activated alkaline earth silicate phosphors composed of fractured particles having a fractured surface and represented by (Ba, Ca, Sr, Mg) 2 SiO 4 : Eu.
  • green phosphors include Eu-activated aluminate phosphors such as Sr 4 Al 14 O 25 : Eu, (Ba, Sr, Ca) Al 2 O 4 : Eu; (Sr, Ba) Al 2 Si 2 O 8 : Eu, (Ba, Mg) 2 SiO 4 : Eu, (Ba, Sr, Ca, Mg) 2 SiO 4 : Eu, (Ba, Sr, Ca) 2 (Mg, Zn) Si 2 O 7 : Eu Eu activated silicate phosphor such as Y 2 SiO 5 : Ce, Tb activated silicate phosphor such as Ce, Tb; Eu activated such as Sr 2 P 2 O 7 —Sr 2 B 2 O 5 : Eu Borate phosphate phosphor; Sr 2 Si 3 O 8 -2SrCl 2 : Eu-activated halosilicate phosphor such as Eu; Zn 2 SiO 4 : Mn-activated silicate phosphor such as Mn; CeMgAl 11 O
  • green phosphors include pyridine-phthalimide condensed derivatives, benzoxazinone-based, quinazolinone-based, coumarin-based, quinophthalone-based, naltalimide-based fluorescent dyes; terbium complexes having hexyl salicylate as a ligand, etc. And organic phosphors.
  • a europium-activated barium magnesium aluminate phosphor composed of grown particles having a substantially hexagonal shape as a regular crystal growth shape and represented by BaMgAl 10 O 17 : Eu; a regular crystal growth shape A europium-activated calcium halophosphate phosphor expressed by (Ca, Sr, Ba) 5 (PO 4 ) 3 Cl: Eu; a substantially cubic shape as a regular crystal growth shape A europium-activated alkaline earth chloroborate-based phosphor represented by (Ca, Sr, Ba) 2 B 5 O 9 Cl: Eu; a fractured particle having a fracture surface (Sr , Ca, Ba) Al 2 O 4: Eu or (Sr, Ca, Ba) 4 Al 1 4O 25: Eu Europium-activated alkaline earth aluminate phosphors represented the like.
  • blue phosphors include Sn-activated phosphate phosphors such as Sr 2 P 2 O 7 : Sn; Sr 4 Al 14 O 25 : Eu, BaMgAl 10 O 17 : Eu, BaAl 8 O 13 : Eu, etc.
  • Eu-activated aluminate phosphors Ce-activated thiogallate phosphors such as SrGa 2 S 4 : Ce, CaGa 2 S 4 : Ce; (Ba, Sr, Ca) MgAl 10 O 17 : Eu, BaMgAl 10 O 17 : Eu-activated aluminate phosphor such as Eu, Tb, Sm; (Ba, Sr, Ca) MgAl 10 O 17 : Eu, Mn-activated aluminate phosphor such as Eu, Mn; (Sr, Ca, Ba, Mg) 10 (PO 4 ) 6 Cl 2 : Eu, (Ba, Sr, Ca) 5 (PO 4 ) 3 (Cl, F, Br, OH): Eu-activated halophosphoric acid such as Eu, Mn, Sb Salt phosphor; B Al 2 Si 2 O 8: Eu , (Sr, Ba) 3 MgSi 2 O 8: Eu -activated silicate phosphors
  • blue phosphors examples include fluorescent dyes such as naphthalic acid imide compounds, benzoxazole compounds, styryl compounds, coumarin compounds, pyrarizone compounds, triazole compounds, and organic phosphors such as thulium complexes. .
  • the average particle diameter of the wavelength conversion material contained in the wavelength conversion sheet of this embodiment is preferably 0.1 to 100 ⁇ m, more preferably 1 to 50 ⁇ m, and even more preferably 2 to 20 ⁇ m. If the average particle diameter of the wavelength conversion material is within this range, a more uniform wavelength conversion sheet is obtained.
  • the content of the wavelength conversion material is preferably 20% by mass to 95% by mass with respect to the total content of the condensed silicone resin cured product and the wavelength conversion material, It is more preferably 30% by mass or more and 90% by mass or less, further preferably 40% by mass or more and 85% by mass or less, and particularly preferably 50% by mass or more and 80% by mass or less.
  • the wavelength conversion sheet of this embodiment may further contain an additive or the like in addition to the condensed silicone resin cured product and the wavelength conversion material.
  • the wavelength conversion sheet of the present embodiment may further include inorganic particles.
  • Inorganic particles can scatter light in the wavelength conversion sheet to excite the wavelength conversion material more effectively, and in the production stage of the wavelength conversion sheet, the wavelength conversion material is contained in a composition containing a condensation type silicone resin. It is possible to suppress sedimentation.
  • the inorganic particles include oxides such as silicon, titanium, zirconia, aluminum, iron, and zinc, carbon black, barium titanate, calcium silicate, and calcium carbonate.
  • oxides such as silicon, titanium, zirconia, and aluminum are preferable.
  • Examples of the shape of the inorganic particles include a substantially spherical shape, a plate shape, a columnar shape, a needle shape, a whisker shape, and a fiber shape, and since a more uniform wavelength conversion sheet can be obtained, a substantially spherical shape is preferable.
  • the inorganic particles contained in the wavelength conversion sheet of this embodiment may be only one type or two or more types.
  • the size of the inorganic particles is preferably 1 to 20 ⁇ m, more preferably 1 to 10 ⁇ m.
  • the average particle diameter of the primary particles of the inorganic particles can be determined by, for example, an image imaging method in which the particles are directly observed with an electron microscope or the like. Specifically, first, a liquid in which inorganic particles to be measured are dispersed in an arbitrary solvent is prepared, and the obtained dispersion liquid is dropped on a slide glass or the like and dried. Alternatively, inorganic particles may be directly sprayed on the adhesive surface of the adhesive tape to produce inorganic particles attached thereto. Next, the average particle diameter of the primary particles of the inorganic particles is obtained by directly observing the particles with a scanning electron microscope (SEM) or a transmission electron microscope (TEM) and determining the size of the inorganic particles from the obtained shape. It is done.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • the content of the inorganic particles is preferably 0.01 parts by mass or more and 100 parts by mass or less, with respect to 100 parts by mass of the condensed silicone resin cured product contained in the wavelength conversion sheet of the present embodiment, and 0.1 mass by mass. More preferably, it is at least 50 parts by mass.
  • the wavelength conversion sheet of this embodiment has a storage elastic modulus at 25 ° C. of 2 GPa or more and 10 GPa or less. Generation
  • production of a wrinkle, a crack, etc. can be suppressed as the storage elastic modulus in 25 degreeC of a wavelength conversion sheet is 2 GPa or more.
  • the storage elastic modulus at 25 ° C. of the wavelength conversion sheet is 10 GPa or less, it becomes easy to produce a laminate including the wavelength conversion sheet and the substrate.
  • the wavelength conversion sheet of this embodiment has a storage elastic modulus at 25 ° C. of preferably 2 GPa or more and 8 GPa or less, and more preferably 2.5 GPa or more and 6 GPa or less.
  • the wavelength conversion sheet of the present embodiment is a material having a storage elastic modulus at 150 ° C. of 0.1 GPa to 5 GPa.
  • the wavelength conversion sheet has a storage elastic modulus at 150 ° C. of 0.1 GPa or more, even when the wavelength conversion sheet is exposed to a high temperature, the molecular weight constituting the cured silicone resin cured product contained in the wavelength conversion sheet Since the mobility is suppressed and the deterioration reaction is suppressed, the occurrence of coloring can be suppressed.
  • the wavelength conversion sheet has a storage elastic modulus at 150 ° C. of 5 GPa or less, when stress is applied to the wavelength conversion sheet, the stress is moderated moderately. Occurrence can be suppressed.
  • the wavelength conversion sheet of the present embodiment has a storage elastic modulus at 150 ° C. of preferably 0.1 Pa to 3 GPa, more preferably 0.3 GPa to 2 GPa, and further preferably 0.5 GPa to 1. 5 GPa or less.
  • the storage elastic modulus of the wavelength conversion sheet refers to a strain or stress applied to a sample piece, and the stress or strain generated with respect to the strain or stress is measured by a viscoelasticity measuring device (for example, a viscosity manufactured by TA Instruments Co., Ltd.). It is a value calculated by measuring with an elasticity measuring device DMA Q-800).
  • a viscoelasticity measuring device for example, a viscosity manufactured by TA Instruments Co., Ltd.
  • the thickness (film thickness) of the wavelength conversion sheet of this embodiment is preferably 10 ⁇ m or more because the wavelength conversion sheet can be stably produced.
  • the thickness of the wavelength conversion sheet of the present embodiment is preferably 1 mm or less, more preferably 200 ⁇ m or less, and more preferably 100 ⁇ m or less from the viewpoint of improving the optical properties and heat resistance of the wavelength conversion sheet. Further preferred. When the thickness of the wavelength conversion sheet is 1 mm or less, light absorption and light scattering due to the condensed silicone resin cured product can be reduced.
  • the film thickness of the wavelength conversion sheet of the present embodiment can be obtained, for example, by measuring the film thickness at a plurality of locations of the wavelength conversion sheet using a micrometer and calculating the average value.
  • the plurality of locations includes a total of five locations including one central portion of the wavelength conversion sheet and four corner portions of the wavelength conversion sheet.
  • the wavelength conversion sheet of this embodiment preferably has a Shore D hardness of 50 or more, and more preferably 60 or more.
  • the hardness measured at a descending speed of 1 mm / sec with a type D durometer is defined as Shore D hardness.
  • the wavelength conversion sheet of this embodiment can be suitably used for the application of a wavelength conversion sheet in solar cells, semiconductor lasers, LEDs, photodiodes, CCDs, CMOSs, and the like.
  • the wavelength conversion sheet of this embodiment is excellent in heat resistance, it can be particularly suitably used for a wavelength conversion sheet for a light emitting part of a semiconductor laser that requires heat resistance.
  • the wavelength conversion sheet of this embodiment is excellent in heat resistance.
  • the laminate of this embodiment includes the wavelength conversion sheet of this embodiment and a base material (support base material) provided on one surface of the wavelength conversion sheet.
  • the support substrate may be appropriately selected depending on the use of the laminate, and for example, a substrate made of a known metal, film, glass, ceramic, paper, or the like can be used.
  • the material for forming the supporting substrate include transparent inorganic oxide glasses such as quartz glass, borosilicate glass, and sapphire; metal plates and foils such as aluminum (including aluminum alloys), zinc, copper, and iron; cellulose acetate Polyethylene terephthalate (PET), polyethylene, polyester, polyamide, polyimide, polyphenylene sulfide, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, aramid and other plastic films; paper laminated with the plastic; paper coated with the plastic; Examples include a paper on which the metal is laminated or vapor-deposited; and a plastic film on which the metal is laminated or vapor-deposited. Among these, inorganic oxide glass or a metal plate is preferable.
  • the thickness of the supporting substrate is preferably 30 ⁇ m or more, and more preferably 50 ⁇ m or more. When the thickness of the support substrate is 30 ⁇ m or more, the support substrate has sufficient strength to protect the shape of the wavelength conversion sheet.
  • the thickness of the supporting substrate is preferably 5000 ⁇ m or less, more preferably 3000 ⁇ m or less, from the viewpoint of economy.
  • the laminate of this embodiment is excellent in heat resistance.
  • the manufacturing method of the wavelength conversion sheet of the present embodiment includes a preparation step S1, a forming step S2, a first heating step S3, and a second heating step S4.
  • a wavelength conversion material-containing silicone resin composition including a condensation-type silicone resin, a wavelength conversion material, and a solvent is prepared.
  • the condensation type silicone resin contained in the wavelength conversion material-containing silicone resin composition may be one kind alone, or two or more kinds.
  • the condensation type silicone resin contained in the wavelength conversion material-containing silicone resin composition preferably contains a structural unit represented by the above formula (A3).
  • the condensation type silicone resin contained in the wavelength conversion material-containing silicone resin composition includes a structural unit represented by the above formula (A1), a structural unit represented by the above formula (A1 ′), and the above formula (A2). It is preferable to further include one or more structural units selected from the group consisting of the structural units represented.
  • the condensation-type silicone resin contained in the wavelength conversion material-containing silicone resin composition is represented by the structural unit represented by the above formula (A1), the structural unit represented by the above formula (A1 ′), and the above formula (A2). And all of the structural units represented by the above formula (A3) are preferably included.
  • condensation-type silicone resin contained in the wavelength conversion material-containing silicone resin composition contains an oligomer component described later
  • all structural units contained in the condensation-type silicone resin include the oligomer component. Contain structural units shall be included.
  • the total content of the structural units represented by the formula (A3) is preferably 50 mol% or more based on the total content of all the structural units contained in the condensation-type silicone resin. It is more preferably at least mol%, more preferably at least 70 mol%, particularly preferably at least 80 mol%, particularly preferably at least 90 mol%.
  • the total content of the T1 body, the T2 body and the T3 body is relative to the total content of all structural units contained in the condensation type silicone resin. It is preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more, particularly preferably 80 mol% or more, and 90 mol% or more. It is even more preferred that it be.
  • the total content of T1 silicon atoms, T2 silicon atoms and T3 silicon atoms is the sum of all silicon atoms contained in the condensed silicone resin.
  • the content is preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more, particularly preferably 80 mol% or more, and 90 mol% or more. More preferably, it is at least mol%.
  • the content of the structural unit represented by the formula (A3) is based on the total content of all the structural units contained in the condensation type silicone resin. , 55 mol% or more, preferably 60 mol% or more, more preferably 65 mol% or more, and particularly preferably 70 mol% or more.
  • the content of the T3 body is 50 mol% or more with respect to the total content of all structural units contained in the condensation type silicone resin. Preferably there is.
  • the content of T3 silicon atoms is 50 mol% or more based on the total content of all silicon atoms contained in the condensation type silicone resin. It is preferable that
  • the condensation-type silicone resin contained in the wavelength conversion material-containing silicone resin composition if the content of the structural unit represented by the above formula (A3) is within this range, the room temperature (25 ° C.) of the obtained wavelength conversion sheet And the storage elastic modulus at a high temperature (150 ° C.) can be controlled within a desired range.
  • the content of the T3 body is 55 mol% or more with respect to the total content of all structural units contained in the condensation type silicone resin. It is preferably 60 mol% or more, more preferably 65 mol% or more, and particularly preferably 70 mol% or more.
  • the content of T3 silicon atoms is 55 mol% or more based on the total content of all silicon atoms contained in the condensation type silicone resin.
  • it is 60 mol% or more, more preferably 65 mol% or more, and particularly preferably 70 mol% or more.
  • the wavelength-conversion material-containing silicone resin composition in the condensation type silicone resin contained in the wavelength conversion material-containing silicone resin composition, if the content of the T-form and the content of the T3-form are within the above ranges, the wavelength-conversion material-containing silicone The wavelength conversion sheet obtained using the resin composition exhibits sufficient heat resistance, and also exhibits high light transmittance even after the heat resistance test. That is, the wavelength conversion sheet obtained using the wavelength conversion material-containing silicone resin composition is excellent in crack resistance and hardly discolored.
  • the content of D-form is 30 mol% or less with respect to the total content of all structural units contained in the condensation-type silicone resin. It is preferably 20 mol% or less, more preferably 10 mol% or less, particularly preferably 5 mol% or less, and particularly preferably 4 mol% or less.
  • the content of T3 silicon atoms contained in the condensation-type silicone resin is obtained by dividing the area of signals attributed as T3 silicon atoms by the total area of signals of all silicon atoms obtained in 29 Si-NMR measurement. be able to.
  • the content of silicon atoms other than T3 silicon atoms can be determined in the same manner.
  • the condensation-type silicone resin contained in the wavelength conversion material-containing silicone resin composition has a structural unit represented by the above formula (C1), formula (C1 ′), formula (C2), formula (C3), or formula (C4). Further, it may be included.
  • the polystyrene-equivalent weight average molecular weight of the condensation-type silicone resin contained in the wavelength conversion material-containing silicone resin composition is usually 1500 to 15000, preferably 2000 to 10000, more preferably 2000 to 8000. If the polystyrene-equivalent weight average molecular weight of the condensation type silicone resin is within this range, the solubility of the condensation type silicone resin in the solvent is improved, and handling properties when using the wavelength conversion material-containing silicone resin composition and Application property is improved.
  • the weight average molecular weight of the silicone resin generally, a value measured by a gel permeation chromatography (GPC) method can be used. Specifically, after dissolving the silicone resin in a soluble solvent, the resulting solution is passed along with the mobile phase solvent through a column using a filler having a large number of pores, and the molecular weight in the column. The content of the separated molecular weight component is detected using a differential refractometer, UV meter, viscometer, light scattering detector or the like as a detector. GPC-dedicated devices are widely commercially available, and the weight average molecular weight is generally measured by standard polystyrene conversion. The weight average molecular weight in this specification is measured by this standard polystyrene conversion.
  • GPC gel permeation chromatography
  • the condensation-type silicone resin contained in the wavelength conversion material-containing silicone resin composition includes a silicone resin as a main component (hereinafter sometimes referred to as “silicone resin A”) and a modifying silicone resin (oligomer component) described later. And are preferably mixed.
  • the silicone resin A preferably contains a structural unit represented by the above formula (A3).
  • the silicone resin A is selected from the group consisting of a structural unit represented by the above formula (A1), a structural unit represented by the above formula (A1 ′), and a structural unit represented by the above formula (A2). It is preferable that a structural unit of more than seeds is further included.
  • the total content of the T1 body, the T2 body, and the T3 body is usually 70 mol% or more with respect to the total content of all the structural units of the silicone resin A.
  • the content of the T3 body is usually 60 mol% or more and 90 mol% or less with respect to the total content of all the structural units of the silicone resin A.
  • the weight average molecular weight in terms of polystyrene of the silicone resin A is a resin that is usually 1500 or more and 8000 or less.
  • the total content of the T1, T2 and T3 bodies is preferably 80 mol% or more and 90 mol% or more with respect to the total content of all structural units of the silicone resin A. More preferably, it is more preferably 95 mol% or more.
  • the content of the T3 body is preferably 65% or more and 90% or less, and more preferably 70% or more and 85% or less with respect to the total content of all the structural units of the silicone resin A. preferable.
  • the polystyrene-reduced weight average molecular weight of the silicone resin A is preferably 1500 or more and 7000 or less, and more preferably 2000 or more and 5000 or less.
  • silicone resin A a commercially available silicone resin can be used.
  • the silicone resin A preferably has a silanol group (Si—OH).
  • the silicon atom having a silanol group is preferably 1 to 30 mol%, more preferably 5 to 27 mol%, based on all silicon atoms contained in the silicone resin A. More preferably, it is ⁇ 25 mol%.
  • the silicone resin A if the content of the silicon atom having a silanol group is within the above range, a hydrogen bond is formed between the silicone resin A and the surface of the wavelength conversion material. Become good.
  • the curing reaction of the wavelength conversion material-containing silicone resin composition of the present embodiment is likely to proceed, a wavelength conversion sheet with high heat resistance can be obtained.
  • the silicon atom having an alkoxy group is preferably more than 0 mol% and not more than 20 mol%, more than 0 mol% and not more than 10 mol% with respect to all silicon atoms contained in the silicone resin A. More preferably, it is 1 mol% or more and 10 mol% or less.
  • silicone resin A if the content of silicon atoms having an alkoxy group is within the above range, the storage stability of the wavelength conversion material-containing silicone resin composition is good and the fluidity is within an appropriate range. The handling property of the wavelength conversion material-containing silicone resin composition is improved.
  • the silicone resin A can be synthesized using an organosilicon compound having a functional group capable of generating a siloxane bond as a starting material.
  • the “functional group capable of generating a siloxane bond” include a halogen atom, a hydroxyl group, and an alkoxy group.
  • the organosilicon compound corresponding to the structural unit represented by the above formula (A3) include organotrihalosilane and organotrialkoxysilane.
  • Silicone resin A is obtained by reacting an organic silicon compound, which is a starting material, with a hydrolysis condensation method in the presence of an acid such as hydrochloric acid or a base such as sodium hydroxide at a ratio corresponding to the existing ratio of each structural unit. Can be synthesized. By appropriately selecting an organic silicon compound that is a starting material, the abundance ratio of T3 silicon atoms contained in the silicone resin A can be adjusted.
  • the content of the silicone resin A is preferably 60% by mass to 100% by mass, and preferably 70% by mass to 95% by mass with respect to the total content of the fully condensed silicone resin contained in the wavelength conversion material-containing silicone resin composition. It is more preferable that
  • the condensation-type silicone resin contained in the wavelength conversion material-containing silicone resin composition may contain the following modifying silicone (oligomer component).
  • the modifying silicone is contained in the condensation type silicone resin, the wavelength conversion sheet of the present embodiment is excellent in flexibility and crack resistance.
  • modifying silicone examples include oligomers containing a structural unit represented by the following formula (B1), formula (B1 ′), formula (B2), or formula (B3).
  • R 3 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.
  • R 4 represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group.
  • a plurality of R 3 and R 4 may be the same or different.
  • the polystyrene-reduced weight average molecular weight of the oligomer containing the structural unit represented by formula (B1), formula (B1 ′), formula (B2), or formula (B3) is preferably 1000 to 10,000, and preferably 2000 to 8000. More preferably, it is 3000 to 6000.
  • the modification includes a structural unit represented by the formula (B1), the formula (B1 ′), the formula (B2), or the formula (B3), and has a polystyrene-equivalent weight average molecular weight of 1000 to 10,000.
  • the silicone is referred to as “Oligomer B”.
  • Oligomer B is preferably (a) an oligomer containing T2 form or (b) an oligomer containing D form, more preferably an oligomer satisfying (a) and (b), that is, (c) an oligomer containing T2 form and D form. .
  • the oligomer containing T2 isomer is a structural unit represented by the formula (B2), wherein R 4 is an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group
  • the T2 isomer content is preferably 30 to 60 mol%, more preferably 40 to 55 mol%.
  • the wavelength conversion material-containing silicone resin composition ensures the solubility of the silicone resin A and the oligomer B if the content of the T2 body is within the above range. However, it exhibits good curing reactivity during thermal curing.
  • the oligomer containing D isomer is a silicone resin containing a structural unit represented by formula (B1), formula (B1 ′), formula (B2) or formula (B3).
  • a silicone resin having an average composition formula represented by the following formula (I) is preferable.
  • R 5 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.
  • R 6 represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a hydrogen atom.
  • n represents a real number satisfying 1 ⁇ n ⁇ 2.
  • m represents a real number satisfying 0 ⁇ m ⁇ 1. ]
  • the oligomer B whose average composition formula is represented by the above formula (I) includes the above-mentioned “T-form” and “D-form”.
  • R 5 is preferably a methyl group
  • R 6 is preferably a methyl group or a hydrogen atom
  • n is a real number satisfying 1 ⁇ n ⁇ 1.5
  • m is preferably a real number satisfying 0.5 ⁇ m ⁇ 1
  • n is a real number satisfying 1.1 ⁇ n ⁇ 1.4.
  • m is a real number that satisfies 0.55 ⁇ m ⁇ 0.75.
  • a structural unit represented by the formula (B1) and a structural unit represented by the formula (B1 ′) one of the two R 4 has 1 to 10 carbon atoms
  • the structural unit in which the alkyl group or aryl group having 6 to 10 carbon atoms and the other is an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group is “D1 form”.
  • the total content of D1 isomer and D2 isomer among all structural units contained in the oligomer B is preferably 5 to 80 mol%. It is more preferably 70 mol%, and further preferably 15 to 50 mol%.
  • the structural unit which is a hydroxyl group is T1 body.
  • the structural unit represented by the formula (B2), in which R 4 is an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group, is a T2 isomer.
  • the structural unit represented by the formula (B3) is a T3 body.
  • the oligomer B is an oligomer containing (c) the T2 form and the D form, among the total structural units contained in the oligomer B, the total content of the T1 form, the T2 form and the T3 form, and the content of the D form
  • the molar ratio (T-form: D-form) is preferably 60:40 to 90:10, and more preferably 75:25 to 85:15. If the molar ratio of T-form: D-form is in the above range, the compatibility between silicone resin A and oligomer B will be good.
  • the oligomer B can be synthesized using an organosilicon compound having a functional group capable of forming a siloxane bond as a starting material corresponding to each of the structural units described above constituting the silicone resin.
  • the “functional group capable of generating a siloxane bond” include a halogen atom, a hydroxyl group, and an alkoxy group.
  • the organosilicon compound corresponding to the structural unit represented by the above formula (B3) include organotrihalosilane and organotrialkoxysilane.
  • Examples of the organosilicon compound corresponding to the structural unit represented by the above formula (B2) include organodihalosilane and organodialkoxysilane.
  • Oligomer B is obtained by reacting an organosilicon compound as a starting material at a ratio corresponding to the abundance ratio of each structural unit in the presence of an acid such as hydrochloric acid or a base such as sodium hydroxide by a hydrolytic condensation method. Can be synthesized. By appropriately selecting the organosilicon compound as the starting material, the abundance ratio of the T-form silicon atom and the D-form silicon atom contained in the oligomer B can be adjusted.
  • the peak may be single or plural.
  • the total area of peaks existing in a region having a polystyrene-equivalent weight average molecular weight of 7500 or more is 20% or more of the total area of all peaks, and the polystyrene-equivalent weight.
  • the sum total of the peak areas existing in the region having an average molecular weight of 1000 or less may be 30% or more with respect to the total sum of the areas of all the peaks.
  • the content of the oligomer B is preferably 0.1 to 20% by mass, and preferably 0.2 to 15% by mass with respect to the total content of the silicone resin contained in the wavelength conversion material-containing silicone resin composition. More preferably, the content is 0.5 to 10% by mass.
  • the content of the oligomer B is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass with respect to the content of the silicone resin A, and 5 to 12% by mass. More preferably it is.
  • the structural unit represented by the above formula (A1), the structural unit represented by the above formula (A1 ′), the structural unit represented by the above formula (A2), and the above A silicone resin having a polystyrene-equivalent weight average molecular weight of less than 1500, with respect to the total content of structural units represented by the formula (A3), can be given.
  • such a silicone resin is referred to as “oligomer C”.
  • the oligomer C is represented by the structural unit represented by the above formula (A1), the structural unit represented by the above formula (A1 ′), the structural unit represented by the above formula (A2), and the above formula (A3).
  • the structural units it may be a silicone resin containing one or more types of structural units, and may be a silicone resin containing all four types of structural units.
  • Oligomer C is a silicone in which the ratio of the content of T3 silicon atoms to the total content of T1 silicon atoms, T2 silicon atoms and T3 silicon atoms is 0 to 30 mol%, and the weight average molecular weight in terms of polystyrene is less than 1500 Resin.
  • the ratio of the content of T3 silicon atoms to the total content of T1 silicon atoms, T2 silicon atoms, and T3 silicon atoms is preferably 0 to 25 mol%.
  • the oligomer C preferably has substantially no silicon atom (hydrosilyl group) bonded to a hydrogen atom and silicon atom bonded to an alkenyl group.
  • the heat resistance of the wavelength conversion sheet of the present embodiment is lowered.
  • the oligomer C is preferably an oligomer having an organopolysiloxane structure represented by the following formula (1).
  • R 1 and R 2 represent the same meaning as described above.
  • a plurality of R 1 and R 2 may be the same or different.
  • R 1 is one or more groups selected from the group consisting of a methyl group, an ethyl group and a phenyl group
  • R 2 is a methoxy group, an ethoxy group, an iso group. It is preferably one or more groups selected from the group consisting of a propoxy group and a hydroxyl group
  • R 1 is one or more groups selected from the group consisting of a methyl group and an ethyl group
  • R 2 is a methoxy group
  • R 1 is preferably a methyl group.
  • the abundance ratio of each silicon atom in the oligomer C can be adjusted by appropriately adjusting the numerical values of p 2 , q 2 , r 2 , a 2 and b 2 .
  • the organopolysiloxane structure represented by formula (1) the number of T2 silicon atoms and x 2, the number of T3 silicon atoms and y 2, and the number of T1 silicon atoms and z 2, formula (2)
  • the abundance ratio of the T3 silicon atom in the organopolysiloxane structure represented by is represented by [y 2 / (x 2 + y 2 + z 2 )].
  • [A 2 ⁇ q 2 ] / [(p 2 + b 2 ⁇ q 2 ) + a 2 ⁇ q 2 + (r 2 + q 2 )] is a T3 silicon atom in the organopolysiloxane structure represented by the formula (1)
  • the oligomer C that may be contained in the wavelength conversion material-containing silicone resin composition is a silicone resin having an organopolysiloxane structure represented by the formula (1), and includes a T1 silicon atom, a T2 silicon atom, and a T3 silicon atom.
  • Ratio of content of T3 silicon atom with respect to total content: [y 2 / (x 2 + y 2 + z 2 )] is 0 to 0.3 and the polystyrene-reduced weight average molecular weight is less than 1500 Is preferred.
  • the abundance ratio of T3 silicon atoms is within this range, the abundance ratio of T2 silicon atoms: [x 2 / (x 2 + y 2 + z 2 )] and the abundance ratio of T1 silicon atoms: [z 2 / (x 2 + y 2 + z 2 )] is not particularly limited.
  • the oligomer C [y 2 / (x 2 + y 2 + z 2 )] is preferably in the range of 0 to 0.25, more preferably in the range of 0.05 to 0.2.
  • Oligomer C has a relatively low abundance ratio of T3 silicon atoms, and therefore has a small branched chain structure and contains many linear and cyclic molecules.
  • the oligomer C may contain only cyclic molecules, but preferably contains many linear molecules.
  • an abundance ratio of T1 silicon atom: [z 2 / (x 2 + y 2 + z 2 )] is preferably in the range of 0 to 0.80, preferably 0.30 to 0.80. Those within the range are more preferred, those within the range of 0.35 to 0.75 are still more preferred, and those within the range of 0.35 to 0.55 are particularly preferred.
  • the weight average molecular weight in terms of polystyrene of the oligomer C measured by GPC method is less than 1500.
  • the weight average molecular weight in terms of polystyrene of the oligomer C is too large, the crack resistance of the wavelength conversion sheet of this embodiment may be insufficient.
  • the polystyrene-converted weight average molecular weight of the oligomer C may be less than 1000.
  • the number of T1 silicon atoms, T2 silicon atoms, and T3 silicon atoms in one molecule of oligomer C is appropriately adjusted so that the resin having an organopolysiloxane structure represented by formula (2) has a desired molecular weight. .
  • the sum of the number of T1 silicon atoms, the number of T2 silicon atoms and the number of T3 silicon atoms in the oligomer C1 molecule is preferably 2 or more.
  • the oligomer C can be synthesized using an organosilicon compound having a functional group capable of generating a siloxane bond corresponding to each structural unit described above constituting the oligomer C as a starting material.
  • the “functional group capable of generating a siloxane bond” has the same meaning as described above.
  • Examples of the organosilicon compound corresponding to the structural unit represented by the above formula (A3) include organotrihalosilane and organotrialkoxysilane.
  • the oligomer C can be synthesized by reacting such an organic silicon compound as a starting material at a ratio corresponding to the abundance ratio of each structural unit by a hydrolytic condensation method.
  • an organosilicon compound corresponding to the structural unit represented by the above formula (A1) and an organosilicon compound corresponding to the structural unit represented by the above formula (A1 ′) are mixed. Will be.
  • these organosilicon compounds are polymerized by hydrolytic condensation reaction, these organosilicon compounds are bonded to the terminals of the polymerization reaction to stop the polymerization reaction.
  • the content of the oligomer C is preferably 0.1 to 20% by mass, and preferably 0.2 to 15% by mass with respect to the total content of the silicone resin contained in the wavelength conversion material-containing silicone resin composition. More preferably, the content is 0.5 to 10% by mass.
  • the content of the oligomer C is preferably 0.1 to 20% by mass, more preferably 0.3 to 10% by mass with respect to the content of the silicone resin A, and 0.5 to More preferably, it is 5 mass%.
  • the condensation type silicone resin contained in the wavelength conversion material-containing silicone resin composition preferably contains oligomer B or oligomer C in addition to silicone resin A, and more preferably contains silicone resin A, oligomer B and oligomer C. .
  • the wavelength conversion material-containing silicone resin composition preferably includes silicone resin A, a solvent, a wavelength conversion material, and oligomer B or oligomer C. Silicone resin A, a solvent, a wavelength conversion material, and oligomer B And oligomer C is more preferable.
  • modifying silicone examples include, for example, a silicone resin containing a structural unit represented by the above formula (A1) and a structural unit represented by the above formula (A2).
  • the said silicone resin is a silicone resin containing D body.
  • the wavelength conversion material contained in the wavelength conversion material-containing silicone resin composition is the same as the wavelength conversion material contained in the wavelength conversion sheet of this embodiment.
  • the wavelength conversion material tends to settle in the wavelength conversion material-containing silicone resin composition.
  • condensation type silicone resin composition Since the condensation type silicone resin contained in the wavelength conversion material-containing silicone resin composition has a high T3 content, it contains a solvent for the purpose of improving handling properties.
  • a composition containing a condensation type silicone resin and a solvent and not containing a wavelength conversion material is referred to as a “condensation type silicone resin composition”.
  • the solvent is not particularly limited as long as it can dissolve the silicone resin (silicone resin A) and the oligomer (oligomer B and oligomer C). Since the silicone resin and the oligomer can be mixed uniformly and the stability of the condensation type silicone resin composition and the wavelength conversion material-containing silicone resin composition can be improved, the solvent has different boiling points. It is preferable to use more than one type of solvent (hereinafter referred to as solvent P and solvent Q).
  • an organic solvent having a boiling point of less than 100 ° C. is preferable.
  • ketone solvents such as acetone and methyl ethyl ketone
  • alcohol solvents such as methanol, ethanol, isopropyl alcohol, and normal propyl alcohol
  • hydrocarbon solvents such as hexane, cyclohexane, heptane, and benzene
  • An acetate solvent such as diethyl ether or tetrahydrofuran is preferred.
  • alcohol solvents such as methanol, ethanol, isopropyl alcohol, and normal propyl alcohol are more preferable.
  • Solvent Q is preferably an organic solvent having a boiling point of 100 ° C. or higher. Specifically, glycol ether solvents, glycol ester solvents and the like are preferable.
  • glycol ether solvent examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monoethyl hexyl ether, ethylene glycol monophenyl ether, ethylene Glycol monobenzyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monoethyl hexyl ether, diethylene glycol monophenyl ether, di Tylene glycol monobenzyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glyco
  • glycol ester solvent examples include ethylene glycol monoethyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monohexyl ether acetate, ethylene glycol monoethyl hexyl ether acetate, ethylene glycol monophenyl ether acetate, And ethylene glycol monobenzyl ether acetate.
  • ethylene glycol monobutyl ether dipropylene glycol monomethyl ether, diethylene glycol monobutyl ether, and ethylene glycol monobutyl ether acetate are more preferable.
  • the viscosity of the condensation type silicone resin composition is preferably 100 to 500,000 mPa ⁇ s at 25 ° C.
  • the content of the solvent is preferably 10 to 40% by mass with respect to the total content of all components contained in the wavelength conversion material-containing silicone resin composition. If content of a solvent exists in said range, it will become easy to adjust the viscosity of a wavelength conversion material containing silicone resin composition to the range from which applicability
  • the wavelength conversion material-containing silicone resin composition is preferably a liquid composition having a viscosity of 1000 to 500,000 mPa ⁇ s at 25 ° C. because it is easy to suppress sedimentation of the wavelength conversion material and has good coatability.
  • the wavelength conversion material-containing silicone resin composition can be easily applied onto the substrate by, for example, screen printing. Moreover, the wavelength conversion material containing silicone resin composition is easy to remove a solvent and air bubbles at the time of heat-hardening. Therefore, a highly heat resistant wavelength conversion sheet can be obtained.
  • the viscosity of the wavelength conversion material-containing silicone resin composition can be measured, for example, by a method of detecting the resistance (viscosity resistance) that the cone plate receives from the fluid with a rotational torque using a cone plate E-type viscometer.
  • the viscosity at 25 ° C. of the wavelength conversion material-containing silicone resin composition is preferably 8000 to 100,000 mPa ⁇ s, more preferably 10,000 to 80,000 mPa ⁇ s. When the viscosity of the wavelength conversion material-containing silicone resin composition is within this range, the coating property is good.
  • the dispersibility of the wavelength conversion material was maintained by adding an anti-settling agent such as silica.
  • an anti-settling agent such as silica.
  • the wavelength conversion material-containing silicone resin composition does not substantially contain silica particles.
  • substantially free of silica particles means that the wavelength conversion material-containing silicone resin composition does not contain any silica particles and the light transmittance of a cured product of the wavelength conversion material-containing silicone resin composition. It means a form containing silica particles to such an extent that does not decrease.
  • the extent that does not decrease the light transmittance of the cured product means that the degree of decrease in the light transmittance is such that there is no practical problem.
  • the degree of decrease in light transmittance of the cured product of the wavelength conversion material-containing silicone resin composition containing silica particles is such that the light transmission of the cured product of the wavelength conversion material-containing silicone resin composition not containing silica particles. It means that it is 10% or less, and preferably 5% or less.
  • the content of silica particles is preferably about 1% by mass or less, and more preferably 0.1% by mass or less.
  • the cured product of the wavelength conversion material-containing silicone resin composition is applied to the wavelength conversion material of the semiconductor light emitting device because the wavelength conversion material-containing silicone resin composition is substantially free of silica particles, A decrease in light transmittance of the matrix resin to be formed can be suppressed. As a result, a decrease in light extraction efficiency of the semiconductor light emitting device is suppressed, and a decrease in light output of the semiconductor light emitting device can be suppressed.
  • the wavelength conversion material-containing silicone resin composition may contain various materials as necessary.
  • the wavelength conversion material-containing silicone resin composition may contain, for example, additives such as inorganic particles and an adhesion aid for the purpose of diffusing the wavelength conversion material and improving coating properties.
  • the wavelength conversion material-containing silicone resin composition preferably contains a curing catalyst or a silane coupling agent.
  • Examples of the curing catalyst include R 2 in the structural unit represented by the above formula (A1), the structural unit represented by the above formula (A1 ′), and the structural unit represented by the above formula (A2).
  • inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid
  • organic acids such as formic acid, acetic acid, succinic acid, citric acid, propionic acid, butyric acid, lactic acid and succinic acid are used to promote the hydrolysis and condensation reaction.
  • inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid
  • organic acids such as formic acid, acetic acid, succinic acid, citric acid, propionic acid, butyric acid, lactic acid and succinic acid are used to promote the hydrolysis and condensation reaction.
  • the curing catalyst not only an acidic compound but also an alkaline compound can be used. Specifically, ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, or the like can be used as a curing catalyst.
  • An organometallic compound catalyst can also be used as the curing catalyst.
  • an organometallic compound catalyst containing aluminum, zirconium, tin, titanium, or zinc can be used as the curing catalyst.
  • organometallic compound catalyst containing aluminum examples include aluminum triacetyl acetate and aluminum triisopropoxide.
  • organometallic compound catalyst containing zirconium examples include zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium dibutoxydiacetylacetonate, zirconium tetranormal propoxide, zirconium tetraisopropoxide, zirconium tetranormal butoxide, Examples include zirconium acylate and zirconium tributoxy systemate.
  • organometallic compound catalyst containing tin examples include tetrabutyltin, monobutyltin trichloride, dibutyltin dichloride, dibutyltin oxide, tetraoctyltin, dioctyltin dichloride, dioctyltin oxide, tetramethyltin, dibutyltin laurate, dioctyltin laurate Rate, bis (2-ethylhexanoate) tin, bis (neodecanoate) tin, di-n-butylbis (ethylhexylmalate) tin, di-normal butylbis (2,4-pentanedionate) tin, di-normal Examples thereof include butyl butoxychlorotin, di-normal butyl diacetoxy tin, di-normal butyl dilaurate tin, and dimethyl dineodecanoate
  • titanium-containing organometallic compound catalyst examples include titanium tetraisopropoxide, titanium tetranormal butoxide, butyl titanate dimer, tetraoctyl titanate, titanium acetylacetonate, titanium octylene glycolate, and titanium ethyl acetoacetate.
  • organometallic compound catalyst containing zinc examples include zinc triacetylacetonate.
  • phosphoric acid ester or phosphoric acid is preferable, and phosphoric acid is particularly preferable.
  • the curing catalyst In order to add the curing catalyst to the wavelength conversion material-containing silicone resin composition at a predetermined concentration, the curing catalyst is diluted with water, an organic solvent, a silicone monomer, an alkoxysilane oligomer, etc., and then the wavelength conversion material-containing silicone is used. It is preferable to add to the resin composition.
  • the content of the curing catalyst can be appropriately adjusted in consideration of the heating temperature and time of the curing reaction of the wavelength conversion material-containing silicone resin composition, the type of catalyst, and the like.
  • the content of the curing catalyst is preferably 0.01 parts by mass or more and 10 parts by mass or less, and 0.01 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the wavelength conversion material-containing silicone resin composition. More preferably, it is 0.1 to 1 part by mass.
  • the curing catalyst may be added in advance to the wavelength conversion material-containing silicone resin composition, or added to the wavelength conversion material-containing silicone resin composition immediately before the curing reaction of the wavelength conversion material-containing silicone resin composition is performed. May be.
  • silane coupling agent examples include at least one selected from the group consisting of vinyl group, epoxy group, styryl group, methacryl group, acrylic group, amino group, ureido group, mercapto group, sulfide group, and isocyanate group. Silane coupling agents are preferred. Among these, a silane coupling agent having an epoxy group or a mercapto group is preferable.
  • silane coupling agent examples include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxy.
  • examples thereof include propylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropyltrimethoxysilane.
  • silicon atoms contained in the silane coupling agent are also detected as 29 Si-NMR signals.
  • the signal of the silane coupling agent shall be included when calculating the signal area of the silicone resin composition.
  • the content of the silane coupling agent is preferably 0.0001 parts by mass or more and 1.0 parts by mass or less with respect to 100 parts by mass of the condensation type silicone resin contained in the wavelength conversion material-containing silicone resin composition. It is more preferable that the amount be 0.001 part by mass or more and 0.1 part by mass or less.
  • the inorganic particles contained in the wavelength conversion material-containing silicone resin composition are the same as the inorganic particles that may be contained in the wavelength conversion sheet of this embodiment. Inorganic particles can scatter light in the wavelength conversion sheet to excite the wavelength conversion material more effectively, and in the production stage of the wavelength conversion sheet, the wavelength conversion material is contained in a composition containing a condensation type silicone resin. It is possible to suppress sedimentation.
  • the wavelength conversion material-containing silicone resin composition may contain additives other than the above-described materials as necessary.
  • specific examples of the additive include a dispersant, a leveling agent, and an antifoaming agent.
  • the wavelength conversion material-containing silicone resin composition is obtained by mixing a silicone resin (silicone resin A), a wavelength conversion material, a solvent, and other components (oligomer B, oligomer C, etc.) as necessary.
  • the wavelength conversion material-containing silicone resin composition preferably contains silicone resin A, oligomer B and oligomer C.
  • the silicone resin A contains a smaller amount of the oligomer B than the silicone resin A and a smaller amount of the oligomer C than the silicone A.
  • a silicone resin for example, silicone resin A, oligomer B, and oligomer C.
  • the mixing method of the silicone resin A, the oligomer B, and the oligomer C is not particularly limited, and any of known methods performed when mixing two or more kinds of polymers may be used.
  • the silicone resin A, the oligomer B, the oligomer C, and other components as necessary may be dissolved in an organic solvent, and then the obtained solution may be mixed.
  • the silicone resin can be mixed more uniformly and the stability of the prepared silicone resin composition can be improved, after dissolving the silicone resin in an organic solvent having high volatility and solubility, It is preferable to substitute the organic solvent with another solvent.
  • solvent P a highly volatile and highly soluble organic solvent
  • the mixture is heated to a temperature near the boiling point of the solvent P and stirred.
  • solvent P a solvent having a lower volatility than the solvent P
  • solvent Q a solvent having a lower volatility than the solvent P
  • the wavelength conversion material-containing silicone resin composition can be prepared using a known stirring and kneading machine.
  • known stirring and kneading machines include a homogenizer, a self-revolving stirrer, a three-roller, a ball mill, a planetary ball mill, and a bead mill.
  • the wavelength conversion material-containing silicone resin composition may be defoamed under vacuum or under reduced pressure as necessary.
  • the wavelength conversion material-containing silicone resin composition is usually molded into a sheet shape on a supporting base material to obtain a molded body on the supporting base material.
  • the support substrate may be peeled after the molded body is obtained, or may not be peeled off.
  • the molding method is not particularly limited as long as the wavelength conversion material-containing silicone resin composition can be molded into a sheet shape, and can be performed using a known coating apparatus.
  • Known coating devices include, for example, reverse roll coaters, blade coaters, slit die coaters, direct gravure coaters, offset gravure coaters, reverse roll coaters, blade coaters, kiss coaters, natural roll coaters, air knife coaters, roll blade coaters, varistors.
  • Examples include a bar roll blade coater, a two stream coater, a rod coater, a wire bar coater, an applicator, a dip coater, a curtain coater, a spin coater, and a knife coater.
  • a bar roll blade coater a two stream coater
  • a rod coater a rod coater
  • a wire bar coater a wire bar coater
  • an applicator a dip coater
  • a curtain coater a spin coater
  • a knife coater a knife coater.
  • Examples of other molding methods include printing methods such as screen printing, gravure printing, and lithographic printing. Among these, screen printing is preferable from the viewpoint of workability.
  • a method for coating the wavelength conversion material-containing silicone resin composition on the support substrate by a screen printing method will be described.
  • the surface of the supporting substrate is covered with a mask having openings of a required pattern, and the wavelength conversion material-containing silicone resin composition is put into the squeegee portion.
  • the wavelength conversion material-containing silicone resin composition is filled into the opening of the mask by moving the squeegee and moving the wavelength conversion material-containing silicone resin composition on the mask while applying pressure (filling step).
  • the mask is removed.
  • the pattern of the wavelength conversion material containing silicone resin composition can be formed on a support base material.
  • First heating step S3 In 1st heating process S3 and 2nd heating process S4 mentioned later, the obtained molded object is heat-hardened and a wavelength conversion sheet is obtained.
  • the molded body is usually heated by using a device such as a natural convection oven, a blower oven, a vacuum oven, an inert oven, a hot plate, a hot press machine, or an infrared heater.
  • a blower oven it is preferable to use a blower oven from the viewpoint of productivity.
  • the obtained molded body is left in an atmosphere heated from room temperature (25 ° C.) to 120 ° C. so as to satisfy the requirement of 0.60 ⁇ E / D ⁇ 0.97. And let it harden.
  • D represents the mass of the molded body before the first heating step S3.
  • E represents the mass of the molded body after the first heating step S3.
  • the first heating step S3 preferably satisfies the requirement of 0.70 ⁇ E / D ⁇ 0.97, and satisfies the requirement of 0.80 ⁇ E / D ⁇ 0.96. It is more preferable that the requirement 0.85 ⁇ E / D ⁇ 0.96 is satisfied, and it is particularly preferable that the requirement 0.90 ⁇ E / D ⁇ 0.95 is satisfied.
  • E / D When the value of E / D is 0.60 or more, a sheet free from cracks and wrinkles can be formed while ensuring the dispersibility of the wavelength conversion material. When the value of E / D is 0.97 or less, it is possible to reduce the components that volatilize in the second heating step, and it is possible to suppress the fixation of bubbles in the sheet.
  • B represents content of T3 body (structural unit represented by said Formula (A3)) with respect to the total content of all the structural units contained in the molded object after 1st heating process S3. In other words, it represents the content of T3 silicon atoms relative to the total content of all silicon atoms contained in the molded body after the first heating step S3.
  • C represents content of T3 body (structural unit represented by said Formula (A3)) with respect to the total content of all the structural units contained in the molded object after 2nd heating process S4. In other words, it represents the content of T3 silicon atoms with respect to the total content of all silicon atoms contained in the molded body after the second heating step S4.
  • the second heating step S4 preferably satisfies 1.02 ⁇ C / B ⁇ 1.20, and satisfies the requirement of 1.03 ⁇ C / B ⁇ 1.10. More preferred.
  • the value of C / B is 1.01 or more, it is possible to achieve the strength of a sheet that can be actually used.
  • the value of C / B is 1.30 or less, it is possible to obtain a sheet in which bubbles are not easily fixed and wrinkles and cracks are hardly generated.
  • the wavelength conversion sheet of this embodiment can be obtained.
  • the condensation reaction of the silicone resin (silicone resin A) and the oligomer (oligomer B, oligomer C) proceeds while reducing the solvent and water contained in the wavelength conversion material-containing silicone resin composition. Do not at temperatures.
  • the second heating step S4 is performed at a temperature at which the condensation reaction of the silicone resin (silicone resin A) and the oligomer (oligomer B, oligomer C) proceeds.
  • the network structure of the cured silicone product while maintaining the dispersibility of the phosphor (wavelength converting material) in the phosphor solvent (wavelength converting material-containing silicone resin composition) by the first heating step S3 and the second heating step S4. Can be controlled appropriately. Thereby, the obtained wavelength conversion sheet can suppress a wrinkle, a crack, and the entrapment of a bubble.
  • the present inventors presume that the mobility of the phosphor (wavelength conversion material) is limited by reducing the solvent and water in the first heating step S3, and as a result, the sedimentation of the phosphor can be suppressed. Furthermore, it is estimated that silicone molecules (silicone resin molecules) can be arranged closely. By condensing the silicone resin and oligomer in such a state in the second heating step S4, it is possible to form a wavelength conversion sheet having an appropriate storage elastic modulus. The wavelength conversion sheet thus obtained is difficult to break and discoloration during high temperature use is also unlikely to occur.
  • a wavelength conversion sheet having excellent heat resistance can be obtained.
  • FIG. 1 is a cross-sectional view showing the structure of a light emitting device provided with the wavelength conversion sheet of this embodiment.
  • the light emitting device 1000 includes a substrate 110, a semiconductor laser element (light source) 120, a light guide unit 130, a wavelength conversion sheet 140, and a reflecting mirror 150.
  • the wavelength conversion sheet 140 can be configured as described above.
  • the semiconductor laser element 120 is set on the substrate 110.
  • the light guide unit 130 receives the laser beam La emitted from the semiconductor laser element 120 and guides the laser beam La therein.
  • the semiconductor laser element 120 is optically connected to one end of the light guide unit 130, and the wavelength conversion sheet 140 is optically connected to the other end.
  • the light guide unit 130 has a weight shape in which the width gradually decreases from one end side to the other end side, and the laser light La emitted from the semiconductor laser element 120 is focused on the wavelength conversion sheet 140. .
  • the reflecting mirror 150 is a bowl-shaped member disposed around the wavelength conversion sheet 140, and a curved surface facing the wavelength conversion sheet 140 is a light reflecting surface.
  • the reflecting mirror 150 deflects the light emitted from the wavelength conversion sheet 140 toward the front of the apparatus (irradiation direction of the laser light La).
  • the laser light La irradiated on the wavelength conversion sheet 140 is converted into white light Lb by the wavelength conversion material contained in the wavelength conversion sheet 140 and output from the light emitting device 1000.
  • the light emitting device 1000 has one semiconductor laser element 120, but may have two or more.
  • FIG. 2 is a cross-sectional view showing a modification of the light emitting device. 2 and the following description, the same components as those described in FIG. 1 are denoted by the same reference numerals as those in FIG.
  • the light emitting device 1100 includes a plurality of substrates 110, a plurality of semiconductor laser elements (light sources) 120, a plurality of optical fibers 180, a light guide unit 130, a wavelength conversion sheet 140, a reflecting mirror 150, and a transparent support 190. have.
  • the optical fiber 180 receives the laser beam La emitted from the semiconductor laser element 120 and guides the laser beam La therein.
  • a semiconductor laser element 120 is optically connected to one end of each of the plurality of optical fibers 180.
  • the plurality of optical fibers 180 are bundled on the other end side, and are optically connected to the light guide unit 130 at the other end in a bundled state.
  • the light guide unit 130 receives the laser beam La emitted from the semiconductor laser element 120 therein, guides the laser beam La therein, and then emits the laser beam La toward the front of the apparatus.
  • the light guide unit 130 may have a function of condensing the laser light La emitted to the front of the apparatus.
  • the wavelength conversion sheet 140 is disposed so as to be separated from the light guide unit 130 and opposed to the light guide unit 130 while being supported by the transparent support 190.
  • the transparent support 190 is provided in front of the apparatus so as to cover the opening of the reflecting mirror 150.
  • the transparent support 190 is a member made of a transparent material that does not deteriorate due to heat generated during use of the apparatus, and for example, a glass plate can be used.
  • the laser light La irradiated on the wavelength conversion sheet 140 is converted into white light Lb by the wavelength conversion material contained in the wavelength conversion sheet 140 and is output from the light emitting device 1100.
  • the light source semiconductor laser element 120
  • the light emitting unit wavelength conversion sheet 140
  • oligomer C polystyrene equivalent weight average molecular weight: ⁇ 1000, measurement condition 1
  • oligomer B polystyrene equivalent weight average molecular weight: 3400, measurement condition 1
  • oligomer C and oligomer B were dissolved in the solvent by stirring for 1 hour or longer.
  • 274.49 g of 2-butoxyethyl acetate and 0.223 g of 3-glycidoxypropyltrimethoxysilane (silane coupling agent) were added.
  • the obtained mixture is set in an evaporator, the temperature of the mixture is 85 ° C., and the degree of vacuum of the evaporator is 2.0 kPa. Then, the total concentration of propyl acetate and isopropyl alcohol in the mixture is 1% by mass or less. Until then, propyl acetate and isopropyl alcohol were distilled off.
  • Synthesis Example 1 The structural units contained in the silicone resin A used, the structural units contained in the oligomer C, and the structural units contained in the oligomer B are shown in the table below.
  • Oligomer B contained 95% or more of a resin composed of repeating units and abundance ratios shown in Table 3.
  • the oligomer B has a peak area existing in a region having a weight average molecular weight of 7500 or more and a total area of peaks of 20% or more of the total area of the peaks and a weight average molecular weight of 1000 or less. The total area was 30% or more with respect to the total peak area.
  • condensation type silicone resin composition of Synthesis Example 3 was obtained.
  • silicone resin P and silicone resin Q are mixed at a mass ratio of 60:40.
  • Wavelength conversion material YAG phosphor (YAG: Ce, particle size: 5.4 ⁇ m, 13.6 ⁇ m and 17.8 ⁇ m) (manufactured by Tokyo Chemical Research Laboratories)
  • Curing catalyst solution curing catalyst: solution containing 15% by mass of phosphoric acid Silica particles: X-52-7042 (manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size 4 ⁇ m
  • Examples 1 to 3 and Comparative Examples 1 and 3 The molded bodies of Examples 1 to 3 and Comparative Examples 1 and 3 were cured by raising the temperature from room temperature (25 ° C.) to 120 ° C. at a rate of 4 ° C./min in an oven (first heating step) ). Thereafter, the temperature was raised from 120 ° C. to 150 ° C. at a rate of 7 ° C./min, and further cured by leaving it to stand at 150 ° C. for 5 hours (second heating step). In this way, a wavelength conversion sheet having a diameter of 4 cm and a thickness of 1 mm was obtained.
  • Table 6 shows E / D values in the first heating step of Example 1.
  • the E / D value in the first heating step of Example 1 was 0.93.
  • Example 2 The molded body of Example 1 was placed in an oven preheated to 160 ° C. and cured by leaving it to stand at 160 ° C. for 5 hours. As a result, many bubbles were confirmed.
  • Table 6 shows E / D values in the first heating step of Comparative Example 2. The E / D value in the first heating step of Comparative Example 2 was 1.00.
  • T3 body weights B and C Using Solid 29 Si-NMR For the wavelength conversion sheet of Example 1, solid 29 Si-NMR was measured under the following measurement conditions, and the content of T3 silicon atoms relative to the total content of all silicon atoms contained in the wavelength conversion sheet of Example 1 (hereinafter, The values of B and C, which are referred to as “T3 body weight”, were calculated. C / B calculated using the calculated B and C is shown as “T3 body mass ratio” in Table 6.
  • Table 6 shows C / B values in the second heating step of Example 1.
  • the value of C / B in the first heating step of Example 1 was 1.05.
  • the T3 body amount (C) in the wavelength conversion sheet of Example 1 was 80% with respect to the total content of all structural units included in the wavelength conversion sheet.
  • Measuring device Viscoelasticity measuring device DMA Q-800 (manufactured by TA Instruments) Strain: 0.1% Angular frequency: 10 Hz Temperature range: 25 ° C to 150 ° C Temperature increase rate: 5 ° C / min Measurement atmosphere: In air
  • Table 7 shows the storage elastic modulus values at 25 ° C. and 150 ° C. of the wavelength conversion sheets obtained in Examples 1 to 3 and Comparative Examples 1 and 3.
  • a durometer GS-720G (type D) mounted on a durometer (rubber / plastic hardness meter) automatic low-pressure loader GS-610 manufactured by Teclock Co., Ltd. was used.
  • the Shore D hardness of the wavelength conversion sheets obtained in Examples 1 to 3 and Comparative Examples 1 and 3 was measured at a descending speed of 1 mm / second. Measurement was carried out at five locations, and the average value was calculated.
  • Table 7 shows the Shore D hardness of the wavelength conversion sheets obtained in Examples 1 to 3 and Comparative Examples 1 and 3.
  • Table 7 shows the visual evaluation results of the heat resistance of the wavelength conversion sheets obtained in Examples 1 to 3 and Comparative Examples 1 and 3. In addition, wrinkles and cracks were not confirmed in any of the wavelength conversion sheets obtained in Examples 1 to 3 and Comparative Examples 1 and 3 in the wavelength conversion sheet after heating.
  • Measuring device Color difference meter “CM-3600d” (manufactured by Konica Minolta Co., Ltd.) Measurement diameter: 4 mm Measurement mode: SCE + SCI Light source: D65 Color difference formula: CIE1994
  • Table 8 shows the measurement results of the color difference meter for the wavelength conversion sheets obtained in Examples 1 to 3 and Comparative Example 1.
  • the wavelength conversion sheets obtained in Examples 1 to 3 have a storage elastic modulus at 25 ° C. of 2 GPa to 10 GPa, and a storage elastic modulus at 150 ° C. of 0.1 GPa to 5 GPa. Within the following range.
  • the wavelength conversion sheets obtained in Examples 1 to 3 had a Shore D hardness of 50 or more. In the wavelength conversion sheets obtained in Examples 1 to 3, no wrinkles, cracks and coloring were observed even after heating in an oven at 250 ° C. for 24 hours, and the heat resistance was excellent.
  • the wavelength conversion sheet obtained in Comparative Example 1 has a storage elastic modulus at 25 ° C. in the range of 2 GPa to 10 GPa, but a storage elastic modulus at 150 ° C. of 0.1 GPa. Was less than.
  • the wavelength conversion sheet obtained in Comparative Example 1 had a Shore D hardness of less than 50.
  • the wavelength conversion sheet obtained in Comparative Example 1 was confirmed to be colored after being heated in an oven at 250 ° C. for 24 hours, and was inferior in heat resistance.
  • the wavelength conversion sheet obtained in Comparative Example 3 had a storage elastic modulus at 25 ° C. of less than 2 GPa and a storage elastic modulus at 150 ° C. of less than 0.1 GPa.
  • the wavelength conversion sheet obtained in Comparative Example 3 was inferior in heat resistance because large deformation of the shape was confirmed after heating in an oven at 250 ° C. for 1 hour.
  • the wavelength conversion sheets obtained in Examples 1 to 3 had smaller absolute values of ⁇ L * , ⁇ a *, and ⁇ b * than the wavelength conversion sheets obtained in Comparative Example 1. From this, it was clarified that the wavelength conversion sheets obtained in Examples 1 to 3 were excellent in heat resistance as compared with the wavelength conversion sheet obtained in Comparative Example 1.
  • the present invention it is possible to provide a wavelength conversion sheet having excellent heat resistance, a laminate including the wavelength conversion sheet, a light emitting device, and a method for manufacturing the wavelength conversion sheet.

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PCT/JP2017/031730 2016-09-07 2017-09-04 波長変換シート、積層体および発光装置、並びに、波長変換シートの製造方法 Ceased WO2018047758A1 (ja)

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EP17848698.1A EP3511611A4 (en) 2016-09-07 2017-09-04 WAVELENGTH CONVERSION FILM, LAMINATE, LIGHT-EMITTING DEVICE AND METHOD FOR PRODUCING A WAVELENGTH CONVERSION FILM
CN201780054505.8A CN109690367A (zh) 2016-09-07 2017-09-04 波长转换片材、层叠体及发光装置、以及波长转换片材的制造方法
KR1020197009938A KR20190041020A (ko) 2016-09-07 2017-09-04 파장 변환 시트, 적층체 및 발광 장치, 및, 파장 변환 시트의 제조 방법
US16/330,427 US20210284903A1 (en) 2016-09-07 2017-09-04 Wavelength conversion sheet, laminate and light-emitting device, and method for producing wavelength conversion sheet

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019189495A1 (ja) * 2018-03-27 2019-10-03 日立化成株式会社 波長変換部材、バックライトユニット、画像表示装置及び硬化性組成物

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7842647B2 (en) 2006-02-03 2010-11-30 Bayer Cropscience Lp Stable, concentrated herbicidal compositions
TWI808178B (zh) * 2019-05-21 2023-07-11 隆達電子股份有限公司 波長轉換物質及發光裝置
TWI705123B (zh) * 2019-10-29 2020-09-21 隆達電子股份有限公司 波長轉換物質以及發光裝置
US11584882B2 (en) * 2020-02-14 2023-02-21 Osram Opto Semiconductors Gmbh Wavelength converter; method of its making and light-emitting device incorporating the element
EP4574920A1 (fr) * 2023-12-21 2025-06-25 The Swatch Group Research and Development Ltd Matériau photoluminescent plus performant

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012230309A (ja) * 2011-04-27 2012-11-22 Kaneka Corp 貼り合せ光学部品
JP2012233118A (ja) * 2011-05-06 2012-11-29 Kaneka Corp 硬化性組成物
JP2012255125A (ja) * 2011-05-17 2012-12-27 Mitsubishi Chemicals Corp 熱硬化性樹脂組成物、半導体デバイス用部材、及びそれを用いた半導体デバイス
JP2013001792A (ja) 2011-06-16 2013-01-07 Toray Ind Inc 蛍光体含有シート、それを用いたｌｅｄ発光装置およびその製造方法
JP2014116587A (ja) * 2012-11-16 2014-06-26 Toray Ind Inc 蛍光体含有樹脂シート、これを用いたｌｅｄ素子およびその製造方法
WO2015042285A1 (en) * 2013-09-18 2015-03-26 Dow Corning Corporation Compositions of resin-linear organosiloxane block copolymers
JP2015513328A (ja) * 2012-01-16 2015-05-07 ダウ コーニング コーポレーションＤｏｗ Ｃｏｒｎｉｎｇ Ｃｏｒｐｏｒａｔｉｏｎ 光学物品及び形成方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5101762B2 (ja) * 1999-11-29 2012-12-19 東レ・ダウコーニング株式会社 室温硬化性シリコーンゴム組成物
JP5117654B2 (ja) * 2001-09-27 2013-01-16 ホーユー株式会社 ヘアマスカラ
WO2009119841A1 (ja) * 2008-03-28 2009-10-01 三菱化学株式会社 硬化性ポリシロキサン組成物、並びに、それを用いたポリシロキサン硬化物、光学部材、航空宇宙産業用部材、半導体発光装置、照明装置、及び画像表示装置
JP5646855B2 (ja) * 2010-02-01 2014-12-24 日東電工株式会社 シリコーン樹脂組成物
EP2537899B1 (en) * 2010-02-19 2014-11-26 Toray Industries, Inc. Phosphor-containing cured silicone, process for production of same, phosphor-containing silicone composition, precursor of the composition, sheet-shaped moldings, led package, light -emitting device, and process for production of led-mounted substrate
JP5566785B2 (ja) * 2010-06-22 2014-08-06 日東電工株式会社 複合シート
EP2653502A4 (en) * 2010-12-13 2014-04-30 Toray Industries PHOSPHORUS FILM, LED AND LIGHT EMITTING DEVICE AND METHOD FOR PRODUCING AN LED
JP5545601B2 (ja) * 2011-11-07 2014-07-09 信越化学工業株式会社 蛍光体高充填波長変換シート、それを用いた発光半導体装置の製造方法、及び該発光半導体装置
JP5819774B2 (ja) * 2012-05-01 2015-11-24 株式会社ニューギン 遊技機

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012230309A (ja) * 2011-04-27 2012-11-22 Kaneka Corp 貼り合せ光学部品
JP2012233118A (ja) * 2011-05-06 2012-11-29 Kaneka Corp 硬化性組成物
JP2012255125A (ja) * 2011-05-17 2012-12-27 Mitsubishi Chemicals Corp 熱硬化性樹脂組成物、半導体デバイス用部材、及びそれを用いた半導体デバイス
JP2013001792A (ja) 2011-06-16 2013-01-07 Toray Ind Inc 蛍光体含有シート、それを用いたｌｅｄ発光装置およびその製造方法
JP2015513328A (ja) * 2012-01-16 2015-05-07 ダウ コーニング コーポレーションＤｏｗ Ｃｏｒｎｉｎｇ Ｃｏｒｐｏｒａｔｉｏｎ 光学物品及び形成方法
JP2014116587A (ja) * 2012-11-16 2014-06-26 Toray Ind Inc 蛍光体含有樹脂シート、これを用いたｌｅｄ素子およびその製造方法
WO2015042285A1 (en) * 2013-09-18 2015-03-26 Dow Corning Corporation Compositions of resin-linear organosiloxane block copolymers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3511611A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019189495A1 (ja) * 2018-03-27 2019-10-03 日立化成株式会社 波長変換部材、バックライトユニット、画像表示装置及び硬化性組成物

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