WO2018047756A1 - シリコーン樹脂組成物、波長変換材料含有シリコーン樹脂組成物および波長変換材料含有シート - Google Patents

シリコーン樹脂組成物、波長変換材料含有シリコーン樹脂組成物および波長変換材料含有シート Download PDF

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WO2018047756A1
WO2018047756A1 PCT/JP2017/031728 JP2017031728W WO2018047756A1 WO 2018047756 A1 WO2018047756 A1 WO 2018047756A1 JP 2017031728 W JP2017031728 W JP 2017031728W WO 2018047756 A1 WO2018047756 A1 WO 2018047756A1
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Prior art keywords
silicone resin
resin composition
formula
structural unit
oligomer
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PCT/JP2017/031728
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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 CN201780054475.0A priority Critical patent/CN109689789A/zh
Priority to KR1020197009934A priority patent/KR20190051015A/ko
Priority to EP17848696.5A priority patent/EP3511377A4/en
Priority to US16/330,435 priority patent/US20210284843A1/en
Publication of WO2018047756A1 publication Critical patent/WO2018047756A1/ja
Anticipated expiration legal-status Critical
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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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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
    • 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
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • 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
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • 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
    • C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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

Definitions

  • the present invention relates to a silicone resin composition, a wavelength conversion material-containing silicone resin composition, and a wavelength conversion material-containing 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.
  • a light-emitting device in which a sheet containing a phosphor as a wavelength conversion material (hereinafter sometimes referred to as “phosphor sheet”) is disposed on a light-emitting surface of a light-emitting diode (LED, Light Emitting Diode) element is known.
  • LED Light Emitting Diode
  • Patent Document 1 Also known is a wavelength conversion member in which inorganic phosphor powder is dispersed in a glass matrix (see, for example, Patent Document 2).
  • the phosphor sheet for LD is required to have higher heat resistance than the phosphor sheet for LED.
  • the phosphor sheet described in Patent Document 1 may not have sufficient heat resistance as a phosphor sheet for LD. Specifically, when the light emitted from the semiconductor laser is irradiated onto the phosphor sheet described in Patent Document 1, the resin contained in the phosphor sheet deteriorates due to heat generated by light irradiation with high energy density. , Cracks, coloring, wrinkles, etc. may occur.
  • the wavelength conversion member described in Patent Document 2 is excellent in heat resistance, but since the sintering temperature of the glass matrix is 350 to 900 ° C., the inorganic phosphor powder deteriorates during the sintering of the glass matrix. There is. Moreover, the wavelength conversion member described in Patent Document 2 is difficult to apply on a base material, and is difficult to process after sintering.
  • the present invention has been made in view of such circumstances, and an object of the present invention is to provide a silicone resin composition having a good coating property and a cured product having excellent heat resistance.
  • the present invention provides the following [1] to [15].
  • a silicone resin composition comprising a silicone resin and a solvent
  • the silicone resin composition is a liquid composition having a viscosity of 100 to 50000 mPa ⁇ s at 25 ° C.
  • the silicone resin includes a structural unit represented by the following formula (A3), The structural unit represented by the following formula (A1), the structural unit represented by the following formula (A1 ′), the structural unit represented by the following formula (A2), and the following formula (A3) contained in the silicone resin.
  • the total content of the structural units is 80 mol% or more based on the total content of all the structural units contained in the silicone resin. Silicone resin composition.
  • 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 silicone resin is 55 mol% or more based on the total content of all the structural units contained in the silicone resin.
  • the content of the solvent contained in the silicone resin composition is 10 to 40% by mass with respect to the total content of all components contained in the silicone resin composition.
  • the silicone resin composition of description [4] The silicone resin composition according to any one of [1] to [3], wherein the silicone resin is substantially composed of a condensation type silicone resin. [5] The silicone resin composition according to any one of [1] to [4], wherein R 1 is a methyl group, and R 2 is an alkoxy group having 1 to 3 carbon atoms or a hydroxyl group. [6] The silicone resin composition according to any one of [1] to [5], wherein the silicone resin has a weight average molecular weight in terms of polystyrene of 1500 to 15000.
  • the silicone resin contains a first oligomer,
  • the first oligomer includes a structural unit represented by the following formula (B2),
  • the polystyrene equivalent weight average molecular weight of the first oligomer is 1000 to 10,000.
  • the silicone resin composition according to any one of [6].
  • 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.
  • the silicone resin composition according to [7] which is 30 to 60 mol% with respect to the total content of all structural units contained in the first oligomer.
  • the first oligomer includes a structural unit represented by the following formula (B1), the following formula (B1 ′), the following formula (B2), or the following 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.
  • (R 5 ) n Si (OR 6 ) m O (4-n ⁇ m) / 2 (I) [Where: 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.
  • T-form means a structural unit containing a silicon atom bonded to three oxygen atoms.
  • the D form means a structural unit containing a silicon atom bonded to two oxygen atoms.
  • the silicone resin contains a second oligomer,
  • the second oligomer includes a structural unit represented by the formula (A1), the formula (A1 ′), the formula (A2), or the formula (A3),
  • the content of the structural unit represented by the formula (A3) contained in the second oligomer is a structural unit represented by the formula (A1), a structural unit represented by the formula (A1 ′), 0 to 30 mol% based on the total content of the structural unit represented by the formula (A2) and the structural unit represented by the formula (A3)
  • the polystyrene equivalent weight average molecular weight of the second oligomer is less than 1500. [1] to [10]
  • the silicone resin composition according to any one of [10].
  • a wavelength conversion material-containing silicone resin composition comprising the silicone resin composition according to any one of [1] to [11] and a wavelength conversion material.
  • the wavelength conversion material-containing silicone resin composition according to [12] which is a liquid composition having a viscosity of 1,000 to 500,000 mPa ⁇ s at 25 ° C.
  • the content of the wavelength conversion material is 40% by mass or more based on the total content of all components contained in the wavelength conversion material-containing silicone resin composition, according to [12] or [13].
  • a wavelength conversion material-containing silicone resin composition [15] A wavelength conversion material-containing sheet comprising a cured product of the wavelength conversion material-containing silicone resin composition according to any one of [12] to [14].
  • the structural unit contained in the silicone resin is preferably contained in the silicone resin as a repeating unit.
  • the silicone resin composition of this embodiment is Including a silicone resin and a solvent, A liquid composition having a viscosity of 100 to 50,000 mPa ⁇ s at 25 ° C .; Including a structural unit represented by the following formula (A3), The structural unit represented by the following formula (A1) contained in the silicone resin, the structural unit represented by the following formula (A1 ′), the structural unit represented by the following formula (A2), and the following formula (A3) The total content of structural units is 80 mol% or more based on the total content of all structural units contained in the silicone resin.
  • 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 silicone resin composition of the present embodiment has good coatability, and the cured product (matrix) after curing is excellent in heat resistance. Therefore, the silicone resin composition of this embodiment is suitable for the formation material of the fluorescent substance sheet for LD, for example, and is suitable for the formation material of the sealing layer of LED. Since the silicone resin composition of this embodiment is excellent in all of application property, heat resistance, and filler receptivity, it is particularly suitable as a material for forming a phosphor sheet for LD.
  • the viscosity of the silicone resin composition of the present embodiment is preferably 300 to 20000 mPa ⁇ s, more preferably 400 to 15000 mPa ⁇ s, and further preferably 500 to 10,000 mPa ⁇ s at 25 ° C. . If the viscosity of the silicone resin composition of the present embodiment is within the above range at 25 ° C., when mixed with the wavelength conversion material, the mixing property with the wavelength conversion material is good and the wavelength conversion material is settled. Is suppressed.
  • silicone resin contained in the silicone resin composition of this embodiment may be one kind alone, or two or more kinds.
  • 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”.
  • D-form a structural unit containing a silicon atom bonded to two oxygen atoms
  • M body A structural unit containing a silicon atom bonded to one oxygen atom
  • 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 the end of the organopolysiloxane chain contained in the condensed silicone resin.
  • the structural unit represented by the formula (A3) constitutes a branched structure of an organopolysiloxane chain contained in the condensation type silicone resin. That is, the structural unit represented by the formula (A3) forms a part of a network structure or a ring structure in the condensed silicone resin.
  • 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 content of T-form (that is, the total content of T1-form, T2-form and T3-form) is the total content of all structural units contained in the silicone resin. It is preferable that it is 80 mol% or more. In other words, the total content of T1 silicon atoms, T2 silicon atoms, and T3 silicon atoms is preferably 80 mol% or more with respect to the total content of all silicon atoms contained in the silicone resin.
  • the silicone resin contained in the silicone resin composition of the present embodiment includes a structural unit represented by the above formula (A3), a structural unit represented by the above formula (A1), and represented by the above formula (A1 ′). And one or more structural units selected from the group consisting of the structural unit represented by the formula (A2) may be further included.
  • the silicone resin contained in the silicone resin composition of the present embodiment includes a structural unit represented by the above formula (A1), a structural unit represented by the above formula (A1 ′), and a structure represented by the above formula (A2). It is preferable that all of the unit and the structural unit represented by the above formula (A3) are included.
  • silicone resin contained in the silicone resin composition of the present embodiment contains an oligomer component to be described later, “all structural units contained in the silicone resin contained in the silicone resin composition of the present embodiment”. "Includes a structural unit contained in the oligomer component.
  • the content of the structural unit represented by the above formula (A3) is 55 mol% with respect to the total content of all the structural units contained in the silicone resin.
  • it is 60 mol% or more, more preferably 65 mol% or more, and particularly preferably 70 mol% or more.
  • the content of the T3 body is preferably 55 mol% or more with respect to the total content of all structural units contained in the silicone resin. More preferably, it is 60 mol% or more, still more preferably 65 mol% or more, and particularly preferably 70 mol% or more.
  • the content of T3 silicon atoms contained in the silicone resin is preferably 55 mol% or more, and preferably 60 mol% or more with respect to the total content of all silicon atoms contained in the silicone resin. More preferably, it is more preferably 65 mol% or more, and particularly preferably 70 mol% or more.
  • the silicone resin contained in the silicone resin composition of the present embodiment if the content of the T isomer and the content of the T3 isomer are within the above ranges, the silicone resin composition is cured.
  • the object exhibits sufficient heat resistance and also exhibits high light transmittance even after the heat resistance test.
  • the content of T3 silicon atoms can be determined as a ratio of the area of signals attributed as T3 silicon atoms to the total area of signals of all silicon atoms determined in 29 Si-NMR measurement.
  • the contents of T1 silicon atom and T2 silicon atom can also be determined by the same method.
  • R 1 is preferably an alkyl group, and is preferably a methyl group from the viewpoint of heat resistance.
  • the C 1-10 represented by R 1 may be a linear alkyl group, a branched alkyl group, or an alkyl group having a cyclic structure. Among these, a linear or branched alkyl group is preferable, a linear alkyl group is more preferable, and a methyl group is more 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, an n-propyl group, and an n-butyl group.
  • Examples of the aryl group having 6 to 10 carbon atoms represented by R 1 include unsubstituted aryl groups such as a phenyl group and a naphthyl group; and alkylaryl groups such as a methylphenyl group, an ethylphenyl group and a propylphenyl group. It is done. Among these, a phenyl group is preferable.
  • R 2 represents methoxy group, ethoxy group, isopropoxy A group or a hydroxyl group is preferred.
  • 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.
  • the silicone resin contained in the silicone resin composition of the present embodiment is preferably substantially composed of a condensation type silicone resin.
  • 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.
  • An addition-type silicone resin is a resin that is polymerized by an addition reaction between a hydrosilyl group and a carbon-carbon double bond.
  • substantially composed of a condensation type silicone resin means that the silicone resin contained in the wavelength conversion material-containing silicone resin composition is composed only of the condensation type silicone resin and the wavelength conversion material-containing silicone resin composition
  • the extent that does not reduce the heat resistance of the cured product means that the degree of reduction in heat resistance is such that there is no practical problem. Specifically, it means that the content of other silicone resins is 1% by mass or less with respect to the total content of silicone resins contained in the wavelength conversion material-containing silicone resin composition, and 0.1 mass % Or less is preferable.
  • the silicone resin contained in the silicone resin composition of the present embodiment is a resin substantially composed of a condensation type silicone resin
  • the cured product of the silicone resin composition maintains a higher light transmittance after the heat test. Can do.
  • the silicone resin contained in the silicone resin composition of the present embodiment includes a structural unit represented by the above formula (A1), a structural unit represented by the above formula (A1 ′), and a structure represented by the above formula (A2).
  • R 1 is preferably a methyl group
  • R 2 is preferably an alkoxy group having 1 to 3 carbon atoms or a hydroxyl group.
  • the polystyrene-reduced weight average molecular weight of the silicone resin contained in the silicone resin composition of the present embodiment is preferably 1500 to 15000, more preferably 2000 to 10000, and more preferably 2000 to 8000. Further preferred is 2500 to 6000.
  • the weight average molecular weight in terms of polystyrene of the silicone resin is within the above range, the curability and the solubility in a solvent are excellent, so that the handling property and the coating property when using the silicone resin composition are 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 silicone resin contained in the silicone resin composition of the present embodiment further includes a structural unit represented by the following formula (C1), formula (C1 ′), formula (C2), formula (C3), or formula (C4). You may go out.
  • 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 isomers.
  • 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 isomer.
  • 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.
  • Silicone resin A The silicone resin contained in the silicone resin composition of the present embodiment is preferably a mixture of a silicone resin as a main ingredient (hereinafter referred to as “silicone resin A”) and an oligomer component described later.
  • Silicone resin A includes 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 to further include a structural unit of a species or more.
  • 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 polystyrene-reduced weight average molecular weight of the silicone resin A 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 weight average molecular weight in terms of polystyrene of the silicone resin A is preferably 1500 or more and 7000 or less, and more preferably 2000 or more and 5000 or less. When the weight average molecular weight in terms of polystyrene of the silicone resin A is within this range, the mixing property with the phosphor described later is good.
  • 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 when mixed with the wavelength conversion material described later. Therefore, the mixing property with the wavelength conversion material is improved.
  • 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.
  • the storage stability of the silicone resin composition of the present embodiment is good and the fluidity is within an appropriate range. The handling property of the 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 contained in the silicone resin composition of the present embodiment is preferably 60% by mass to 100% by mass with respect to the total content of all silicone resins contained in the silicone resin composition. More preferably, it is 70 to 95% by mass.
  • the silicone resin contained in the silicone resin composition of this embodiment may contain an oligomer component in addition to the silicone resin A.
  • the cured product of the silicone resin composition of the present embodiment is excellent in flexibility and crack resistance.
  • Oligomer B (first oligomer)
  • Examples of the oligomer component include an oligomer 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 weight average molecular weight in terms of polystyrene of the oligomer containing the structural unit represented by the formula (B1), formula (B1 ′), formula (B2) and formula (B3) is preferably 1000 to 10,000, and 2000 to 8000. More preferably, it is more preferably 3000 to 6000.
  • the weight-average molecular weight of the oligomer in terms of polystyrene is within this range, the miscibility with the silicone resin A and the oligomer C described later is good.
  • oligomer B an oligomer component having a structural unit represented by formula (B1), formula (B1 ′), formula (B2), and formula (B3) and having a polystyrene-equivalent weight average molecular weight of 1000 to 10,000 is used. , 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 silicone resin composition of this embodiment contains an oligomer that satisfies (c), it is easy to produce a phosphor sheet free from wrinkles and cracks.
  • 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 silicone resin composition of this embodiment ensures the solubility of silicone resin A and oligomer B. 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.
  • a functional group capable of generating a siloxane bond include a halogen atom, a hydroxyl group, and an alkoxy group.
  • organosilicon compound corresponding to the structural unit represented by the above formula (B3) examples include organotrihalosilane, organotrialkoxysilane and the like.
  • organosilicon compound corresponding to the structural unit represented by the above formula (B2) examples 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 content of the oligomer B contained in the silicone resin composition of the present embodiment is preferably 0.1 to 20% by mass with respect to the total content of all silicone resins contained in the silicone resin composition. More preferably, it is 2 to 15% by mass, and further preferably 0.5 to 10% by mass.
  • the content of the oligomer B contained in the silicone resin composition of the present embodiment is 0.1 to 20% by mass with respect to the content of the silicone resin A contained in the silicone resin composition of the present embodiment. It is preferably 1 to 15% by mass, more preferably 5 to 12% by mass.
  • 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 peaks.
  • Oligomer C (second oligomer)
  • Other examples of the oligomer component include, for example, a silicone resin containing a structural unit represented by the above formula (A1), formula (A1 ′), formula (A2), or formula (A3), and the above formula (A3 ),
  • 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 alkenyl group or hydrosilyl group. That is, 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).
  • R 2 in the structural unit is preferably not having an alkenyl group or a hydrogen atom.
  • the oligomer C is preferably an oligomer having an organopolysiloxane structure represented by the following formula (2).
  • 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 .
  • [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 (2) Abundance ratio: equal to [y 2 / (x 2 + y 2 + z 2 )]. That is, p 2 , q 2 , r 2 , a 2 and b 2 in the formula (2) are appropriately adjusted so that the abundance ratio of T3 silicon atoms is in the range of 0 to 0.3.
  • the oligomer C that may be contained in the silicone resin composition of the present embodiment is a silicone resin having an organopolysiloxane structure represented by the formula (2), and includes T1 silicon atoms, T2 silicon atoms, and T3 silicon atoms. 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 include only cyclic molecules, but preferably includes 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 content of the oligomer C contained in the silicone resin composition of the present embodiment is preferably 0.1 to 20% by mass with respect to the total content of all silicone resins contained in the silicone resin composition. More preferably, it is 2 to 15% by mass, and further preferably 0.5 to 10% by mass.
  • the content of the oligomer C contained in the silicone resin composition of the present embodiment is 0.1 to 20% by mass with respect to the content of the silicone resin A contained in the silicone resin composition of the present embodiment. It is preferably 0.3 to 10% by mass, more preferably 0.5 to 5% by mass.
  • 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 of the oligomer C in terms of polystyrene is too large, the crack resistance of the cured product of the silicone resin composition 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 silicone resin composition of the present embodiment preferably contains silicone resin A and oligomer B or oligomer C, and more preferably contains silicone resin A, oligomer B and oligomer C.
  • the silicone resin composition of the present embodiment contains a solvent for the purpose of achieving good coating properties.
  • the solvent is not particularly limited as long as the silicone resin can be dissolved.
  • the solvent for example, two or more kinds of solvents having different boiling points (hereinafter referred to as “solvent P” and “solvent Q”) can be used.
  • 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, a glycol ether solvent and a glycol ester solvent 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 diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and ethylene glycol monobutyl ether acetate are more preferable.
  • the content of the solvent is usually 5 to 60% by mass and 10 to 40% by mass with respect to the total content of all components contained in the silicone resin composition. It is preferably 15 to 35% by mass. Since the silicone resin composition of the present embodiment is a liquid composition having a viscosity of 100 to 50000 mPa ⁇ s at 25 ° C., the coating property is good. Moreover, even when the silicone resin composition of this embodiment further contains the wavelength conversion material mentioned later, it is easy to adjust applicability
  • the viscosity of the silicone resin composition can be measured by, for example, a method in which a cone plate type E-type viscometer detects a resistance (viscosity resistance) that the cone plate receives from a fluid with a rotational torque.
  • the silicone resin composition of this embodiment is obtained by mixing silicone resin A, a solvent, and oligomer B, oligomer C, or other components as necessary.
  • the silicone resin composition of the present embodiment preferably contains a silicone resin A, a solvent, an oligomer B, and an oligomer C.
  • the mixing method of the silicone resin A, the oligomer B, and the oligomer C is not particularly limited, and any known method that is performed when two or more kinds of polymers are mixed 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.
  • the silicone resin A is heated to a temperature near the boiling point of the solvent P and stirred to thereby form the silicone. Resin A is dissolved.
  • oligomer B, oligomer C, and other components as needed to the obtained solution oligomer B, oligomer C, and other components as needed in the same manner as above.
  • the ingredients are dissolved in solvent P.
  • a solvent having a lower volatility than the solvent P for example, the solvent Q described above
  • solvent P is distilled by heating until the concentration of the solvent P becomes 1% or less.
  • solvent Q can be performed. In order to efficiently perform solvent replacement, heat distillation may be performed under reduced pressure.
  • Residual solvent, water, and the like that can be contained in each of the silicone resin A, the oligomer B, the oligomer C, and other components can be removed by performing solvent substitution. Therefore, the stability of the silicone resin composition can be improved by solvent replacement.
  • the silicone resin composition of the present embodiment may contain other components such as a curing catalyst, a silane coupling agent, inorganic particles, a dispersant, a leveling agent, and an antifoaming agent in addition to the silicone resin and the solvent. .
  • 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.
  • a silane coupling agent is mentioned. 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.
  • the content of the silane coupling agent is usually 0.0001 to 1.0 part by mass and 0.001 to 0.1 part per 100 parts by mass of the silicone resin contained in the silicone resin composition of the present embodiment. It is preferable that it is a mass part.
  • inorganic particles examples include oxides such as silicon, titanium, zirconia, aluminum, iron, and zinc; carbon black, barium titanate, calcium silicate, calcium carbonate, and the like. Of these, oxides such as silicon, titanium, zirconia, and aluminum are more preferable as the inorganic particles.
  • 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 a substantially uniform resin composition is obtained.
  • the inorganic particles contained in the silicone resin composition of the present embodiment may be only one type or two or more types, but are preferably two or more types of inorganic particles having different particle sizes. More preferably, the silicone resin composition of the present embodiment includes inorganic particles having an average primary particle size of 100 to 500 nm and inorganic particles having an average primary particle size of less than 100 nm.
  • the excitation efficiency of the wavelength conversion material by light scattering is improved by including two or more kinds of inorganic particles having different average particle sizes of primary particles, and the wavelength conversion material Sedimentation is suppressed.
  • 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 to 100 parts by weight and preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the silicone resin contained in the silicone resin composition of the present embodiment. Is more preferable.
  • the silicone resin composition of the present embodiment comprises a silicone resin A, a solvent, and optionally an oligomer component or other components, and a liquid composition having a viscosity of 100 to 50000 mPa ⁇ s at 25 ° C. It is. As will be described later in Examples, the silicone resin composition of the present embodiment has good coatability, and the cured product after curing is excellent in heat resistance.
  • the curing catalyst examples 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, phosphoric acid and phosphoric acid ester are promoted; formic acid, acetic acid, succinic acid, citric acid, propionic acid, butyric acid, lactic acid, succinic acid, etc.
  • the organic acid can be used.
  • 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 more preferable.
  • the curing catalyst may be diluted with water, an organic solvent, a silicone monomer, an alkoxysilane oligomer, etc., and then added to the silicone resin composition. preferable.
  • the content of the curing catalyst can be appropriately adjusted in consideration of the heating temperature of the curing reaction of the silicone resin composition, the time, the type of catalyst, and the like.
  • the content of the curing catalyst is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the silicone resin composition of the present embodiment.
  • the amount is more preferably 0.1 to 1 part by mass.
  • the curing catalyst may be added to the silicone resin composition in advance, or may be added to the silicone resin immediately before performing the curing reaction of the silicone resin composition.
  • the wavelength conversion material containing silicone resin composition of this embodiment contains the silicone resin composition and wavelength conversion material which were mentioned above.
  • the wavelength conversion material-containing silicone resin composition of the present embodiment is preferably a liquid composition having a viscosity of 1,000 to 500,000 mPa ⁇ s and a liquid composition having a viscosity of 8,000 to 100,000 mPa ⁇ s at 25 ° C. More preferred is a liquid composition having a viscosity of 10,000 to 80,000 mPa ⁇ s. When the viscosity at 25 ° C. of the wavelength conversion material-containing silicone resin composition is within these ranges, the coatability is improved.
  • wavelength conversion material examples include phosphors and quantum dots.
  • the phosphor include a red phosphor that emits fluorescence in the wavelength range of 570 nm to 700 nm, a yellow phosphor that emits fluorescence in the range of 530 nm to 620 nm, a green phosphor that emits fluorescence in the range of 490 nm to 570 nm, and 420 nm to 480 nm. Blue phosphors that emit fluorescence in the range of. 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 content of the wavelength conversion material is 40% by mass or more based on the total content of all components contained in the wavelength conversion material-containing silicone resin composition. Also good.
  • the upper limit of the content of the wavelength conversion material is, for example, 95% by mass with respect to the total content of all components contained in the wavelength conversion material-containing silicone resin composition.
  • the wavelength conversion material-containing silicone resin composition of the present embodiment is a liquid composition having a viscosity of 1,000 to 500,000 mPa ⁇ s at 25 ° C., and thus has good coating properties. Therefore, the wavelength conversion material-containing silicone resin composition of the present embodiment can be easily applied onto a substrate by, for example, an applicator, a slit die coater, or screen printing.
  • the cured product of the wavelength conversion material-containing silicone resin composition of the present embodiment is suitable for use as, for example, a material for forming a wavelength conversion material-containing sheet for a semiconductor laser or a material for forming a wavelength conversion material-containing sheet for an LED.
  • wavelength conversion material-containing sheet of the present embodiment uses a cured product of the wavelength conversion material-containing silicone resin composition of the present embodiment as a forming material.
  • the wavelength conversion sheet of the present embodiment can be suitably used for applications of wavelength conversion sheets in LEDs, solar cells, semiconductor lasers, photodiodes, CCDs, CMOSs, and the like.
  • the wavelength conversion sheet of this embodiment is excellent in heat resistance, it can be 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 may contain the inorganic particles described above.
  • the wavelength conversion material can be effectively excited by scattering light in the wavelength conversion sheet. Moreover, it can suppress that a wavelength conversion material settles in a silicone resin composition in the manufacturing stage of the wavelength conversion sheet of this embodiment.
  • the wavelength conversion sheet of this embodiment can manufacture a wavelength conversion sheet stably, it is preferable that it is 10 micrometers or more.
  • the thickness of the wavelength conversion sheet of the present embodiment is preferably 1 mm or less, more preferably 500 ⁇ m or less, and more preferably 200 ⁇ 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 by the silicone resin 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 an average value thereof.
  • the plural places include a total of five places including one central portion of the wavelength conversion sheet and four corner portions of the wavelength conversion sheet.
  • the wavelength conversion sheet may be formed on a support base material.
  • a support base material a base material using a known metal, film, glass, ceramic, paper, or the like as a forming material 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.
  • Wavelength conversion sheet manufacturing method The manufacturing method of the wavelength conversion sheet concerning this embodiment is explained.
  • a wavelength conversion material-containing silicone resin composition in which a wavelength conversion material is dispersed in the above-described silicone resin composition is prepared.
  • additives such as inorganic particles and an adhesion aid may be added.
  • a wavelength conversion material-containing silicone resin composition can be obtained by uniformly mixing and dispersing 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 reduced pressure as necessary.
  • the obtained wavelength conversion material-containing silicone resin composition is applied onto a supporting substrate.
  • coating of the wavelength conversion material containing silicone resin composition can be performed using a well-known coating device.
  • 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. Among these, since the film thickness of the obtained wavelength conversion sheet tends to be uniform, it is preferable to apply the wavelength length conversion material-containing silicone resin composition with a slit die coater or an applicator.
  • the coating film formed on the support substrate is heated and cured to obtain a wavelength conversion sheet.
  • the coating film is heated using a natural convection oven, a blower oven, a vacuum oven, an inert oven, a hot plate, a hot press, an infrared heater, or the like.
  • a blower oven is preferable from the viewpoint of productivity.
  • Examples of the heating conditions for the coating film include a method of heating at 40 ° C. to 250 ° C. for 5 minutes to 100 hours.
  • the heating time is preferably 1 to 30 hours, more preferably 2 to 10 hours, still more preferably 3 to 8 hours. If the heating time is within this range, the solvent can be sufficiently removed and coloring during heating can be prevented.
  • the coating film After coating the wavelength conversion material-containing silicone resin composition on the support substrate, the coating film may be cured by leaving it in an atmosphere having a temperature of 250 ° C. or lower. The coating film may be cured by leaving it in the atmosphere. Further, when curing the coating film, in order to reduce the solvent and water present in the wavelength conversion material-containing silicone resin composition, and to control the condensation reaction rate between the silicone resin A and the silicone oligomer, for example, The coating film is formed in stages, such as at 40 to 60 ° C. for 5 to 30 minutes, then at 60 to 100 ° C. for 10 to 60 minutes, and then at 140 to 200 ° C. for 30 to 5 hours. It may be cured.
  • the wavelength conversion sheet thus obtained is excellent in heat resistance. Moreover, since the wavelength conversion material containing silicone resin composition of this embodiment is excellent in applicability
  • 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 disposed 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, 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
  • silicone resin composition (sample) was weighed using a pipette and added to the cup of the E type viscometer.
  • the cone “spindle CPE-40” (shear and 7.50 N, cone angle 0.8 °, cone radius 24 mm) or “spindle CPE-52” (shear rate 2.00 N, cone angle 3 °, cone radius) was used. 12 mm).
  • the rotor of the E-type viscometer was rotated to hold the silicone resin composition at 1.5 rpm for 5 minutes, and the measured value of the silicone resin composition was read as the viscosity.
  • the wavelength conversion material-containing silicone resin composition was screen-printed on an aluminum substrate.
  • the model “LS-150” manufactured by Neurong Seimitsu Kogyo Co., Ltd.
  • the model “ST250-30-C57” (frame size: 320 mm square, screen type: stainless steel) is used as the screen mask. used.
  • the screen thickness was 56 ⁇ m
  • the emulsion thickness was 5 ⁇ m
  • the total film thickness was 61 ⁇ m.
  • the squeegee angle angle formed by the horizontal plane and the squeegee was 70 degrees. Subsequently, the appearance of the coating film before curing was evaluated according to the following criteria.
  • Resin 2 polystyrene equivalent weight average molecular weight: ⁇ 1000
  • resin 3 polystyrene equivalent weight average molecular weight: amount 3400
  • Resin 3 contained 95% by mass or more of a resin composed of structural units shown in Table 3 below. Further, the resin 3 has a total area of peaks present in a region having a polystyrene-equivalent weight average molecular weight of 7500 or more, which is 20% or more of the total area of all peaks, and a polystyrene-equivalent weight average. The sum of the areas of the peaks existing in the region having a molecular weight of 1000 or less was 30% or more with respect to the sum of the areas of all the peaks.
  • Resin 1 is dissolved in a solvent by adding 789.60 g of resin 1, 96.00 g of propyl acetate, and 314.40 g of isopropyl alcohol in a flask placed in an oil bath and stirring at 80 ° C. I let you. 8.47 g of resin 2 and 75.08 g of resin 3 were added to the resulting solution, and the mixture was stirred for 1 hour to dissolve resin 2 and resin 3 in a solvent. To the resulting solution, 274.49 g of 2-butoxyethyl acetate and 0.22 g of 3-glycidoxypropyltrimethoxysilane 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. Thereafter, 27.76 g of 2-butoxyethyl acetate was added thereto and stirred uniformly to obtain the silicone resin composition of Example 1.
  • Example 2 In Example 1, the silicone resin composition of Example 2 was obtained in the same manner as in Example 1 except that 32.76 g of dipropylene glycol monomethyl ether was used instead of 27.76 g of 2-butoxyethyl acetate. It was.
  • Comparative Example 1 A two-component thermosetting addition-reaction type silicone resin, A and B of a transparent sealing resin for photo devices (model “SCR-1016 (A / B)”, manufactured by Shin-Etsu Silicone) 50:50 (Mass ratio) was mixed and the silicone resin composition of the comparative example 1 was obtained.
  • the silicone resin composition of Comparative Example 1 was a silicone resin composition containing no T-form.
  • the viscosities in Table 4 are values measured using “LVDV-II + Pro” as an E-type viscometer and “Spindle CPE-52” (shear rate 2.00 N, cone angle 3 °, cone radius 12 mm) as a cone. is there.
  • the silicone resin composition of Comparative Example 1 was cured into a disk shape having a diameter of 4 cm and a thickness of 0.5 mm under heating conditions of 150 ° C. for 5 hours.
  • the heat resistance of the obtained cured product was evaluated by the above-described heat resistance evaluation method. The results are shown in Table 4.
  • the light transmittance indicates the ratio (%) of the light transmittance of the cured product after the heat test to the light transmittance of 100% of the cured product before the heat test.
  • the cured products of the silicone resin compositions of Examples 1 and 2 had a light transmittance of 100% even after a heat test at 250 ° C. for 1000 hours, and no appearance of wrinkles or cracks was observed in appearance.
  • Comparative Example 2 The silicone resin composition of Comparative Example 2 was obtained by further adding 3.7 g of 2-butoxyethyl acetate to 10 g of the silicone resin composition obtained in Example 1.
  • the viscosity of the silicone resin composition of Comparative Example 2 was 32 mPa ⁇ s.
  • “DV2TLVCJ0” was used as the E-type viscometer
  • “Spindle CPE-40” Shearray and 7.50 N, cone angle 0.8 °, cone radius 24 mm
  • a curing accelerator 2 parts by weight of a curing accelerator was added to 100 parts by weight of the silicone resin composition of Comparative Example 2 and stirred.
  • a curing catalyst solution containing 15% by mass of phosphoric acid was used as the curing accelerator.
  • the obtained silicone resin composition was cured into a disk shape having a diameter of 4 cm and a thickness of 0.5 mm under a heating condition of 150 ° C. for 5 hours. Since the resulting cured product had wrinkles, other evaluations could not be performed.
  • Example 3 a silicone resin composition was obtained in the same manner as in Example 1 except that 97.09 g of 2-butoxyethyl acetate was used instead of 27.76 g of 2-butoxyethyl acetate.
  • the silicone resin composition of Comparative Example 3 was obtained by heating 30 g of the obtained silicone resin composition at 40 ° C. for 240 hours.
  • the viscosity of the silicone resin composition of Comparative Example 3 was 66000 mPa ⁇ s.
  • “DV2TLVCJ0” was used as the E-type viscometer
  • spindle CPE-52 spindle CPE-52 (shear rate 2.00 N, cone angle 3 °, cone radius 12 mm) was used as the cone.
  • a curing accelerator 2 parts by weight of a curing accelerator was added to 100 parts by weight of the silicone resin composition of Comparative Example 3 and stirred.
  • a curing catalyst solution containing 15% by mass of phosphoric acid was used as the curing accelerator.
  • the obtained silicone resin composition was cured into a disk shape having a diameter of 4 cm and a thickness of 0.5 mm under a heating condition of 150 ° C. for 5 hours. Since bubbles were generated in the obtained cured product, other evaluation could not be performed.
  • Examples 3 to 5 The wavelength conversion material-containing silicone resin composition of Examples 3 to 5 was added to the silicone resin composition of Example 1 after sufficiently adding the wavelength conversion material with the content shown in Table 5 below, followed by mixing with stirring. Ink) was obtained.
  • the wavelength conversion material Y 3 Al 5 O 12 : Ce (model “C2P”, average particle size 13.6 ⁇ m, manufactured by Tokyo Chemical Research Laboratories) was used.
  • content of the wavelength conversion material in Table 5 is the mass% with respect to the total content of all the components contained in the wavelength conversion material containing silicone resin composition.

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