JP2015073084A - Wavelength conversion sheet, sealed optical semiconductor, and optical semiconductor element device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a wavelength conversion sheet, a sealed optical semiconductor, and an optical semiconductor element device capable of suppressing variation in chromaticity.SOLUTION: A wavelength conversion sheet is formed of silicone resin, an organic particle, and a phosphor resin composition including fluorescence substance, where a refraction index of the organic particle is 1.45 to 1.60.

Description

  The present invention relates to a wavelength conversion sheet, a sealed optical semiconductor element, and an optical semiconductor element device, and more particularly to a wavelength conversion sheet, a sealed optical semiconductor element, and an optical semiconductor element device used for optical applications.

  Conventionally, a white light semiconductor device is known as a light emitting device capable of emitting high energy light.

  The white light semiconductor device includes, for example, an optical semiconductor element that emits blue light, and a sealing material that seals the optical semiconductor element and converts blue light (wavelength) into yellow light. White light emission is realized by mixing yellow and the like.

  As a sealing material for such a white light semiconductor device, for example, a sheet-shaped optical semiconductor sealing material containing a silicone resin, a phosphor, and silica particles has been proposed (see, for example, Patent Document 1). .

JP2011-228525A

  However, the sheet-shaped optical semiconductor encapsulant has a problem that the chromaticity of light that has passed through the encapsulant has a large variation. As a result, color unevenness occurs in white light emitted from the optical semiconductor device.

  An object of the present invention is to provide a wavelength conversion sheet, a sealed optical semiconductor element, and an optical semiconductor element device that can suppress variations in chromaticity.

  The wavelength conversion sheet of the present invention is formed from a phosphor resin composition containing a silicone resin, organic particles, and a phosphor, and the organic particles have a refractive index of 1.45 to 1.60.

  Moreover, in the wavelength conversion sheet | seat of this invention, it is suitable that the content rate of the said organic particle in the said wavelength conversion sheet | seat is 10-25 mass%.

  Moreover, in the wavelength conversion sheet | seat of this invention, it is suitable that the total content rate of the said organic particle and the said fluorescent substance in the said wavelength conversion sheet | seat is 15-70 mass%.

  In the wavelength conversion sheet of the present invention, it is preferable that the organic particles are made of at least one material selected from the group consisting of acrylic resins, acrylic-styrene resins, and styrene resins.

In the wavelength conversion sheet of the present invention, it is preferable that the phosphor contains a CaAlSiN ₃ : Eu phosphor.

  The optical semiconductor element of the present invention is characterized by comprising an optical semiconductor element and the above-described wavelength conversion sheet disposed to face the optical semiconductor element.

  The optical semiconductor device of the present invention includes a substrate, an optical semiconductor element mounted on the substrate, and the above-described wavelength conversion sheet disposed to face the optical semiconductor element.

  Since the wavelength conversion sheet of the present invention contains organic particles having a refractive index of 1.45 to 1.60, it suppresses variation in chromaticity compared to the case of containing other additives. can do.

  Moreover, since the optical semiconductor element and the optical semiconductor device are provided with the wavelength conversion sheet of the present invention, they can emit uniform white light (with little color unevenness).

1A to 1B are process diagrams showing a process of manufacturing an embodiment of the wavelength conversion sheet of the present invention, in which FIG. 1A is a process of preparing a release substrate, and FIG. 1B is a stack of wavelength conversion sheets. The process to perform is shown. 2A to 2D show a process of manufacturing an embodiment of the optical semiconductor device of the present invention using the wavelength conversion sheet shown in FIG. 1B, FIG. 2A shows a sealing layer lamination process, FIG. 2B shows an arrangement process, 2C shows a sealing process, and FIG. 2D shows a peeling process. 3A to 3E show a process of manufacturing a modified example of the optical semiconductor device using the wavelength conversion sheet shown in FIG. 1B. FIG. 3A shows a sealing layer stacking process, FIG. 3B shows an arrangement process, and FIG. FIG. 3D shows the second peeling process, and FIG. 3E shows the mounting process. FIG. 4 shows another embodiment of the optical semiconductor device of the present invention (an embodiment in which the optical semiconductor device includes a housing). FIG. 5 is a plan view illustrating a measurement method for evaluating chromaticity variation.

  In FIG. 1, the upper side of the paper surface is the upper side (first side in the first direction, one side in the thickness direction), and the lower side of the paper surface is the lower side (the other side in the first direction, the other side in the thickness direction). For the drawings other than FIG. 1, the direction of FIG. 1 is used as a reference.

[Wavelength conversion sheet]
The wavelength conversion sheet of the present invention is formed into a sheet shape from a phosphor resin composition containing a silicone resin, organic particles and a phosphor.

  As the silicone resin, for example, a transparent silicone resin used as a sealing material for sealing an optical semiconductor element can be used, and a known or commercially available one can be used. Examples of the silicone resin include a two-stage reaction curable resin and a one-stage reaction curable resin.

  The two-stage reaction curable resin has two reaction mechanisms. In the first stage reaction, the A stage state is changed to the B stage (semi-cured), and then in the second stage reaction, the B stage state is obtained. To C-stage (complete curing). That is, the two-stage reaction curable resin is a thermosetting resin that can be in a B-stage state under appropriate heating conditions. However, the two-stage reaction curable resin can be changed from the A-stage state to the C-stage state at a time without maintaining the B-stage state by intense heating. The B stage state is a state between the A stage state in which the thermosetting resin is liquid and the C stage state in which the thermosetting resin is completely cured. It is a semi-solid or solid state smaller than the elastic modulus in the C-stage state.

  The one-stage reaction curable resin has one reaction mechanism, and can be changed from the A-stage state to the C-stage (completely cured) by the first-stage reaction. The first-stage reaction curable resin can be changed from the A-stage state to the B-stage state in the middle of the first-stage reaction. Is resumed, and includes a thermosetting resin that can be converted into a C stage (completely cured) from the B stage state. That is, such a thermosetting resin is a thermosetting resin that can be in a B-stage state. On the other hand, the first-stage reaction curable resin cannot be controlled to stop in the middle of the first-stage reaction, that is, cannot enter the B stage state, and is changed from the A stage state to the C stage (completely cured). A) thermosetting resin.

Specific examples of the silicone resin include, for example, a condensation / addition reaction curable silicone resin composition, a heteroatom-containing modified silicone resin composition, an addition reaction curable silicone resin composition, an inorganic oxide-containing silicone resin composition, It consists of a silicone resin composition such as a thermoplastic / thermosetting silicone resin composition.

  The silicone resin composition may be used alone or in combination.

  Among silicone resin compositions, from the viewpoint of transparency, durability, heat resistance, light resistance, and suppression of chromaticity variation, addition reaction curable silicone resin compositions, condensation / addition reaction curable silicone resin compositions are preferred. And more preferably, an addition reaction curable silicone resin composition.

  The addition reaction curable silicone resin composition is a one-stage reaction curable resin and contains, for example, an alkenyl group-containing polysiloxane, a hydrosilyl group-containing polysiloxane, and a hydrosilylation catalyst.

  The alkenyl group-containing polysiloxane contains two or more alkenyl groups and / or cycloalkenyl groups in the molecule. The alkenyl group-containing polysiloxane is specifically represented by the following average composition formula (1).

Average composition formula (1):
R ¹ _a R ² _b SiO _{(4-ab) / 2}
(In the formula, R ¹ represents an alkenyl group having 2 to 10 carbon atoms and / or a cycloalkenyl group having 3 to 10 carbon atoms. R ² represents an unsubstituted or substituted monovalent carbon atom having 1 to 10 carbon atoms. A hydrogen group (excluding an alkenyl group and a cycloalkenyl group); a is from 0.05 to 0.50, and b is from 0.80 to 1.80.
In formula (1), examples of the alkenyl group represented by R ¹ include alkenyl having 2 to 10 carbon atoms such as vinyl group, allyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, and octenyl group. Groups. Examples of the cycloalkenyl group represented by R ¹ include cycloalkenyl groups having 3 to 10 carbon atoms such as a cyclohexenyl group and a norbornenyl group.

R ¹ is preferably an alkenyl group, more preferably an alkenyl group having 2 to 4 carbon atoms, and still more preferably a vinyl group.

The alkenyl groups represented by R ¹ may be the same type or a plurality of types.

The monovalent hydrocarbon group represented by R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms other than an alkenyl group and a cycloalkenyl group.

  Examples of the unsubstituted monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, and a pentyl group. , Heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group and other alkyl groups having 1 to 10 carbon atoms such as cyclopropyl, cyclobutyl group, cyclopentyl group and cyclohexyl group. Examples include alkyl groups such as aryl groups having 6 to 10 carbon atoms such as phenyl, tolyl and naphthyl groups, and aralkyl groups having 7 to 8 carbon atoms such as benzyl and benzylethyl groups. Preferably, a C1-C3 alkyl group and a C6-C10 aryl group are mentioned, More preferably, a methyl group and / or a phenyl group are mentioned.

  On the other hand, examples of the substituted monovalent hydrocarbon group include those in which the hydrogen atom in the above-described unsubstituted monovalent hydrocarbon group is substituted with a substituent.

  Examples of the substituent include a halogen atom such as a chlorine atom, for example, a glycidyl ether group.

  Specific examples of the substituted monovalent hydrocarbon group include a 3-chloropropyl group and a glycidoxypropyl group.

  The monovalent hydrocarbon group may be unsubstituted or substituted, and is preferably unsubstituted.

The monovalent hydrocarbon groups represented by R ² may be of the same type or a plurality of types. Preferably, a methyl group and / or a phenyl group are mentioned, More preferably, combined use of a methyl group and a phenyl group is mentioned.

  a is preferably 0.10 or more and 0.40 or less.

  b is preferably 1.5 or more and 1.75 or less.

  The weight average molecular weight of the alkenyl group-containing polysiloxane is, for example, 100 or more, preferably 500 or more, and for example, 10,000 or less, preferably 5000 or less. The weight average molecular weight of the alkenyl group-containing polysiloxane is a conversion value based on standard polystyrene measured by gel permeation chromatography.

  The alkenyl group-containing polysiloxane is prepared by an appropriate method, and a commercially available product can also be used.

  The alkenyl group-containing polysiloxanes may be of the same type or a plurality of types.

  The hydrosilyl group-containing polysiloxane contains, for example, two or more hydrosilyl groups (SiH groups) in the molecule. Specifically, the hydrosilyl group-containing polysiloxane is represented by the following average composition formula (2).

Average composition formula (2):
^{_{H c R 3 d SiO (4}} -c-d) / 2
(In the formula, R ³ represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms (excluding an alkenyl group and / or a cycloalkenyl group). C is 0.30 or more. 1.0, and d is 0.90 or more and 2.0 or less.)
In formula (2), the unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R ³ is an unsubstituted or substituted carbon group having 1 to 10 carbon atoms represented by R ² in formula (1). The same thing as the monovalent hydrocarbon group of is illustrated. Preferably, an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and more preferably a methyl group. And / or a phenyl group.

  c is preferably 0.5 or less.

  d is preferably 1.3 or more and 1.7 or less.

  The weight average molecular weight of the hydrosilyl group-containing polysiloxane is, for example, 100 or more, preferably 500 or more, and for example, 10,000 or less, preferably 5000 or less. The weight average molecular weight of the hydrosilyl group-containing polysiloxane is a conversion value based on standard polystyrene measured by gel permeation chromatography.

  The hydrosilyl group-containing polysiloxane is prepared by an appropriate method, and a commercially available product can also be used.

  Further, the hydrosilyl group-containing polysiloxane may be of the same type or a plurality of types.

Average composition formula described above (1) and the average compositional formula (2), at least one of the hydrocarbon groups R ² and R ³ preferably includes a phenyl group, more preferably, R ² and R ³ Both hydrocarbons contain a phenyl group. When at least one of the hydrocarbon groups of R ² and R ³ contains a phenyl group, the addition reaction curable silicone resin composition is a phenyl silicone resin composition. This phenyl silicone resin composition is a one-stage reaction curable resin that can be in a B-stage state.

On the other hand, when both R ² and R ³ hydrocarbons are methyl groups, the addition reaction curable silicone resin composition is a methyl silicone resin composition. The methyl silicone resin composition is a one-stage reaction curable resin that cannot be in a B-stage state.

  The blending ratio of the hydrosilyl group-containing polysiloxane is the ratio of the number of moles of alkenyl groups and cycloalkenyl groups of the alkenyl group-containing polysiloxane to the number of moles of hydrosilyl groups of the hydrosilyl group-containing polysiloxane (number of moles of alkenyl groups and cycloalkenyl groups). / Number of moles of hydrosilyl group) is adjusted to be, for example, 1/30 or more, preferably 1/3 or more, and for example, 30/1 or less, preferably 3/1 or less.

  The hydrosilylation catalyst is a substance (addition catalyst) that improves the reaction rate of the hydrosilylation reaction (hydrosilyl addition) between the alkenyl group and / or cycloalkenyl group of the alkenyl group-containing polysiloxane and the hydrosilyl group of the hydrosilyl group-containing polysiloxane. If it exists, it will not specifically limit, For example, a metal catalyst is mentioned. Examples of the metal catalyst include platinum catalysts such as platinum black, platinum chloride, chloroplatinic acid, platinum-olefin complexes, platinum-carbonyl complexes, and platinum-acetyl acetate, for example, palladium catalysts such as rhodium catalyst.

  The blending ratio of the hydrosilylation catalyst is, for example, 1.0 ppm or more on a mass basis with respect to the alkenyl group-containing polysiloxane and the hydrosilyl group-containing polysiloxane as the metal amount of the metal catalyst (specifically, metal atom). Yes, for example, 10000 ppm or less, preferably 1000 ppm or less, and more preferably 500 ppm or less.

  The addition reaction curable silicone resin composition is prepared by blending an alkenyl group-containing polysiloxane, a hydrosilyl group-containing polysiloxane, and a hydrosilylation catalyst in the above proportions.

  The above addition reaction curable silicone resin composition is prepared and used in an A stage (liquid) state by blending an alkenyl group-containing polysiloxane, a hydrosilyl group-containing polysiloxane, and a hydrosilylation catalyst.

  The phenyl-based silicone resin composition undergoes a hydrosilylation addition reaction between the alkenyl group and / or cycloalkenyl group of the alkenyl group-containing polysiloxane and the hydrosilyl group of the hydrosilyl group-containing polysiloxane by heating under a desired condition. The hydroaddition reaction stops once. As a result, the A stage state can be changed to the B stage (semi-cured) state. Thereafter, the above-described hydrosilylation addition reaction is resumed and completed by heating under further desired conditions. As a result, the B stage state can be changed to the C stage (fully cured) state.

  When the phenyl silicone resin composition is in the B stage (semi-cured) state, it is solid. The B-staged phenyl silicone resin composition can have both thermoplasticity and thermosetting properties. That is, the B-stage phenyl silicone resin composition is once cured by heating and then completely cured.

  On the other hand, in the above-described methyl silicone resin composition, a hydrosilylation addition reaction between an alkenyl group and / or cycloalkenyl group and a hydrosilyl group occurs and is promoted and completed without stopping. As a result, the A stage state can be changed to the C stage (fully cured) state. A commercial item is used for the methyl silicone resin composition. Examples of commercially available products include ELASTOSIL series (manufactured by Asahi Kasei Wacker Silicone Co., specifically, methyl silicone resin compositions such as ELASTOSIL LR7665), KER series (manufactured by Shin-Etsu Silicone Co., Ltd.), and the like.

  The condensation / addition reaction curable silicone resin composition is a two-stage reaction curable resin, and specifically described in, for example, JP 2010-265436 A, JP 2013-187227 A, and the like. 1 to 8 condensation / addition reaction curable silicone resin compositions, for example, JP2013-091705A, JP2013-001815A, JP2013-001814A, JP2013-001813A, Examples thereof include a cage-type octasilsesquioxane-containing silicone resin composition described in JP2012-102167A. The condensation / addition reaction curable silicone resin composition is solid and has both thermoplasticity and thermosetting properties.

  The content ratio of the silicone resin in the phosphor resin composition is, for example, 25% by mass or more, preferably 35% by mass or more, and for example, 70% by mass or less, preferably 50% by mass or less.

  The refractive index of the silicone resin is, for example, 1.35 or more, preferably 1.40 or more, and for example, 1.65 or less, preferably 1.60 or less. The refractive index of the silicone resin is calculated by an Abbe refractometer. The refractive index of the silicone resin is calculated as a refractive index in a cured state (fully cured state).

  Examples of the material of the organic particles include thermoplastic resins. Specific examples include acrylic resins, styrene resins, acrylic-styrene resins, silicone resins, polycarbonate resins, benzoguanamine resins, polyolefin resins, polyester resins, polyamide resins, and polyimide resins. .

  Such organic particles may be used alone or in combination.

  Among these, from the viewpoint of light diffusibility and availability, preferably, an acrylic resin, a styrene resin, and an acrylic-styrene resin are used.

  The acrylic resin is a poly (meth) acrylic ester obtained by polymerizing a monomer containing a (meth) acrylic ester (acrylic ester and / or methacrylic ester). For example, poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, methyl (meth) acrylate-ethyl (meth) acrylate copolymer Etc.

  The styrene resin is, for example, a styrene polymer obtained by polymerizing a monomer containing a styrene monomer. Examples of the styrene resin include polystyrene and poly-α-methylstyrene.

  The acrylic-styrene resin is an acrylic-styrene copolymer obtained by polymerizing a monomer containing a (meth) acrylic acid ester and a styrene monomer. Examples of the acrylic-styrene resin include (meth) methyl acrylate-styrene copolymer, (meth) ethyl acrylate-styrene copolymer, (meth) ethyl acrylate-styrene copolymer, and the like.

  The acrylic resin, styrene resin, and acrylic-styrene resin may be a copolymer containing a copolymerizable monomer other than the acrylic monomer and the styrene monomer. Preferred examples of the copolymerizable monomer include (meth) acrylic acid, acrylonitrile, ethylene, and butadiene. These copolymerizable monomers can be used alone or in combination of two or more.

  These organic particles may be cross-linked. That is, a cross-linked acrylic resin, a cross-linked acrylic-styrene resin, and a cross-linked styrene resin are preferable.

  The organic particles are in the form of particles, and the shape thereof is not particularly limited, and examples thereof include a substantially spherical shape, a substantially flat plate shape, and a substantially needle shape.

  The average particle diameter (average of the maximum length) of the organic particles is, for example, 1 μm or more, preferably 5 μm or more, and for example, 100 μm or less, preferably 20 μm or less, more preferably 10 μm or less, and further preferably Is 9 μm or less.

  In particular, when an addition reaction curable silicone resin composition (preferably a methyl silicone resin composition having no phenyl group) is used, the average particle diameter of particularly preferable organic particles is 6 μm or more and 9 μm or less, and is most preferable. Is 7 μm or more and 9 μm or less. When a condensation / addition reaction curable silicone resin composition (preferably a phenyl silicone resin composition) is used, the average particle diameter of particularly preferable organic particles is 5 μm or more and 7 μm or less.

  When the average particle diameter of the organic particles is within the above range, variation in chromaticity of the wavelength conversion sheet can be further suppressed. The average particle diameter of the organic particles is measured by a particle size distribution measuring device.

  The refractive index of the organic particles is 1.45 or more, preferably 1.48 or more. The refractive index is 1.60 or less, preferably 1.55 or less, more preferably 1.53 or less, and still more preferably 1.50 or less. The refractive index of the organic particles is calculated by an Abbe refractometer.

  When the refractive index of the organic particles is equal to or lower than the above lower limit, the effect of light diffusion by the organic particles is low, and it is insufficient to suppress variation in chromaticity of the wavelength conversion sheet. On the other hand, when the refractive index of the organic particles exceeds the above upper limit, the refractive index difference between the silicone resin and the organic particles becomes large, and the translucency may be lowered.

  As these organic particles, specifically, SSX series (refractive index 1.49, crosslinked polymethyl methacrylate particles), SBX series (refractive index 1.59, crosslinked polystyrene particles), MSX series from Sekisui Plastics Co., Ltd. (Refractive index 1.495 to 1.595, methyl methacrylate-styrene copolymer crosslinked particles), MB series (refractive index 1.49, polymethyl methacrylate particles), BMX series (refractive index 1.49, crosslinked poly) Butyl methacrylate particles).

  The difference between the refractive index of the silicone resin and the refractive index of the organic particles is, for example, 0.04 or more, preferably 0.05 or more, and for example, 0.20 or less, preferably 0.12 or less. More preferably, it is 0.10 or less. Thereby, the dispersion | variation in chromaticity in a wavelength conversion sheet can be suppressed further.

  The true specific gravity of the organic particles is, for example, 1.00 or more, preferably 1.10 or more, and for example, 1.50 or less, preferably 1.30 or less.

  The content ratio of the organic particles in the phosphor resin composition is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and for example, 30% by mass or less, preferably 25% by mass or less, and more preferably 20% by mass or less. Thereby, the dispersion | variation in chromaticity by an organic particle can be suppressed further.

  The phosphor is a particle having a wavelength conversion function and may be any known phosphor used in an optical semiconductor device, for example, a yellow phosphor capable of converting blue light into yellow light, and blue light as red. Known phosphors such as a red phosphor that can be converted into light and a green phosphor that can convert blue light into green light can be used.

The yellow phosphor, for _{example, Y 3 Al 5 O 12:} Ce (YAG ( yttrium aluminum _{garnet): Ce), Tb 3 Al} 3 O 12: Ce (TAG ( terbium-aluminum-garnet): Ce), etc. Garnet-type phosphors having a garnet-type crystal structure such as oxynitride phosphors such as Ca-α-SiAlON. Preferably, YAG: Ce is mentioned.

Examples of the red phosphor include nitride phosphors such as CaAlSiN ₃ : Eu (CASN) and CaSiN ₂ : Eu. From the viewpoint of availability, CASN is preferable.

The green phosphor, for _{example, Lu 3 Al 5 O 12:} Ce: garnet phosphors (LuAG ruthenium aluminum garnet) and the like.

  Among such phosphors, a yellow phosphor alone or a combination of a red phosphor and a green phosphor is preferable.

  Such phosphors may be used alone or in combination.

  The phosphor is in the form of particles, and the shape thereof is not particularly limited, and examples thereof include a substantially spherical shape, a substantially flat plate shape, and a substantially needle shape.

  The average particle diameter (average of the maximum length) of the phosphor is, for example, 0.1 μm or more, preferably 0.2 μm or more, more preferably 1 μm or more, and for example, 500 μm or less, preferably 200 μm or less, more preferably 50 μm or less. The average particle diameter of the phosphor particles is measured by a particle size distribution measuring device.

  The composition of the phosphor is appropriately adjusted so that the light passing through the wavelength conversion sheet becomes white corresponding to the optical semiconductor element, and the phosphor content in the phosphor resin composition is, for example, 5% by mass or more. , Preferably, it is 10 mass% or more, for example, 65 mass% or less, Preferably, it is 50 mass% or less.

  When the phosphor is a combination of a red phosphor and a green phosphor, the content ratio is, for example, 1 part by mass or more, preferably 5 parts by mass with respect to 100 parts by mass of the green phosphor. Part or more, and for example, 50 parts by mass or less, preferably 30 parts by mass or less.

  Further, the total content ratio of the organic particles and the phosphor in the phosphor resin composition is, for example, 15% by mass or more, preferably 20% by mass or more, and for example, 70% by mass or less, preferably 60% by mass or less.

  The phosphor resin composition can also contain inorganic particles.

The inorganic particles are blended in the phosphor resin composition as necessary in order to improve the film formability. Examples of the inorganic particles include silica (SiO ₂ ), talc (Mg ₃ (Si ₄ O ₁₀ ) (HO) ₂ ), alumina (Al ₂ O ₃ ), boron oxide (B ₂ O ₃ ), calcium oxide (CaO). ), Zinc oxide (ZnO), strontium oxide (SrO), magnesium oxide (MgO), zirconium oxide (ZrO ₂ ), barium oxide (BaO), antimony oxide (Sb ₂ O ₃ ), and other oxides such as aluminum nitride Examples thereof include inorganic particles (inorganic materials) such as nitrides such as (AlN) and silicon nitride (Si ₃ N ₄ ). Preferably, an oxide is mentioned, More preferably, a silica is mentioned.

  The average particle diameter (average of the maximum length) of the inorganic particles is, for example, 1 nm or more, preferably 5 nm or more, and for example, 30 μm or less, preferably 10 μm or less, more preferably 5 μm or less, even more preferably. Is 0.1 μm or less. The average particle size of the inorganic particles is measured by a particle size distribution measuring device.

  The refractive index of the inorganic particles is, for example, 1.35 or more, preferably 1.40 or more, and for example, 1.65 or less, preferably 1.60 or less. The refractive index of the inorganic particles is calculated by an Abbe refractometer.

  In particular, when the phosphor composition contains a phenyl silicone resin composition, it preferably contains inorganic particles. As a result, the viscosity of the phosphor composition can be increased and the film formability can be improved, so that a phenyl silicone resin-containing wavelength conversion sheet in which variations in chromaticity are suppressed can be obtained more reliably. .

  When the phosphor resin composition contains inorganic particles, the content ratio of the inorganic particles in the phosphor resin composition is, for example, 0.1% by mass or more, preferably 0.5% by mass or more. It is 10 mass% or less, preferably 5 mass% or less.

  Furthermore, the above-mentioned phosphor resin composition may contain known additives such as a silane coupling agent, an anti-aging agent, a modifier, a surfactant, a dye, a pigment, a discoloration inhibitor, and an ultraviolet absorber as necessary. Can be added at an appropriate ratio.

  In order to prepare the phosphor resin composition, the silicone resin, the organic particles, the phosphor, and, if necessary, the inorganic particles and additives are blended in the above blending ratio and mixed.

  As mixing conditions, temperature is 10 degreeC or more, for example, Preferably, it is 15 degreeC or more, for example, is 40 degrees C or less, Preferably, it is 35 degrees C or less.

  In addition, the phosphor resin composition is defoamed after its preparation, if necessary.

  Examples of the defoaming method include known defoaming methods such as stirring defoaming, vacuum defoaming (vacuum defoaming), centrifugal defoaming, and ultrasonic defoaming.

  The viscosity of the phosphor resin composition is, for example, at 25 ° C., for example, 1000 mPa · s or more, preferably 2000 mPa · s or more, preferably 50000 mPa · s or less, preferably 30000 mPa · s or less.

  If the viscosity of the phosphor resin composition is less than the lower limit, moldability or processability may be insufficient. On the other hand, when the above upper limit is exceeded, before the silicone resin composition is laminated and formed into a sheet, bubbles do not escape in the defoaming step of the phosphor resin composition (coating liquid) by stirring or the like, and bubbles are generated in the optical semiconductor device. In some cases, a color shift of the optical semiconductor device or a defect in the reliability test may occur.

[Method for producing wavelength conversion sheet]
A method for manufacturing the wavelength conversion sheet 1 will be described with reference to FIG.

  The method for manufacturing the wavelength conversion sheet 1 includes, for example, a preparation process (see FIG. 1A) and a wavelength conversion sheet stacking process (see FIG. 1B). Hereinafter, each process is explained in full detail.

(Preparation process)
In the preparation step, first, as shown in FIG. 1A, a release substrate 2 is prepared.

  The release substrate 2 is used as a protective sheet that covers and protects the surface of the wavelength conversion sheet 1 or a coating substrate of the wavelength conversion sheet 1.

  In order to protect the wavelength conversion sheet 1 until the optical semiconductor element 5 is sealed with the wavelength conversion sheet 1, the release substrate 2 is detachably attached to the back surface of the wavelength conversion sheet 1. That is, the peeling substrate 2 is laminated so as to cover the back surface of the wavelength conversion sheet 1 at the time of shipping, transporting, and storing the wavelength conversion sheet 1, and the back surface of the wavelength conversion sheet 1 immediately before use of the wavelength conversion sheet 1. It is the flexible film formed from resin which can be peeled off so that it may curve in a substantially U shape. That is, the peeling base material 2 consists only of a flexible film. Moreover, the sticking surface of the flexible film is peeled off as necessary.

  Although it does not restrict | limit especially as the peeling base material 2, For example, a polyester film (for example, a polyethylene terephthalate film), a polycarbonate film, a polyolefin film (for example, a polyethylene film, a polypropylene film), a polystyrene film, an acrylic film, a silicone resin film, fluorine A resin sheet such as a resin film, for example, a peeling plate such as a glass plate can be used.

  In addition, in order to improve the peelability from the wavelength conversion sheet | seat 1, the peeling process is performed to the surface (surface on the side in which the wavelength conversion sheet | seat 1 is formed) of the peeling base material 2 as needed.

  The thickness of the release substrate 2 is not particularly limited, but in the case of a resin sheet, for example, from the viewpoint of handleability and cost, it is, for example, 20 to 100 μm, and in the case of a release plate, for example, 0.5 to 10 mm. It is.

(Wavelength conversion sheet lamination process)
In the wavelength conversion sheet laminating step, the wavelength conversion sheet 1 is laminated on the upper surface of the release substrate 2 as shown in FIG. 1B.

  Specifically, for example, the phosphor resin composition is applied to the upper surface of the release substrate 2, for example, and then the phosphor resin composition is cured.

  Examples of the application method include known application methods such as an applicator, cast, spin, and roll.

  The method for curing the phosphor resin composition is appropriately determined according to the type of the silicone resin, and examples thereof include heating.

  As heating conditions, the temperature is, for example, 70 ° C. or higher, preferably 90 ° C. or higher, and for example, 150 ° C. or lower, preferably 130 ° C. or lower. The time is, for example, 1 minute or more, preferably 3 minutes or more, and for example, 30 minutes or less, preferably 15 minutes or less.

  Thereby, the wavelength conversion sheet 1 is laminated on the upper surface of the release substrate 2.

  The wavelength conversion sheet 1 is manufactured by the above.

  The wavelength conversion sheet 1 is preferably formed as a phosphor resin composition in a C stage state (fully cured state).

  When the phosphor resin composition containing a silicone resin that can be in the B-stage state is heat-cured, the C-stage state may be obtained after temporarily maintaining the B-stage state by two-stage heating. By the step heating, the C stage state may be set without maintaining the B stage state.

  The wavelength conversion sheet 1 has a flat plate shape, specifically, has a predetermined thickness, extends in a predetermined direction orthogonal to the thickness direction, and has a flat surface and a flat back surface. The wavelength conversion sheet 1 is not a light emitting device but a component of the light emitting device, that is, a component for producing the light emitting device, does not include an LED and a substrate on which the LED is mounted, and specifically, a phosphor. It is a device that is formed from a resin composition, circulates by itself, and is industrially usable.

  When the silicone resin contains a phenyl silicone resin composition, the reaction of the phenyl silicone resin composition (C-staging reaction) involves the alkenyl group and / or cycloalkenyl group of the alkenyl group-containing polysiloxane, hydrosilyl The hydrosilyl addition reaction with the hydrosilyl group of the group-containing polysiloxane is further accelerated. Thereafter, the alkenyl group and / or the cycloalkenyl group or the hydrosilyl group of the hydrosilyl group-containing polysiloxane disappears, and the hydrosilyl addition reaction is completed, whereby a C-staged phenyl silicone resin composition, that is, a cured product ( Product).

  The above cured product is represented by the following average composition formula (3).

Average composition formula (3):
R ⁵ _e SiO _{(4-e) / 2}
(In the formula, R ⁵ represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms (excluding an alkenyl group and a cycloalkenyl group) including a phenyl group. 3 or less.)
The unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R ⁵ is an unsubstituted or substituted monovalent carbon group having 1 to 10 carbon atoms represented by R ² in the formula (1). Examples thereof are the same as the hydrogen group and the unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R ³ in the formula (2). Preferably, an unsubstituted monovalent hydrocarbon group, more preferably an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and more preferably a combination of a phenyl group and a methyl group is used. Can be mentioned.

  e is preferably 1 or more and 3 or less.

The proportion of the phenyl groups in ^{R 5} in the average composition formula of the cured product (3) is 30 mol% or more, preferably is 35 mol% or more, and 55 mol% or less, preferably 50 mol% It is as follows.

  The thickness of the wavelength conversion sheet 1 is, for example, 10 μm or more, preferably 50 μm or more, and for example, 1000 μm or less, preferably 500 μm or less.

  The variation of the chromaticity CIEx of the wavelength conversion sheet 1, that is, the difference R between the maximum value and the minimum value of the chromaticity CIEx is, for example, 0.0150 or less, preferably in the range where the film thickness of the wavelength conversion sheet 1 is 5 μm or less. 0.0100 or less, more preferably 0.0070 or less. A method for measuring variation in chromaticity will be described later in Examples.

  And this wavelength conversion sheet 1 is formed from the phosphor resin composition containing a silicone resin, the organic particle whose refractive index is 1.45-1.60, and fluorescent substance. Therefore, the organic particles can diffuse light incident from the optical semiconductor element 5 into the wavelength conversion sheet 1 efficiently and uniformly inside the wavelength conversion sheet 1. As a result, the chromaticity of light passing through the wavelength conversion sheet 1 can be made uniform, and variations in chromaticity can be suppressed.

[Method for Manufacturing Optical Semiconductor Device]
Next, a method for manufacturing the optical semiconductor device 8 by sealing the optical semiconductor element 5 using the wavelength conversion sheet 1 described above will be described with reference to FIGS. 2A to 2D.

  The manufacturing method of the optical semiconductor device 8 includes, for example, a sealing layer stacking step (see FIG. 2A), an arranging step (see FIG. 2B), a sealing step (see FIG. 2C), and a peeling step (see FIG. 2D). . Hereinafter, each process is explained in full detail.

(Sealing layer lamination process)
In the sealing layer stacking step, first, as shown in FIG. 2A, the sealing layer 3 is stacked on one surface (the surface on which the release substrate 2 is not stacked) of the wavelength conversion sheet 1 manufactured in FIG. .

  The sealing layer 3 is formed from a sealing resin composition, and such a sealing resin composition includes a known transparent resin used for embedding and sealing an optical semiconductor element, as a transparent resin. Examples thereof include thermosetting resins such as silicone resins (described above), epoxy resins, and urethane resins, and thermoplastic resins such as acrylic resins, styrene resins, polycarbonate resins, and polyolefin resins.

  Among these, from the viewpoint of durability, heat resistance, and light resistance, preferably, a silicone resin is used.

  As a method of forming the sealing layer 3 on the wavelength conversion sheet 1, for example, a method of directly forming the sealing layer 3 on the wavelength conversion sheet 1, a sealing layer 3 on another release substrate, or the like. After forming, the method of transferring the sealing layer 3 from the peeling base material to the wavelength conversion sheet 1 by a laminator, thermocompression bonding, etc. is mentioned.

  In addition, when sealing resin composition contains a thermosetting resin, the sealing layer 3 is heated and the sealing layer 3 which consists of sealing resin compositions is made into a B stage state (semi-hardened state).

  As heating conditions, the temperature is, for example, 50 ° C. or more, preferably 80 ° C. or more, and for example, 150 ° C. or less, preferably 140 ° C. or less, and the heating time is, for example, 1 minute or more, Preferably, it is 5 minutes or more, and for example, 100 minutes or less, preferably 15 minutes or less. Note that whether or not the sealing layer 3 is in the B-stage state can be appropriately set according to the type of the thermosetting resin.

  Thereby, the wavelength conversion sheet 1 and the wavelength conversion sealing sheet 4 including the sealing layer 3 laminated thereon are obtained.

(Arrangement process)
In the arrangement step, as shown in FIG. 2B, the substrate 7 on which the optical semiconductor element 5 is mounted and the wavelength conversion sealing sheet 4 are arranged to face each other. That is, the substrate 7 and the wavelength conversion sealing sheet 4 are arranged to face each other so that the optical semiconductor element 5 and the sealing layer 3 face each other.

  The substrate 7 is made of, for example, an insulating substrate. A conductive pattern (not shown) including electrodes is formed on the surface of the substrate 7.

  The optical semiconductor element 5 is, for example, an element that emits blue light (specifically, a blue LED), and is mounted on the substrate 7. The optical semiconductor element 5 is connected to an electrode (not shown) of the substrate 7 by wire bonding. In the wire bonding connection, a terminal (not shown) provided on the upper surface of the optical semiconductor element 5 and an electrode (not shown) provided on the upper surface of the substrate 7 are connected via a wire 6 (see a virtual line). Electrically connected.

  The optical semiconductor element 5 may be flip-chip mounted on the substrate 7 (see solid line).

(Sealing process)
In the sealing step, as shown in FIG. 2C, the optical semiconductor element 5 is embedded by the sealing layer 3 of the wavelength conversion sealing sheet 4. When the optical semiconductor element 5 is connected to the substrate 7 by wire bonding, the optical semiconductor element 5 and the wire 6 are embedded.

  Specifically, the sealing layer 3 is thermocompression bonded to the substrate 7. Preferably, the wavelength conversion encapsulating sheet 4 and the substrate 7 are pressed flat.

  As thermocompression bonding conditions, the temperature is, for example, 80 to 220 ° C., the pressure is, for example, 0.01 to 1 MPa, and the press time is, for example, 1 to 10 minutes.

  By this thermocompression bonding, the upper surface and side surfaces of the optical semiconductor element 5 and the wire are covered with the sealing layer 3. That is, the optical semiconductor element 5 and the wire are embedded in the sealing layer 3.

  The upper surface of the substrate 7 exposed from the optical semiconductor element 5 is covered with the sealing layer 3.

  Thus, the wavelength conversion sealing sheet 4 is bonded to the optical semiconductor element 5 and the substrate 7.

  And when this sealing resin composition contains a thermosetting resin, the sealing layer 3 will be in a C stage state (completely cured state), respectively.

(Peeling process)
In the peeling step, the peeling substrate 2 is peeled from the wavelength conversion sealing sheet 4 as shown in the phantom line of FIG. 2C and FIG. 2D.

  As a result, an optical semiconductor device 8 in which the optical semiconductor element 5 is sealed by the sealing layer 3 is obtained.

  When the optical semiconductor element 5 is a blue LED, the optical semiconductor device 8 is obtained as a white light emitting device.

  That is, the optical semiconductor device 8 includes the substrate 7, the optical semiconductor element 5 mounted on the substrate 7, the sealing layer 3 formed on the substrate 7 and encapsulating the optical semiconductor element 5, and the optical semiconductor element 5. And a wavelength conversion sheet 1 formed on the sealing layer 3.

  And by encapsulating the optical semiconductor element 5 with the wavelength conversion encapsulating sheet 4, variation in chromaticity of white light emitted from the optical semiconductor device 8 is suppressed, and white with less color unevenness is recognized. Can do.

[Modification]
In the modification, members and processes similar to those in the above-described embodiment are denoted by the same reference numerals, and detailed description thereof is omitted.

  In the embodiment described above, the optical semiconductor element 5 mounted on the substrate 7 is sealed with the wavelength conversion sealing sheet 4 as shown in FIG. 2C. For example, as shown in FIG. It is also possible to seal the optical semiconductor element 5 that is not yet mounted on 7 but supported by the support sheet 9.

  In this modification, the method for manufacturing the optical semiconductor device 8 includes, for example, a sealing layer stacking step (see FIG. 3A), an arranging step (see FIG. 3B), a sealing step (see FIG. 3C), and a first peeling step (FIG. 3C), a second peeling step (see FIG. 3D), and a mounting step (FIG. 3E). Hereinafter, each process is explained in full detail.

(Sealing layer lamination process)
The sealing layer stacking step is the same as the sealing layer stacking step of the above-described embodiment.

(Arrangement process)
In the preparation step, as shown in FIG. 3B, the support sheet 9, the optical semiconductor element 5 supported by the support sheet 9, and the wavelength conversion sealing sheet 4 are disposed to face each other. That is, the support sheet 9 and the wavelength conversion sealing sheet 4 are arranged to face each other so that the optical semiconductor element 5 and the sealing layer 3 face each other.

  The support sheet 9 includes a support plate 10 and an adhesive layer 11 laminated on the upper surface of the support plate 10.

  The support plate 10 has a plate shape extending in the surface direction, is provided at a lower portion of the support sheet 9, and has substantially the same shape as the support sheet 9 in plan view. The support plate 10 is made of a hard material that cannot be stretched in the plane direction. Specifically, examples of such a material include silicon oxide (such as quartz), oxides such as alumina, metals such as stainless steel, An example is silicon. The thickness of the support plate 10 is, for example, 0.1 to 2 mm.

  The adhesive layer 11 is formed on the entire upper surface of the support plate 10. Examples of the pressure-sensitive adhesive material that forms the pressure-sensitive adhesive layer 11 include pressure-sensitive adhesives such as acrylic pressure-sensitive adhesives and silicone-based pressure sensitive adhesives. Further, the adhesive layer 11 is formed by, for example, an active energy ray irradiation release sheet whose adhesive strength is reduced by irradiation with active energy rays (specifically, an active energy ray irradiation release sheet described in JP-A-2005-286003 or the like). ) Or the like. The thickness of the adhesion layer 11 is 0.1-1 mm, for example.

  In order to prepare the support sheet 9, the support plate 10 and the adhesion layer 11 are bonded together, for example. First, a support plate 10 is prepared, and then a varnish prepared from the above-mentioned adhesive material and a solvent blended as necessary is applied to the support plate 10, and then, if necessary, an application method in which the solvent is distilled off. Thus, the pressure-sensitive adhesive layer 11 can be directly laminated on the support plate 10.

  The thickness of the support sheet 9 is, for example, 0.2 to 6 mm.

  Next, the optical semiconductor element 5 is laminated on the support sheet 9. Specifically, the lower surface of the optical semiconductor element 5 is brought into contact with the upper surface of the adhesive layer 11.

  Thereby, the optical semiconductor element 5 is arranged (placed) on the support sheet 9. That is, the optical semiconductor element 5 is supported on the support sheet 9.

(Sealing process and first peeling process)
As shown in FIG. 3C, each of the sealing step and the first peeling step is the same as each of the sealing step and the peeling step of the above-described embodiment.

  The optical semiconductor element 5, the sealing layer 3 for sealing the optical semiconductor element 5, and the wavelength formed on the sealing layer 3 so as to face the optical semiconductor element 5 by the sealing process and the first peeling process. A sealed optical semiconductor element 12 including the conversion sheet 1 is obtained. The sealing layer 3 covers the upper surface and side surfaces of the optical semiconductor element 5. The lower surface of the optical semiconductor element 5 is exposed from the sealing layer 3 and is in contact with the upper surface of the adhesive layer 11.

(Second peeling step)
In the second peeling step, the sealed optical semiconductor element 12 is peeled off from the upper surface of the adhesive layer 11 as indicated by an arrow in FIG. 3D. Specifically, when the adhesive layer 11 is an active energy ray irradiation release sheet, the active energy ray is irradiated to the adhesive layer 11.

  As a result, the optical semiconductor element 5, the sealing layer 3 that seals the optical semiconductor element 5, and the wavelength conversion sheet 1 that is disposed opposite to the optical semiconductor element 5 and is formed on the sealing layer 3 are sealed. The light-stopping semiconductor element 12 is obtained.

(Mounting process)
In the mounting process, thereafter, the sealed optical semiconductor element 12 is mounted on the substrate 7 as shown in FIG. 3E. Specifically, a terminal (not shown) provided on the lower surface of the optical semiconductor element 5 and an electrode (not shown) of the substrate 7 are connected, and the sealed optical semiconductor element 12 is flip-chip mounted on the substrate 7. .

  Thus, the optical semiconductor device 8 including the substrate 7, the optical semiconductor element 5, the sealing layer 3, and the wavelength conversion sheet 1 is manufactured.

  Also by this method, the same effects as described above can be achieved.

  In the embodiment described above, as shown in FIG. 2C, the optical semiconductor device 8 is formed on the substrate 7, the optical semiconductor element 5 mounted on the substrate 7, and the substrate 7, and the optical semiconductor element 5 is sealed. The optical semiconductor device 8 is mounted on the substrate 7 and the substrate 7, for example, although not shown, although the sealing layer 3 to be formed and the wavelength conversion sheet 1 formed on the sealing layer 3 are provided. The wavelength conversion sheet 1 which is formed on the optical semiconductor element 5 and the substrate 7 and seals the optical semiconductor element 5 can also be provided. That is, the optical semiconductor device 8 may not include the sealing layer 3.

  This optical semiconductor device 8 is, for example, known in the art that a phosphor resin composition is formed on a substrate 7 on which an optical semiconductor element 5 is mounted so that the optical semiconductor element 5 (and the wire 6) is sealed. It can manufacture by apply | coating by the apply | coating method of this, and hardening.

  In the above embodiment, as shown in FIG. 3D, the sealed optical semiconductor element 12 is formed on the optical semiconductor element 5, the sealing layer 3 that seals the optical semiconductor element 5, and the sealing layer 3. For example, although not illustrated, the sealed optical semiconductor element 12 may include the optical semiconductor element 5 and the wavelength conversion sheet 1 that seals the optical semiconductor element 5. That is, the optical semiconductor device 8 may not include the sealing layer 3.

  For example, the sealing optical semiconductor element 12 may be formed by applying a phosphor resin composition to a support sheet 9 on which the optical semiconductor element 5 is supported so that the optical semiconductor element 5 is sealed. It can manufacture by peeling the support sheet 9 after apply | coating and hardening by a method.

  In the above-described embodiment, as shown in FIG. 2C, the optical semiconductor device 8 does not include a housing disposed on the substrate 7 so as to surround the optical semiconductor element 5, but for example, as shown in FIG. In addition, the optical semiconductor device 8 may include a housing 13.

  The optical semiconductor device 8 of the embodiment of FIG. 4 includes a substrate 7, an optical semiconductor element 5 mounted on the substrate 7, a housing 13 formed on the substrate 7, and a sealing for sealing the optical semiconductor element 5. A layer 3 and a wavelength conversion sheet 1 formed on the sealing layer 3 are provided.

  The housing 13 has a substantially frame shape in a plan view, and is formed in a substantially trapezoidal cylindrical shape that becomes gradually narrower upward. Further, the housing 13 is disposed so as to surround the optical semiconductor element 5 and spaced from the optical semiconductor element 5.

  The sealing layer 3 is filled in the housing 13.

  The wavelength conversion sheet 1 is also formed on the entire upper surface of the sealing layer 3 and the inner end of the upper surface of the housing 13.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples. The numerical values in the following examples can be substituted for the numerical values (that is, the upper limit value or the lower limit value) described in the above embodiment.

Example 1
In a disposable cup, 4.0 g of a silicone resin (LR7665, addition reaction curable silicone resin composition, manufactured by Asahi Kasei Wacker Silicone), 4.0 g of YAG phosphor (Y468, average particle size of 17 μm, manufactured by Nemoto Lumi Materials), 4.0 g And 2.0 g of cross-linked polymethyl methacrylate particles (SSX-108, organic particles, refractive index 1.49, average particle size 8 μm, manufactured by Sekisui Plastics Co., Ltd.) and stirred for 5 minutes with a spatula, Stirring and defoaming were carried out for 3 minutes using a stirrer / deaerator (Mazerustar, Kurabo Industries). Thereby, the composition (varnish) for wavelength conversion sheets was prepared. The viscosity of the composition for wavelength conversion sheets was 19000 mPa · s to 25000 mPa · s.

  On a slide glass (length 76 mm × width 52 mm × thickness 1.2 to 1.5 mm, manufactured by Matsunami Glass Industrial Co., Ltd.), applicator (Yoshimitsu Seiki Co., Ltd., “Baker Applicator YBA type”, scale is 2.2-2 The composition for wavelength conversion sheet thus prepared was applied so that the length direction was 60 mm and the width direction was 52 mm.

  Next, the glass slide was placed on a hot plate and heated at 105 ° C. for 5 minutes to cure the wavelength conversion sheet composition to produce a wavelength conversion sheet (C stage, film thickness 170 to 210 μm) ( (See FIG. 5 described later).

Examples 2 to 13 and Comparative Examples 1 to 3
A wavelength conversion sheet (C stage, film thickness: 170 to 210 μm) was produced in the same manner as in Example 1 except that the formulation for the wavelength conversion sheet was changed to the formulation described in Table 1 and Table 2.

Examples 14 to 22 and Comparative Example 4
A phenyl silicone resin composition A was prepared according to the following synthesis examples and preparation examples. Using this phenyl-based silicone resin composition A in place of LR7665, the wavelength conversion sheet (C stage, C stage, etc.) was used in the same manner as in Example 1 except that the formulation of the wavelength conversion sheet was changed to the formulation shown in Table 3. A film thickness of 170 to 210 μm) was produced.

(Synthesis Example 1)
In a four-necked flask equipped with a stirrer, reflux condenser, charging port and thermometer, 93.2 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 140 g of water, trifluoromethanesulfone 0.38 g of acid and 500 g of toluene were added and mixed. While stirring, a mixture of 729.2 g of methylphenyldimethoxysilane and 330.5 g of phenyltrimethoxysilane was added dropwise over 1 hour, and then heated under reflux for 1 hour. Then, it cooled, the lower layer (water layer) was isolate | separated and removed, and the upper layer (toluene solution) was washed with water 3 times. 0.40 g of potassium hydroxide was added to the toluene solution washed with water, and the mixture was refluxed while removing water from the water separation tube. After completion of water removal, the mixture was further refluxed for 5 hours and cooled. Thereafter, 0.6 g of acetic acid was added for neutralization, and then the toluene solution obtained by filtration was washed with water three times. Then, liquid alkenyl group containing polysiloxane A was obtained by concentrating under reduced pressure. The average unit formula and average composition formula of the alkenyl group-containing polysiloxane A are as follows.

Average unit formula:
((CH ₂ = CH) (CH ₃ ) ₂ SiO _1/2 ) _0.15 (CH ₃ C ₆ H ₅ SiO _2/2 ) _0.60 (C ₆ H ₅ SiO _3/2 ) _0.25
Average composition formula:
(CH ₂ = CH) _0.15 (CH ₃ ) _0.90 (C ₆ H ₅ ) _0.85 SiO _1.05
That is, the alkenyl group-containing polysiloxane A is represented by the above average composition formula (1) in which R ¹ is a vinyl group, R ² is a methyl group and a phenyl group, and a = 0.15 and b = 1.75. .

  Moreover, it was 2300 when the weight average molecular weight of polystyrene conversion of the alkenyl group containing polysiloxane A was measured by the gel permeation chromatography.

(Synthesis Example 2)
In a four-necked flask equipped with a stirrer, reflux condenser, charging port and thermometer, 93.2 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 140 g of water, trifluoromethanesulfone 0.38 g of acid and 500 g of toluene were added and mixed. While stirring, a mixture of 173.4 g of diphenyldimethoxysilane and 300.6 g of phenyltrimethoxysilane was added dropwise over 1 hour. After completion of the addition, the mixture was heated to reflux for 1 hour. Then, it cooled, the lower layer (water layer) was isolate | separated and removed, and the upper layer (toluene solution) was washed with water 3 times. 0.40 g of potassium hydroxide was added to the toluene solution washed with water, and the mixture was refluxed while removing water from the water separation tube. After completion of water removal, the mixture was further refluxed for 5 hours and cooled. After neutralizing by adding 0.6 g of acetic acid, the toluene solution obtained by filtration was washed with water three times. Then, liquid alkenyl group containing polysiloxane B was obtained by concentrating under reduced pressure. The average unit formula and average composition formula of the alkenyl group-containing polysiloxane B are as follows.

Average unit formula:
(CH ₂ = CH (CH ₃ ) ₂ SiO _1/2 ) _0.31 ((C ₆ H ₅ ) ₂ SiO _2/2 ) _0.22 (C ₆ H ₅ SiO _3/2 ) _0.47
Average composition formula:
(CH ₂ = CH) _0.31 (CH ₃ ) _0.62 (C ₆ H ₅ ) _0.91 SiO _1.08
That is, the alkenyl group-containing polysiloxane B is represented by the above average composition formula (1) in which R ¹ is a vinyl group, R ² is a methyl group and a phenyl group, and a = 0.31 and b = 1.53. .

  Moreover, it was 1000 when the weight average molecular weight of polystyrene conversion of the alkenyl group containing polysiloxane B was measured by gel permeation chromatography.

(Synthesis Example 3)
Diphenyldimethoxysilane (325.9 g), phenyltrimethoxysilane (564.9 g), and trifluoromethanesulfonic acid (2.36 g) were added to a four-necked flask equipped with a stirrer, reflux condenser, inlet, and thermometer. Then, 134.3 g of 1,1,3,3-tetramethyldisiloxane was added, and 432 g of acetic acid was added dropwise over 30 minutes while stirring. After completion of dropping, the mixture was heated to 50 ° C. with stirring and reacted for 3 hours. After cooling to room temperature, toluene and water were added, mixed well and allowed to stand, and the lower layer (aqueous layer) was separated and removed. Thereafter, the upper layer (toluene solution) was washed with water three times and then concentrated under reduced pressure to obtain hydrosilyl group-containing polysiloxane C (crosslinking agent C).

  The average unit formula and average composition formula of the hydrosilyl group-containing polysiloxane C are as follows.

Average unit formula:
(H (CH ₃ ) ₂ SiO _1/2 ) _0.33 ((C ₆ H ₅ ) ₂ SiO _2/2 ) _0.22 (C ₆ H ₅ PhSiO _3/2 ) _0.45
Average composition formula:
H _0.33 (CH ₃ ) _0.66 (C ₆ H ₅ ) _0.89 SiO _1.06
That is, the hydrosilyl group-containing polysiloxane C is represented by the above average composition formula (2) in which R ³ is a methyl group and a phenyl group, and c = 0.33 and d = 1.55.

  Moreover, it was 1000 when the weight average molecular weight of polystyrene conversion of hydrosilyl group containing polysiloxane C was measured by gel permeation chromatography.

(Preparation Example 1)
20 g of alkenyl group-containing polysiloxane A (Synthesis Example 1), 25 g of alkenyl group-containing polysiloxane B (Synthesis Example 2), 25 g of hydrosilyl group-containing polysiloxane C (Synthesis Example 3, cross-linking agent C), and platinum carbonyl complex (product) The name “SIP6829.2”, manufactured by Gelest, platinum concentration of 2.0% by mass (5 mg) is mixed to obtain a phenyl-based silicone resin composition (addition reaction curable silicone resin composition, B-stage 1) A step reaction curable resin) was prepared.

Comparative Example 5
After adding 6.0 g of silicone resin (LR7665) and 4.0 g of YAG phosphor (Y468) to the disposable cup and stirring for 5 minutes with a spatula, further stirring and defoaming with a stirrer / deaerator 3 Conducted for a minute. Thereby, the composition (varnish) for wavelength conversion layers was prepared.

  On the slide glass, the prepared composition for wavelength conversion layer was apply | coated with the applicator.

  Next, the glass slide was placed on a hot plate and heated at 105 ° C. for 5 minutes to cure the wavelength conversion layer composition, thereby forming a wavelength conversion sheet (film thickness 200 μm).

  Thereby, the wavelength conversion sheet of Comparative Example 5 was obtained.

Comparative Example 6
To the disposable cup, 9.0 g of silicone resin (LR7665) and 1.0 g of crosslinked polymethyl methacrylate particles (SSX-108) are added and stirred for 5 minutes with a spatula, and further with a stirrer / defoaming device. Stirring and degassing were carried out for 3 minutes. This prepared the composition for diffusion layers (varnish).

  Subsequently, the prepared composition for diffusion layers was applied to the surface of the wavelength conversion sheet of Comparative Example 5 with an applicator.

  Next, the wavelength conversion sheet coated with the diffusion layer composition is placed on a hot plate and heated at 105 ° C. for 5 minutes to cure the diffusion layer composition, and the diffusion layer (film thickness 100 μm) is formed. Formed.

  Thus, a wavelength conversion sheet of Comparative Example 6 having a two-layer structure of wavelength conversion layer / diffusion layer was manufactured.

(Evaluation of refractive index of cured state of silicone resin)
The refractive index of the cured state was measured for each of LR7665 and the phenyl silicone resin composition.

  Specifically, each of LR7665 and phenyl-based silicone resin composition A is allowed to react (ie, completely cured, C stage) at 100 ° C. for 1 hour without containing particles and phosphors. A cured product was obtained. Next, the obtained cured product was measured with an Abbe refractometer.

  The cured products of LR7665 and phenyl silicone resin composition A both had a refractive index of 1.42.

(Measurement of phenyl group content in hydrocarbon group (R ⁵ ) of cured product obtained from phenyl-based silicone resin composition A)
Hydrocarbon groups (average composition formula (3)) directly bonded to silicon atoms in the cured product obtained by the reaction of phenyl silicone resin composition A (that is, phenyl silicone resin composition A containing no inorganic filler) The content (mol%) of the phenyl group in R ⁵ ) was calculated by ¹ H-NMR and ²⁹ Si-NMR.

  Specifically, the A-stage phenyl-based silicone resin composition A is reacted (completely cured, C-staged) at 100 ° C. for 1 hour without adding an inorganic filler to obtain a cured product (fully cured state). Got.

Next, by measuring ¹ H-NMR and ²⁹ Si-NMR of the obtained cured product, the proportion (mol%) of the phenyl group in the hydrocarbon group (R ⁵ ) directly bonded to the silicon atom is calculated. did.

  As a result, it was 48 mol%.

(Evaluation of chromaticity variation)
In each example and each comparative example, as shown in FIG. 5, a point 3 mm away from the corner of the slide glass 14 on which the wavelength conversion sheet 1 was manufactured was used as a reference point X. Measure the chromaticity and film thickness of the wavelength conversion sheet of each example and each comparative example at a pitch of 5 mm within a range of 70 mm from the reference point X in the length direction and 35 mm in the width direction (inside the phantom line in FIG. 5). did. The chromaticity CIEx was measured by a chromaticity measuring device (DF-1000A, manufactured by Otsuka Electronics Co., Ltd.), and the film thickness was measured by a laser displacement meter (LT-9030M, manufactured by Keyence Corporation).

  The measured film thickness was plotted on the x-axis and the chromaticity CIEx was plotted on the y-axis. In order to eliminate the influence of the protruding light, the measurement data of 15 mm at both ends in the length direction was deleted.

  Then, a difference (y-axis direction length) between the maximum value and the minimum value of chromaticity CIEx was calculated for each width unit (x-axis direction) having a film thickness of 5 μm.

  At this time, a width of a film thickness of 5 μm that minimizes the difference between the maximum value and the minimum value is selected (for example, a film thickness of 195 to 200 μm in Example 1), and the maximum value of chromaticity CIEs in this film thickness range. Tables 1 to 3 show the difference R between the minimum value and the minimum value.

  The difference R in Comparative Example 5 was 0.0170, and the difference R in Comparative Example 6 was 0.0190.

In addition, the numerical value in each component of Table 1-Table 3 shows a mass part number, when there is no special description. Details of the components in Tables 1 to 3 are shown below.
LR7665: trade name “ELASTOSIL LR7665”, addition reaction curable silicone resin composition (methyl silicone resin composition, one-stage reaction curable resin that cannot be in B-stage state), manufactured by Asahi Kasei Wacker Silicone Co., Ltd., crosslinked methacrylic Acid methyl particles: “SSX-108”, organic particles, refractive index 1.49, average particle diameter 8 μm, manufactured by Sekisui Plastics Co., Ltd., cross-linked methyl methacrylate particles: “SSX-105”, organic particles, refractive index 49, average particle size 5 μm, Sekisui Plastics Co., Ltd., cross-linked methyl methacrylate particles: “SSX-106”, organic particles, refractive index 1.49, average particle size 6 μm, Sekisui Plastics Co., Ltd., cross-linked methacrylic acid Methyl particles: “SSX-110”, organic particles, refractive index 1.49, average particle size 10 μm, manufactured by Sekisui Plastics Co., Ltd. Methyl laurate particles: “SSX-108LXE”, organic particles, refractive index 1.545, average particle size 8 μm, manufactured by Sekisui Plastics Co., Ltd./crosslinked methyl methacrylate particles: “XX-227AA”, organic particles, refractive index 1 525, average particle size 8 μm, Sekisui Plastics Co., Ltd., silica particles: “3 sdc”, refractive index 1.45, average particle size 3.4 μm, Denki Kagaku Kogyo Co., Ltd., silicone particles: “Tospearl 2000B”, refraction 1.42, average particle size 6.0 μm, manufactured by Momentive Performance Materials Japan, Aerosil particles: “R976S”, refractive index 1.46, average particle size 7 nm, manufactured by Evonik, YAG phosphor: “ Y468 ”, YAG: Ce, average particle size 17 μm, manufactured by Nemoto Lumimaterial, LuAG phosphor:“ LP-6906 ”, Lu ₃ Al ₅ O ₁₂ : Ce, average particle size 15 μm, manufactured by LWB, CASN phosphor: “ER6238”, CaAlSiN ₃ : Eu, average particle size 15 μm, manufactured by Intematix

DESCRIPTION OF SYMBOLS 1 Wavelength conversion sheet 5 Optical semiconductor element 7 Substrate 8 Optical semiconductor device 12 Sealing optical semiconductor element

Claims (7)

Formed from a phosphor resin composition containing silicone resin, organic particles and phosphor,
A wavelength conversion sheet, wherein the organic particles have a refractive index of 1.45 to 1.60.   The wavelength conversion sheet according to claim 1, wherein a content ratio of the organic particles in the wavelength conversion sheet is 10 to 25% by mass.   The wavelength conversion sheet according to claim 1 or 2, wherein a total content ratio of the organic particles and the phosphor in the wavelength conversion sheet is 15 to 70 mass%.   The said organic particle consists of at least 1 sort (s) of material selected from the group which consists of acrylic resin, acrylic-styrene-type resin, and styrene-type resin, It is any one of Claims 1-3 characterized by the above-mentioned. Wavelength conversion sheet. The wavelength conversion sheet according to claim 1, wherein the phosphor contains a CaAlSiN ₃ : Eu phosphor. A substrate,
An optical semiconductor element mounted on the substrate;
An optical semiconductor device comprising: the wavelength conversion sheet according to any one of claims 1 to 5 disposed to face the optical semiconductor element. An optical semiconductor element;
A sealed optical semiconductor device comprising: the wavelength conversion sheet according to claim 1, which is disposed to face the optical semiconductor device.

Images