JP2013256622A - Fluorescent particle-containing composition, fluorescent particle-containing film and optical semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorescent particle-containing composition which can form a fluorescent layer containing uniformly dispersed fluorescent particles by adding a small amount of fine particles such as fine silica particles, even when the content of the fluorescent particles is high.SOLUTION: A fluorescent particle-containing composition comprising fluorescent particles (A), fine particles (B), a binder resin component (C), and a compound (D) having at least one structure (d1) selected from diaryl silicone structures, dialkyl silicone structures, fluorinated alkyl structures, fluorinated alkenyl structures and ≥8C alkyl structures, and at least one structure (d2) selected from polyoxyalkylene structures, ammonium salt-having structures, carboxylic acid salt-having structures, phosphate group-having structures, phosphate salt-having structures, sulfone group-having structures, sulfonate salt-having structures, hydroxy group-having structures and ester group-having structures, is characterized in that, when the total amount of the fluorescent particles (A), the fine particles (B), the binder resin component (C), and the compound (D) is 100 wt.%, the amount of the fluorescent particles (A) is ≥30 wt.%, and the amount of the fine particles (B) is >0 wt.% and ≤10 wt.%, and the amount of the compound (D) is 0.01-2 pts.wt. per 100 pts.wt. of the fluorescent particles (A). According to the present invention, a fluorescent layer containing the uniformly dispersed fluorescent particles can be formed by adding a small amount of fine silica particles, even when the content of the fluorescent particles is high.

Description

  The present invention relates to a phosphor particle-containing composition, a phosphor particle-containing film, and an optical semiconductor device having the phosphor particle-containing film.

  The full-wavelength (whitening) of a light-emitting diode (LED) is usually performed by forming a phosphor layer containing phosphor particles around the LED and converting the wavelength of the LED light with the phosphor particles. ing. If the phosphor particles are not uniformly dispersed in the phosphor layer, it is impossible to stably achieve the full wavelength. However, since the phosphor particles vary in particle size and have a large specific gravity, it is difficult to uniformly and stably disperse the phosphor particles in the phosphor layer. For this reason, a method of making the dispersion of the phosphor particles uniform in the phosphor layer by adding fine particles such as silica fine particles to the phosphor layer has been studied.

  Patent Document 1 discloses a technique for suppressing sedimentation of a phosphor by adding a thixotropic agent composed of silica fine particles and a metal oxide to a phosphor-containing composition containing the phosphor and a liquid medium. Patent Document 2 discloses a phosphor-containing composition in which a phosphor and a liquid medium are mixed, then silica fine particles are mixed, and the viscosity of the liquid medium is adjusted within a predetermined range, thereby enabling uniform dispersion of the phosphor. A manufacturing method is disclosed. In Patent Document 3, the curable resin composition has a refractive index difference of ± 0.03 from the cured product of the curable resin composition and a thermal conductivity of 0.5 W / m · K or more. A resin composition for encapsulating an optical semiconductor element obtained by blending a silica filler is disclosed.

  At least two types of phosphor layers are known. FIG. 1 and FIG. 2 show schematic diagrams of LEDs on which a phosphor layer is formed. FIG. 1 shows a type in which a light emitting element portion is sealed only with a phosphor layer. In FIG. 1, a layer made of a sealing material 51 and phosphor particles 54 dispersed therein is a phosphor layer, and this phosphor layer covers the light emitting element portion 50. FIG. 2 shows a type in which a light emitting element portion is sealed with a phosphor layer and a layer not containing a phosphor. In FIG. 2, a phosphor layer 52 composed of a binder 53 and phosphor particles 54 dispersed therein covers the light emitting element portion 50, and a sealing material 51 that does not contain a phosphor on the phosphor layer 52. Is covered.

  In the case of the type shown in FIG. 2, it is necessary to increase the content ratio of the phosphor particles 54 included in the phosphor layer 52 in order to realize the full-wavelength LED. When a large amount of phosphor particles 54 are present in the phosphor layer 52, it is necessary to increase the amount of silica particles added in order to uniformly disperse the phosphor particles 54 by adding the silica particles to the phosphor layer 52. is there. However, the silica fine particles do not contribute to the emission of light from the LED, but rather totally reflect the light. Therefore, if a large amount of silica fine particles are present in the phosphor layer 52, the luminance is lowered. In addition, when the content of the phosphor particles 54 and the silica fine particles in the phosphor layer 52 is large, the ratio of the binder 53 is reduced, so that the gas barrier property and crack resistance may be lowered.

JP 2008-260930 A JP 2009-102514 A JP 2011-144360 A

  The present invention provides a phosphor particle-containing composition capable of forming a phosphor layer in which phosphor particles are uniformly dispersed by addition of a small amount of fine particles such as silica fine particles even if the content ratio of the phosphor particles is high. The purpose is to provide.

  As a result of intensive studies, the inventor has obtained a phosphor particle-containing composition containing a specific compound, and even when the phosphor particle content is high, the phosphor particles can be made uniform by adding a small amount of silica fine particles or the like. The present inventors have found that a dispersed phosphor layer can be formed and have completed the present invention.

That is, the present invention relates to the following [1] to [9], for example.
[1] Selected from phosphor particles (A), fine particles (B), binder resin component (C), and diaryl silicone structure, dialkyl silicone structure, fluorinated alkyl structure, fluorinated alkenyl structure, and alkyl structure having 8 or more carbon atoms At least one structure (d1), and a polyoxyalkylene structure, a structure having an ammonium salt, a structure having a carboxylate, a structure having a phosphate group, a structure having a phosphate, a structure having a sulfone group, a sulfone A phosphor particle-containing composition comprising a compound (D) having at least one structure (d2) selected from a structure having an acid salt, a structure having a hydroxyl group, and a structure having an ester group,
When the total of the phosphor particles (A), the fine particles (B), the binder resin component (C) and the compound (D) is 100% by weight, the phosphor particles (A) are 30% by weight or more and the fine particles ( B) is contained in an amount of more than 0% by weight and not more than 10% by weight,
A phosphor particle-containing composition comprising 0.01 to 2 parts by weight of the compound (D) with respect to 100 parts by weight of the phosphor particles (A).

[2] The phosphor particle-containing composition according to [1], wherein 0.01 to 2 parts by weight of the fine particles (B) are contained with respect to 100 parts by weight of the phosphor particles (A).
[3] The phosphor particle-containing composition according to [1] or [2], which contains polysiloxane as the binder resin component (C).

  [4] The fluorescence according to [1] or [2], wherein the binder resin component (C) contains an alkenyl group-containing polysiloxane (C1), a hydrogen polysiloxane (C2), and a hydrosilylation catalyst (C3). Body particle-containing composition.

[5] The phosphor particle-containing composition according to any one of [1] to [4], wherein the fine particles (B) are silica fine particles.
[6] The phosphor particle-containing composition according to any one of [1] to [5], wherein the structure (d2) is a polyoxyalkylene structure.

[7] A phosphor particle-containing film obtained from the phosphor particle-containing composition according to any one of [1] to [6].
[8] Selected from phosphor particles (A), fine particles (B), binder resin component (C), and diaryl silicone structure, dialkyl silicone structure, fluorinated alkyl structure, fluorinated alkenyl structure, and alkyl structure having 8 or more carbon atoms At least one structure (d1), a polyoxyalkylene structure, a structure having an ammonium salt, a structure having a carboxylate, a structure having a phosphate group, a structure having a phosphate, a structure having a sulfone group, a sulfone A phosphor particle-containing film containing a compound (D) having at least one structure (d2) selected from a structure having an acid salt, a structure having a hydroxyl group, and a structure having an ester group,
When the total of the phosphor particles (A), the fine particles (B), the binder resin component (C) and the compound (D) contained in the phosphor particle-containing film is 100% by weight, the phosphor particles (A) 30 wt% or more, containing the fine particles (B) more than 0 wt% and 10 wt% or less,
A phosphor particle-containing film comprising 0.01 to 2 parts by weight of the compound (D) with respect to 100 parts by weight of the phosphor particles (A).

  [9] An optical semiconductor device having the phosphor particle-containing film according to [7] or [8].

  The phosphor particle-containing composition of the present invention is a phosphor particle-containing film such as a phosphor layer in which phosphor particles are uniformly dispersed by addition of a small amount of silica fine particles, etc., even when the phosphor particle content ratio is high. Can be formed. As a result, full-wavelength (whitening) of LEDs and the like can be realized without reducing brightness, gas barrier properties, crack resistance, and the like.

FIG. 1 is a schematic view of an LED in which a light emitting element portion is sealed only with a phosphor layer. FIG. 2 is a schematic view of an LED in which a light emitting element portion is sealed with a phosphor layer and a layer not containing a phosphor.

<Phosphor particle-containing composition>
The phosphor particle-containing composition of the present invention comprises phosphor particles (A), fine particles (B), a binder resin component (C), a diaryl silicone structure, a dialkyl silicone structure, a fluorinated alkyl structure, a fluorinated alkenyl structure, and carbon. At least one structure (d1) selected from an alkyl structure of 8 or more, and a polyoxyalkylene structure, a structure having an ammonium salt, a structure having a carboxylate, a structure having a phosphate group, and a structure having a phosphate , A phosphor particle-containing composition containing a compound (D) having at least one structure (d2) selected from a structure having a sulfone group, a structure having a sulfonate, a structure having a hydroxyl group, and a structure having an ester group Because
When the total of the phosphor particles (A), the fine particles (B), the binder resin component (C) component and the compound (D) is 100 wt%, the phosphor particles (A) are 30 wt% or more, and the fine particles Containing (B) more than 0 wt% and 10 wt% or less,
The compound (D) is contained in an amount of 0.01 to 2 parts by weight with respect to 100 parts by weight of the phosphor particles (A).
Phosphor particles (A)
The phosphor particles (A) are not particularly limited, and any particles used for wavelength conversion of light emitting devices such as LEDs can be used. For example, (Sr, Ca) S: Eu, Y _{3 (Al, Ga) 5 O} 12: Ce, (Y, Gd) 3 A l5 O 12: Ce, CaGa 2 S 4: Eu, (Ca, Sr) 2 Si 5 N 8: Eu, SrSiO 2 N 2: _{Eu, CaSiN 2: Eu, Ca} 3 Sc 2 Si 3 O 12: Ce, CaGa 2 S 4: Eu, 2SiO 4: Eu , and the like.

  The number average particle diameter of the phosphor particles (A) is usually 1 to 30 μm, preferably 5 to 20 μm, as measured by a dynamic light scattering method. When the number average particle diameter of the phosphor particles (A) is within the above range, wavelength conversion of an LED or the like can be efficiently realized by the phosphor particle-containing film formed from the present composition.

The content of the phosphor particles (A) is 30% by weight or more when the total of the phosphor particles (A), the fine particles (B), the binder resin component (C) component and the compound (D) is 100% by weight. Yes, preferably 40 to 90% by weight, more preferably 50 to 85% by weight, still more preferably 60 to 80% by weight. When the content of the phosphor particles (A) is within the above range, when the phosphor layer shown in FIG. 2 is formed from the present composition, the wavelength conversion of the LED can be suitably realized.
Fine particles (B)
The fine particles (B) are fine particles other than the phosphor particles (A). The fine particles (B) are not particularly limited, and any fine particles used for uniform dispersion of the phosphor particles used for wavelength conversion of light emitting devices such as LEDs in the phosphor layer should be used. Can do. Examples of the fine particles (B) include silicon dioxide (silica), aluminum oxide (alumina), titanium dioxide, zirconium oxide (zirconium), germanium oxide, and yttrium oxide, and one of these may be used alone. You may use, and may use 2 or more types together. Among these, silica fine particles are particularly preferable because the uniform dispersion of the phosphor particles (A) can be efficiently realized.

  The number average particle diameter of the fine particles (B) is usually 5 to 40 nm, preferably 7 to 20 nm, as measured by a dynamic light scattering method. When the number average particle diameter of the fine particles (B) is within the above range, uniform dispersion of the phosphor particles (A) can be efficiently realized in the phosphor particle-containing film formed from the present composition.

  Usually, the number average particle size of the fine particles (B) is smaller than the number average particle size of the phosphor particles (A). When the number average particle size of the fine particles (B) is smaller than the number average particle size of the phosphor particles (A), uniform dispersion of the phosphor particles (A) is efficient in the phosphor particle-containing film formed from the present composition. To be realized.

The content of the fine particles (B) is more than 0 wt% and 10 wt% when the total of the phosphor particles (A), the fine particles (B), the binder resin component (C) component and the compound (D) is 100 wt%. % Or less, preferably 0.5 to 8% by weight, more preferably 2 to 7% by weight. When the content of the fine particles (B) is within the above range, uniform dispersion of the phosphor particles (A) can be suitably realized in the phosphor particle-containing film formed from the present composition.
Binder resin component (C)
The binder resin component (C) is a component having a function of supporting the phosphor particles (A) and the fine particles (B) in the phosphor particle-containing film formed from the present composition. And a component such as a mixture of a polymer compound capable of forming the binder resin and a crosslinking reaction catalyst.

  The binder resin component (C) is not particularly limited, and any binder resin component used for a phosphor layer used in a light emitting device such as an LED can be used. The binder resin component (C) can be used alone or in combination of two or more.

  Examples of the binder resin component (C) include a transparent resin in the visible light region and a component capable of forming the resin. For example, an organic resin such as an acrylic resin, an inorganic resin such as polysiloxane, and an acrylic siloxane type. Organic / inorganic hybrid resins such as resins and epoxy silicon resins can be mentioned. The organic resin, inorganic resin, and organic / inorganic hybrid resin are exemplified in Patent Documents 1 and 2, for example.

  The binder resin component (C) preferably contains polysiloxane from the viewpoints of heat resistance and light resistance. Among them, alkenyl group-containing polysiloxane (C1), hydrogen polysiloxane (C2) and hydrosilylation catalyst (C3) are particularly suitable. The alkenyl group-containing polysiloxane (C1) and the hydrogen polysiloxane (C2) are crosslinked by a hydrosilylation reaction in the presence of the hydrosilylation catalyst (C3) to form a binder resin.

In the present invention, “polysiloxane” means a siloxane having a molecular skeleton in which two or more siloxane units (Si—O) are bonded.
(Alkenyl group-containing polysiloxane (C1))
Examples of the alkenyl group of the alkenyl group-containing polysiloxane (C1) include vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, heptenyl group, hexenyl group, and cyclohexenyl group. Can be mentioned. Among these, a vinyl group, an allyl group, and a hexenyl group are preferable. The alkenyl group-containing polysiloxane (C1) preferably has two or more alkenyl groups per molecule.

  The content of the alkenyl group-containing polysiloxane (C1) contained in the binder resin component (C) is preferably 30 to when the total content of all components contained in the binder resin component (C) is 100% by mass. It is 95 mass%, More preferably, it is 40-90 mass%, More preferably, it is 50-80 mass%.

  The alkenyl group-containing polysiloxane (C1) preferably has a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography in the range of 100 to 50000, and more preferably in the range of 500 to 5000.

  As the production method of the alkenyl group-containing polysiloxane (C1), JP-A-6-9659, JP-A-2003-183582, JP-A-2007-008996, JP-A-2007-106798, JP-A-2007- 169427 and Japanese Patent Application Laid-Open No. 2010-059359, for example, a method of cohydrolyzing chlorosilane and alkoxysilane as each unit source, and a cohydrolyzate is equilibrated with an alkali metal catalyst or the like. And the like.

(Hydrogen polysiloxane (C2))
Hydrogen polysiloxane (C2) is a polysiloxane having at least two silicon-bonded hydrogen atoms per molecule. That is, hydrogen polysiloxane (C2) has at least two Si—H groups (hydrosilyl groups) per molecule. The hydrogen polysiloxane (C2) is a crosslinking agent for the alkenyl group-containing polysiloxane (C1), and forms a cured product by a hydrosilylation reaction with the alkenyl group-containing polysiloxane (C1).

  The hydrogen polysiloxane (C2) is particularly limited as long as it is a polysiloxane having at least two silicon-bonded hydrogen atoms per molecule, which is used as a crosslinking agent in conventional hydrosilyl polysiloxane compositions. Can be used without

  Specific examples of the hydrogenpolysiloxane (C2) include organohydrogenpolysiloxanes described in JP2007-327019A, JP2007-008996A, and JP2010-229402A. it can.

  The hydrogen polysiloxane (C2) is obtained, for example, by reacting an alkoxysilane such as phenyltrimethoxysilane or diphenyldimethoxysilane with a hydrogensiloxane such as 1,1,3,3-tetramethyldisiloxane by a known method. Can be obtained.

  The content of the hydrogen polysiloxane (C2) in the binder component resin (C) is the mole of the silicon-bonded hydrogen atom in the hydrogen polysiloxane (C2) relative to the amount of the alkenyl group in the alkenyl group-containing polysiloxane (C1). The amount is preferably such that the ratio is 0.1 to 5, more preferably 0.5 to 2, and even more preferably 0.7 to 1.4.

(Catalyst for hydrosilylation (C3))
The hydrosilylation catalyst (C3) is a catalyst for the hydrosilylation reaction between the alkenyl group-containing polysiloxane (C1) and the hydrogen polysiloxane (C2).

  The hydrosilylation catalyst (C3) can be used without any particular limitation as long as it is a catalyst used as a hydrosilylation reaction catalyst in a conventional hydrosilyl polysiloxane composition.

  Specific examples of the hydrosilylation catalyst (C3) include a platinum-based catalyst, a rhodium-based catalyst, and a palladium-based catalyst. Among these, a platinum-based catalyst is preferable from the viewpoint of promoting the curing of the present composition. Examples of the platinum-based catalyst include a platinum-alkenylsiloxane complex. Examples of the alkenylsiloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane. Etc. In particular, from the viewpoint of the stability of the complex, 1,3-divinyl-1,1,3,3-toteramethyldisiloxane is preferable.

The hydrosilylation reaction catalyst (C) in the phosphor particle-containing composition of the present invention is used in such an amount that the hydrosilylation reaction of the polysiloxane (A) and the polysiloxane (B) actually proceeds.
Compound (D)
The compound (D) has a structure (d1) and a structure (d2). When the composition contains the compound (D), the phosphor particle-containing film formed from the composition has a high amount of phosphor particles (A) and a small amount of fine particles (B). Uniform dispersion of the body particles (A) can be realized.

(Structure (d1))
The structure (d1) is at least one structure selected from a diaryl silicone structure, a dialkyl silicone structure, a fluorinated alkyl structure, a fluorinated alkenyl structure, and an alkyl structure having 8 or more carbon atoms. When the compound (D) has such a structure (d1), an effect that the affinity between the compound (D) and the binder resin component (C) is improved can be expected.

  The diaryl silicone structure is represented by, for example, formulas (d1-1) and (d1-1 ′).

式（ｄ１−１）中、Ａｒ¹およびＡｒ²は、それぞれ独立に、炭素数６〜１５のアリール基、好ましくは炭素数６〜１０のアリール基である。式（ｄ１−１'）中、Ａｒ¹は、炭素数６〜１５のアリール基、好ましくは炭素数６〜１０のアリール基であり、Ａｒ^2'は、炭素数６〜１５のアリーレン基、好ましくは炭素数６〜１０のアリーレン基であり、＊は、ポリオキシアルキレン構造等の構造（ｄ２）との結合手である。

In formula (d1-1), Ar ¹ and Ar ² are each independently an aryl group having 6 to 15 carbon atoms, preferably an aryl group having 6 to 10 carbon atoms. In the formula (d1-1 ′), Ar ¹ is an aryl group having 6 to 15 carbon atoms, preferably an aryl group having 6 to 10 carbon atoms, and Ar ^{2 ′} is an arylene group having 6 to 15 carbon atoms, preferably Is an arylene group having 6 to 10 carbon atoms, and * is a bond with a structure (d2) such as a polyoxyalkylene structure.

  The dialkyl silicone structure is represented by, for example, formulas (d1-2) and (d1-2 ′).

式（ｄ１−２）中、Ｒ¹およびＲ²は、それぞれ独立に、炭素数１〜３０のアルキル基、好ましくは炭素数１〜２０のアルキル基である。式（ｄ１−２'）中、Ｒ¹は、炭素数１〜３０のアルキル基、好ましくは炭素数１〜２０のアルキル基であり、Ｒ^2'は、メチレン基、または炭素数２〜３０のアルキレン基、好ましくはメチレン基、または炭素数２〜２０のアルキレン基であり、＊は、ポリオキシアルキレン構造等の構造（ｄ２）との結合手である。

In formula (d1-2), R ¹ and R ² are each independently an alkyl group having 1 to 30 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms. In formula (d1-2 ′), R ¹ is an alkyl group having 1 to 30 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, and R ^{2 ′} is a methylene group or 2 to 30 carbon atoms. An alkylene group, preferably a methylene group or an alkylene group having 2 to 20 carbon atoms, and * is a bond with a structure (d2) such as a polyoxyalkylene structure.

  The fluorinated alkyl structure is, for example, a fluorinated alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms (a group in which one or more hydrogen atoms in the alkyl group are replaced with fluorine), and particularly preferably perfluorocarbon. It is an alkyl group.

  The fluorinated alkenyl structure is, for example, a fluorinated alkenyl group having 3 to 25 carbon atoms, preferably 5 to 20 carbon atoms (a group in which one or more hydrogen atoms of the alkenyl group are replaced with fluorine), and particularly preferably a compound of the formula ( a perfluoroalkenyl group such as a group represented by d1-3) or (d1-4).

アルキル構造は、たとえば、炭素数８以上、好ましくは８〜４０のアルキル基であり、具体的には、デカニル基、オクチル基が挙げられる。

The alkyl structure is, for example, an alkyl group having 8 or more carbon atoms, preferably 8 to 40, and specific examples include a decanyl group and an octyl group.

(Structure (d2))
The structure (d2) includes a polyoxyalkylene structure, a structure having an ammonium salt, a structure having a carboxylate, a structure having a phosphate group (H ₂ PO ₄ —), a structure having a phosphate, and a sulfone group (—SO ₃ H), at least one structure selected from a structure having a sulfonate, a structure having a hydroxyl group (—OH), and a structure having an ester group (—COO—). When the compound (D) has such a structure (d2), an effect of improving the affinity between the compound (D) and the phosphor particles (A) and / or fine particles (B) can be expected.

The polyoxyalkylene structure has, for example, the formula — (A—O) _n — (wherein A is a methylene group or an alkylene group having 2 to 20 carbon atoms, preferably a methylene group or an alkylene having 2 to 12 carbon atoms. And n is an integer of 2 to 50, preferably 2 to 40). The structure having an ammonium salt is represented by, for example, —NR ₃ X, —NR ₂ X— or the following formula (d2-1) (wherein R is a hydrogen atom or an alkyl group, and X is a halogen). It is a structure having a group to be formed. The structure having a carboxylate is, for example, a structure having a group represented by —COOM (wherein M is an alkali metal such as sodium). The structure having a phosphate is, for example, a structure having a group represented by the following formula (d2-2) or (d2-3) (wherein M is an alkali metal such as sodium). The structure having a sulfonate is, for example, a structure having a group represented by —SO ₃ M (wherein M is an alkali metal such as sodium).

（化合物（Ｄ）の具体例）
以下、化合物（Ｄ）の具体例を示す。

(Specific examples of compound (D))
Specific examples of compound (D) are shown below.

  Examples of the compound having a dialkyl silicone structure or a diaryl silicone structure and a polyoxyalkylene structure include, for example, Polyflow KL-245, KL-270, KL-700 (manufactured by Kyoeisha Chemical Co., Ltd.), TEGO WET 270 (Evonik Degussa And a polyether-modified polysiloxane such as a compound represented by the following formula (D1) (particularly the following formula (D2)).

式（Ｄ１）中、Ｒは、炭素数６〜１５のアリール基または炭素数１〜３０のアルキル基であり、Ｒ'は炭素数６〜１５のアリーレン基またはメチレン基もしくは炭素数２〜３０のアルキレン基であり、Ａはメチレン基、または炭素数２〜２０のアルキレン基であり、Ｒａは水素原子または炭素数１〜５のアルキル基であり、ｎは２〜５０の整数であり、ｘおよびｙは、それぞれ独立に２〜１００の整数である。

In the formula (D1), R is an aryl group having 6 to 15 carbon atoms or an alkyl group having 1 to 30 carbon atoms, and R ′ is an arylene group or methylene group having 6 to 15 carbon atoms or a C 2 to 30 carbon atom. An alkylene group, A is a methylene group or an alkylene group having 2 to 20 carbon atoms, Ra is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n is an integer of 2 to 50, x and y is an integer of 2-100 each independently.

In formula (D2), Ra is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n is an integer of 2 to 20, and x and y are each independently an integer of 2 to 100.
As a commercial item of the compound represented by the formula (D2), for example, SH-28PA, SH-30PA, SH-8400, SH-190, SH-193, SF-8428 (manufactured by Toray Dow Corning Co., Ltd.) Is mentioned.

  Examples of the compound (D) having an alkyl structure having 8 or more carbon atoms and a polyoxyalkylene structure include polyoxyalkylene alkyl ethers. Moreover, as a commercial item, a brand name "Neugen TDS-50" (Daiichi Kogyo Seiyaku Co., Ltd. make) is mentioned, for example.

  Examples of the compound (D) having a fluorinated alkyl structure or a fluorinated alkenyl structure and a polyoxyalkylene structure include diglycerin ethylene oxide adduct perfluorononenyl ether and hydroxy-bridged fluoropolyether. Moreover, as a commercial item, a brand name "PolyFox PF-151N" (made by Omninova Solutions, Inc.), Footent 209F, NBX-15 (made by Neos Co., Ltd.) is mentioned, for example.

  Examples of the compound (D) having a structure having an ammonium salt, a carboxylate, a phosphate group, a phosphate, a sulfone group, a sulfonate, a hydroxyl group or an ester group include perfluorooctane sulfonic acid. As a commercial item, a brand name "mega fuck" series (made by DIC Corporation) and a brand name "Emulgen" series (made by Kao Corporation) are mentioned, for example. Moreover, polyoxyethylene alkyl ether phosphate ester is mentioned. As a commercial item, a brand name "Blysurf A208F" (Daiichi Kogyo Seiyaku Co., Ltd. make) is mentioned, for example.

  Among these, the compound (D) having a polyoxyalkylene structure as the structure (d2) is preferable. When the compound (D) has a polyoxyalkylene structure, a phosphor layer in which phosphor particles are uniformly dispersed with the addition of a small amount of silica fine particles, etc., even when the content ratio of the phosphor particles is high, using this composition Can be formed efficiently.

  Content of a compound (D) is 0.01-2 weight part with respect to 100 weight part of fluorescent substance particles (A), Preferably it is 0.03-1.5 weight part, More preferably, 0.05- 1 part by weight. When the content of the compound (D) is within the above range, uniform dispersion of the phosphor particles (A) can be suitably realized in the phosphor particle-containing film formed from the present composition. When content of a compound (D) is larger than the said upper limit, there exists a possibility of the fall of the transmittance | permeability of the cured film formed from this composition, and the fall of heat resistance.

  As long as the object of the present invention is achieved, the phosphor particle-containing composition of the present invention can contain, for example, a retarder such as cyclo-tetramethyltetravinyltetrasiloxane, diphenylbis ( Diluents such as dimethylvinylsiloxy) silane and phenyltris (dimethylvinylsiloxy) silane, flame retardants, heat-resistant agents, antioxidants and the like can be contained.

The phosphor particle-containing composition of the present invention can be prepared by uniformly mixing the above components by a known method such as a mixer.
The viscosity at 25 ° C. of the phosphor particle-containing composition of the present invention is preferably 1 to 1000000 mPa · s, more preferably 3,000 to 30,000 mPa · s. When the viscosity is within this range, the operability of the composition is improved.

The phosphor particle-containing composition of the present invention can be prepared as one liquid, or can be prepared by dividing into two liquids, and the two liquids can be mixed and used at the time of use. If necessary, a small amount of a curing inhibitor such as acetylene alcohol may be added.
<Fluorescent particle-containing film>
The phosphor particle-containing film of the present invention can be obtained, for example, by applying the phosphor particle-containing composition to a substrate and curing it. When the phosphor particle-containing composition is applied on the light emitting element portion of the LED and cured, a phosphor particle-containing film that is a phosphor layer is obtained.

Examples of the method for curing the phosphor particle-containing composition include a method in which the composition is applied on a substrate and then heated at 100 to 180 ° C. for 1 to 13 hours.
The phosphor particle-containing film of the present invention comprises phosphor particles (A), fine particles (B), a binder resin component (C), a diaryl silicone structure, a dialkyl silicone structure, a fluorinated alkyl structure, a fluorinated alkenyl structure, and At least one structure (d1) selected from an alkyl structure having 8 or more carbon atoms, a polyoxyalkylene structure, a structure having an ammonium salt, a structure having a carboxylate, a structure having a phosphate group, and a phosphate A phosphor particle containing a structure, a structure having a sulfone group, a structure having a sulfonate, a structure having a hydroxyl group, and a compound (D) having at least one structure (d2) selected from a structure having an ester group A phosphor particle (A), a fine particle (B), and a binder, which are films, which are contained in the phosphor particle-containing film When the total of the fat component (C) and the compound (D) is 100 wt%, the phosphor particles (A) are contained in an amount of 30 wt% or more, and the fine particles (B) are contained in an amount of more than 0 wt% to 10 wt%. The compound (D) is contained in an amount of 0.01 to 2 parts by weight with respect to 100 parts by weight of the phosphor particles (A). Each component contained in the phosphor particle-containing film of the present invention is as described in the phosphor particle-containing composition.

As described above, the phosphor particles (A) are uniformly dispersed in the phosphor particle-containing film of the present invention.
<Optical semiconductor device>
The optical semiconductor device of the present invention has the phosphor particle-containing film. The optical semiconductor device of the present invention is, for example, a device in which the phosphor layer 52 is the phosphor particle-containing film in the optical semiconductor device shown in FIG. In the optical semiconductor device of the present invention, for example, the phosphor particle-containing composition is applied on a semiconductor light emitting element, and the phosphor particle-containing film, which is a phosphor layer, is formed by curing the composition. It can be manufactured by filling a sealing material. The method for curing the phosphor particle-containing composition is as described above.

Examples of the optical semiconductor device include an LED and an LD (Laser Diode).
As described above, in the phosphor particle-containing film, even if the content of silica fine particles or the like is small, the high content of phosphor particles (A) is uniformly dispersed, so that brightness, gas barrier properties, crack resistance, etc. It is possible to realize the full wavelength (whitening) of an optical semiconductor device such as an LED without causing a decrease in.

1. Preparation of binder resin component
1-1. Structural analysis The structure of the synthesized compound was analyzed by ²⁹ Si NMR and ¹³ C NMR.
1-2. Weight average molecular weight Weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) under the following conditions and was determined as a polystyrene equivalent value.

Apparatus: HLC-8120C (manufactured by Tosoh Corporation)
Column: TSK-gel Multipore HXL-M (manufactured by Tosoh Corporation)
Eluent: THF, flow rate 0.5 mL / min, load 5.0%, 100 μL
1-3. Synthesis of polysiloxane
[Synthesis Example 1] Synthesis of alkenyl group-containing polysiloxane (C1-1) 1,3-divinyl-1,1,3,3-tetramethyldithiol in a four-necked flask equipped with a stirrer, reflux condenser, inlet, and thermometer 20 g of siloxane, 120 g of phenyltrimethoxysilane, 6 g of 2- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 15 g of water, 0.1 g of trifluoromethanesulfonic acid and 500 g of toluene were mixed and heated to reflux for 1 hour. . After cooling, 2.5 g of a 0.5 wt% potassium hydroxide aqueous solution was added to the reaction solution, and the mixture was heated to reflux for 4 hours, and then excess water was removed by azeotropic dehydration. After cooling, the reaction solution was neutralized with acetic acid and washed with water. Polysiloxane (C1-1) was obtained by removing the solvent from the reaction solution.
[Synthesis Example 2] Synthesis of alkenyl group-containing polysiloxane (C1-2) 1,3-divinyl-1,1,3,3-tetramethyldiethyl in a four-necked flask equipped with a stirrer, a reflux condenser, an inlet, and a thermometer 59 g of siloxane, 441 g of phenyltrimethoxysilane, 143 g of water, 0.4 g of trifluoromethanesulfonic acid and 500 g of toluene were added and mixed, followed by heating under reflux for 1 hour. After cooling, the lower layer was separated and removed, and the upper toluene solution layer was washed with water. To the toluene solution layer washed with water, 228 g of 3-glycidoxypropylmethyldimethoxysilane, 130 g of water and 0.5 g of potassium hydroxide were added and heated under reflux for 1 hour. Subsequently, methanol was distilled off and excess water was removed by azeotropic dehydration. Subsequently, the mixture was heated to reflux for 4 hours. The toluene solution after the reaction was cooled, neutralized with 0.6 g of acetic acid and washed with water. After water removal, toluene was distilled off under reduced pressure and concentrated to obtain a polysiloxane having 25 mol% of alkenyl groups and 40 mol% of epoxy groups (with the total number of Si atoms contained in the polysiloxane being 100 mol%). C1-2) was obtained. It was 3,000 when the polystyrene conversion weight average molecular weight of (C1-2) was measured by the gel permeation chromatography. The chemical formula of polysiloxane (C1-2) is (ViMe ₂ SiO _1/2 ) ₁₈ (PhSiO _3/2 ) ₆₃ (EpMeSiO _2/2 ) ₂₉ (Vi is a vinyl group, Me is a methyl group, Ph is a phenyl group, Ep Represents a glycidoxypropyl group, and the number attached to each structural unit is a numerical value indicating the ratio of the structural unit to the total of all structural units in mol%).
[Synthesis Example 3] Hydrogensiloxane (C2-1)
403 g of diphenyldimethoxysilane, 0.1 g of trifluoromethanesulfonic acid, 450 g of 1,1,3,3-tetramethyldisiloxane were added to the reaction kettle, and then 130 g of acetic acid was added, followed by reaction at 50 ° C. for 3 hours. After completion of the reaction, liquid separation extraction was performed using toluene and water to obtain hydrogensiloxane (C2-1) shown below.

１−４．バインダー樹脂成分の調製
［調製例１］バインダー樹脂成分（Ｃ１）の調製
アルケニル基含有ポリシロキサン（Ｃ１−１）を５７部、アルケニル基含有ポリシロキサン（Ｃ１−２）を３部、フェニルトリス（ジメチルビニルシロキシ）シランを１０部、ハイドロジェンシロキサン（Ｃ２−１）を３０部、白金と１，３−ジビニル−１，１，３，３−テトラメチルジシロキサンとの錯体（白金金属量３質量％）を０．０１部、およびエチニルシクロヘキサノールを０．０１部混合し、バインダー樹脂成分（Ｃ１）を調製した。
２．蛍光体粒子含有組成物の調製
［実施例１〜６および比較例１〜２］
下記表１に示す成分を混合することにより実施例１〜６および比較例１〜２の蛍光体粒子含有組成物を調製した。なお、各成分の詳細は以下の通りである。

1-4. Preparation of binder resin component [Preparation Example 1] Preparation of binder resin component (C1) 57 parts of alkenyl group-containing polysiloxane (C1-1), 3 parts of alkenyl group-containing polysiloxane (C1-2), phenyltris (dimethyl) 10 parts of vinylsiloxy) silane, 30 parts of hydrogensiloxane (C2-1), complex of platinum and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (platinum metal amount 3 mass%) ) And 0.01 part of ethynylcyclohexanol were mixed to prepare a binder resin component (C1).
2. Preparation of phosphor particle-containing composition [Examples 1-6 and Comparative Examples 1-2]
The phosphor particle-containing compositions of Examples 1 to 6 and Comparative Examples 1 to 2 were prepared by mixing the components shown in Table 1 below. The details of each component are as follows.

蛍光体粒子（Ａ１）：商品名「Ｙ３９５７」（Ｉｎｔｅｍａｔｉｅｘ製）
微粒子（Ｂ１）：商品名「ＲＸ３００」（日本アエロジル（株）製）
化合物（Ｄ１）：ポリオキシアルキレンアルキルエーテル（商品名「ノイゲンＴＤＳ―５０」、第一工業製薬株式会社製、下記式に示す構造の化合物）

Phosphor particles (A1): trade name “Y3957” (manufactured by Intematex)
Fine particles (B1): trade name “RX300” (manufactured by Nippon Aerosil Co., Ltd.)
Compound (D1): Polyoxyalkylene alkyl ether (trade name “Neugen TDS-50”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., compound having the structure shown in the following formula)

化合物（Ｄ２）：商品名：「ＦＴＸ−２１８」（ネオス（株）製、下記式に示す構造の化合物）

Compound (D2): Trade name: “FTX-218” (manufactured by Neos Co., Ltd., compound having the structure shown in the following formula)

（式中、Ｒは水素原子または-Ｃ(ＣＦ₃)＝Ｃ[ＣＦ(ＣＦ₃)₂]₂であり、Ｒのうちの少なくとも１つは-Ｃ(ＣＦ₃)＝Ｃ[ＣＦ(ＣＦ₃)₂]₂である。ｎは１５〜２５の整数であって、平均が１８である。ｍは０〜２の整数である。）
化合物（Ｄ３）：シリコーン系界面活性剤（東レ・ダウコーニング・シリコーン（株）製、商品名「ＳＨ−２８ＰＡ」、下記式に示す構造の化合物）

Wherein R is a hydrogen atom or —C (CF ₃ ) ═C [CF (CF ₃ ) ₂ ] ₂ , and at least one of R is —C (CF ₃ ) ═C [CF (CF _{3 2} ] _2. n is an integer of 15 to 25, and the average is 18. m is an integer of 0 to 2.)
Compound (D3): Silicone surfactant (trade name “SH-28PA” manufactured by Toray Dow Corning Silicone Co., Ltd., a compound having a structure represented by the following formula)

（式中、ａは１〜１０の整数であり、ｎは１〜２０の整数である。）
化合物（Ｄ４）：ポリオキシエチレンアルキルエーテルリン酸エステル（商品名「ブライサーフＡ２０８Ｆ」、第一工業製薬株式会社製、下記式に示す構造の化合物）

(In the formula, a is an integer of 1 to 10, and n is an integer of 1 to 20.)
Compound (D4): Polyoxyethylene alkyl ether phosphate ester (trade name “Blysurf A208F”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., compound having a structure represented by the following formula)

（式中、Ｒは炭素数が１〜２０のアルキル基である。）
３．評価
３−１．蛍光体粒子含有組成物中における蛍光体粒子の分散性
実施例１〜６および比較例１〜２の蛍光体粒子含有組成物を２３℃で１日間保存した後の蛍光体粒子の分散状態を目視にて観察した。なお、目視での評価基準は下記の通りである。結果を表１に示す。
「Ａ」：蛍光体粒子の沈降なし。
「Ｂ」：蛍光体粒子の沈降あり。
３−２．硬化膜中における蛍光体粒子の分散性
実施例１〜６および比較例１〜２の蛍光体粒子含有組成物をシリコンウェハ上に塗布後、１００℃で１時間、次いで１５０℃で５時間加熱し、膜厚２００μｍの硬化膜（蛍光体粒子含有膜）を形成した。得られた硬化膜を電子顕微鏡で観察し、下記の評価基準にて硬化膜における蛍光体の分散性を評価した。評価結果を表１に示す。

(In the formula, R is an alkyl group having 1 to 20 carbon atoms.)
3. Evaluation
3-1. Dispersibility of phosphor particles in phosphor particle-containing composition Phosphor particles after the phosphor particle-containing compositions of Examples 1 to 6 and Comparative Examples 1 and 2 were stored at 23C for 1 day The dispersion state was visually observed. The visual evaluation criteria are as follows. The results are shown in Table 1.
“A”: No precipitation of phosphor particles.
“B”: There is sedimentation of phosphor particles.
3-2. Dispersibility of phosphor particles in cured film After the phosphor particle-containing compositions of Examples 1 to 6 and Comparative Examples 1 and 2 were applied on a silicon wafer, they were heated at 100 ° C. for 1 hour and then at 150 ° C. for 5 hours. A cured film (phosphor particle-containing film) having a thickness of 200 μm was formed. The obtained cured film was observed with an electron microscope, and the dispersibility of the phosphor in the cured film was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1.

“A”: The phosphor particles are uniformly dispersed in the cured film.
“B”: The phosphor particles are unevenly distributed on the substrate side of the cured film.
3-3. Viscosity The viscosity of the phosphor particle-containing compositions of Examples 1 to 6 and Comparative Examples 1 and 2 was measured at 25 ° C. using an E-type viscometer. The results are shown in Table 1.

50 light emitting element portion 51 sealing material 52 phosphor layer 53 binder 54 phosphor particles

Claims (9)

Phosphor particles (A), fine particles (B), binder resin component (C), and at least one selected from a diaryl silicone structure, a dialkyl silicone structure, a fluorinated alkyl structure, a fluorinated alkenyl structure, and an alkyl structure having 8 or more carbon atoms. Seed structure (d1), and polyoxyalkylene structure, structure having ammonium salt, structure having carboxylate, structure having phosphate group, structure having phosphate, structure having sulfonate group, sulfonate A phosphor particle-containing composition comprising a compound (D) having at least one structure (d2) selected from a structure having, a structure having a hydroxyl group, and a structure having an ester group,
When the total of the phosphor particles (A), the fine particles (B), the binder resin component (C) and the compound (D) is 100% by weight, the phosphor particles (A) are 30% by weight or more and the fine particles ( B) is contained in an amount of more than 0% by weight and 10% by weight or less,
A phosphor particle-containing composition comprising 0.01 to 2 parts by weight of the compound (D) with respect to 100 parts by weight of the phosphor particles (A).   The phosphor particle-containing composition according to claim 1, comprising 0.01 to 2 parts by weight of the fine particles (B) with respect to 100 parts by weight of the phosphor particles (A).   The phosphor particle-containing composition according to claim 1 or 2, which contains polysiloxane as the binder resin component (C).   The phosphor particle-containing composition according to claim 1 or 2, which contains, as the binder resin component (C), an alkenyl group-containing polysiloxane (C1), a hydrogen polysiloxane (C2), and a hydrosilylation catalyst (C3).   The phosphor particle-containing composition according to any one of claims 1 to 4, wherein the fine particles (B) are silica fine particles.   Structure (d2) is a polyoxyalkylene structure, The fluorescent substance particle containing composition in any one of Claims 1-5.   A phosphor particle-containing film obtained from the phosphor particle-containing composition according to claim 1. Phosphor particles (A), fine particles (B), binder resin component (C), and at least one selected from a diaryl silicone structure, a dialkyl silicone structure, a fluorinated alkyl structure, a fluorinated alkenyl structure, and an alkyl structure having 8 or more carbon atoms. Seed structure (d1), as well as polyoxyalkylene structure, structure with ammonium salt, structure with carboxylate, structure with phosphate group, structure with phosphate, structure with sulfonate group, sulfonate A phosphor particle-containing film comprising a compound (D) having at least one structure (d2) selected from a structure having, a structure having a hydroxyl group, and a structure having an ester group,
When the total of the phosphor particles (A), the fine particles (B), the binder resin component (C) and the compound (D) contained in the phosphor particle-containing film is 100% by weight, the phosphor particles (A) 30 wt% or more, containing the fine particles (B) more than 0 wt% and 10 wt% or less,
A phosphor particle-containing film comprising 0.01 to 2 parts by weight of the compound (D) with respect to 100 parts by weight of the phosphor particles (A).   An optical semiconductor device comprising the phosphor particle-containing film according to claim 7 or 8.

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