WO2015060289A1

WO2015060289A1 - Phosphor composition, phosphor sheet, phosphor sheet laminate, led chip and led package each using said phosphor composition, phosphor sheet or phosphor sheet laminate, and method for manufacturing led package

Info

Publication number: WO2015060289A1
Application number: PCT/JP2014/077914
Authority: WO
Inventors: 石田豊; 重田和樹; 諏訪充史
Original assignee: 東レ株式会社
Priority date: 2013-10-24
Filing date: 2014-10-21
Publication date: 2015-04-30
Also published as: CN105765744A; JPWO2015060289A1; TWI657599B; TW201521238A; KR102035511B1; CN105765744B; KR20160075495A

Abstract

[Problem] [Solution] Provided is a phosphor composition which contains a phosphor, a matrix resin and metal compound particles, and which is characterized in that: the metal compound particles have a refractive index of 1.7 or more and an average particle diameter of 1-50 nm; the average refractive index (N1) of the metal compound particles and the matrix resin and the refractive index (N2) of the phosphor satisfy the relation described below; and the metal compound particles are grafted. A sheet is able to be formed by a single coating process using this phosphor composition, and this phosphor composition is capable of improving the luminance of an LED package that employs this phosphor composition. 0.20 ≥ |N1 - N2|

Description

Phosphor composition, phosphor sheet, phosphor sheet laminate, LED chip using them, LED package, and method for producing the same

The present invention relates to a phosphor composition, a phosphor sheet, a phosphor sheet laminate, an LED chip using them, an LED package, and a method for producing the same.

Light-emitting diodes (LEDs) are used for LCD backlights, in-vehicle headlights, spotlights, and general lighting applications, featuring low power consumption, long service life, and design with a dramatic improvement in luminous efficiency. The market is expanding rapidly.

Since the emission spectrum of an LED depends on the material forming the LED, its emission color is limited. Therefore, in order to obtain white light for LCD backlights and general illumination using LEDs, it is necessary to arrange phosphors suitable for the respective chips on the LED chips and convert the emission wavelength to obtain white light. . Specifically, a method of disposing a yellow phosphor on a blue light emitting LED chip, a method of disposing red and green phosphors on a blue light emitting LED chip, red, green, blue on a LED chip emitting ultraviolet light. A method of arranging the phosphors has been proposed. Among these, the method of arranging the yellow phosphor on the blue LED chip and the method of arranging the red and green phosphors on the blue LED chip are currently most widely adopted from the viewpoint of the luminous efficiency and cost of the LED chip. ing.

As one of the specific methods for arranging the phosphor on the LED chip, there has been proposed a method (phosphor sheet method) in which a resin in which a high concentration phosphor is uniformly distributed is molded into a sheet in advance and used. (For example, refer to Patent Document 1). In this method, a uniform film thickness, phosphor concentration distribution, and light resistance can be obtained by molding a resin containing a high concentration phosphor into a sheet in advance. Therefore, the color variation of the LED package can be suppressed when it is attached to the LED package or the LED chip. However, since the refractive index of the LED chip or phosphor is higher than the refractive index of the resin contained in the phosphor sheet, the light generated in the LED chip is sufficiently externally reflected by the reflection at the LED chip or phosphor interface. It cannot be taken out.

In order to suppress reflection due to a difference in refractive index, it has been studied to stack thin films having different refractive indexes in order of refractive index and continuously change the refractive index. For example, 2 to 20 sealing layers having different refractive indexes are formed, and the refractive index n _{1 of} the lowermost sealing layer (first sealing layer) is in the range of 1.55 to 1.85. , the top layer of the sealing layer (n-th sealing layer, n = 2 ~ 20) refractive index _{n n} of the range 1.30 to 1.65 sealing at least two or more layers having different refractive indices It has been proposed that layers are stacked in order of decreasing refractive index, and each sealing layer includes hydrophobic zirconium particles and / or hydrophobic silica-based hollow particles and a matrix resin to form a refractive index gradient. (For example, refer to Patent Document 2).

In addition, it is disclosed that a conversion layer disposed on an LED chip contains a fluorescent agent, a binder material, and a plurality of nanoparticles, and the nanoparticles are dispersed so as to closely match the refractive index of the fluorescent agent particles. (For example, refer to Patent Document 3).

Japanese Patent Laid-Open No. 5-152609 JP 2012-121941 A Japanese Patent No. 5227252

However, the above method has a problem in that the cost increases because the number of processes such as etching by dry etching or the like on the LED chip, or by laminating thin layers having different refractive indexes many times. There is also a problem that the brightness of the LED package is not improved.

In particular, the present inventors have found that the brightness of the LED package is not improved due to the following two reasons. (1) When using a conversion layer in which a plurality of nanoparticles are dispersed in a binder material, the nanoparticles are aggregated. (2) A void or crack such as air is generated between the light emitting surface of the LED chip and the phosphor sheet, and the adhesion between the LED chip and the phosphor sheet is lowered, so that the light extraction efficiency from the LED chip is lowered. To do.

The present invention focuses on the above problems and aims to reduce the LED package manufacturing process and improve the brightness of the LED package.

One feature of the present invention is a phosphor composition containing a phosphor, a matrix resin, and metal compound particles, wherein the metal compound particles have a refractive index of 1.7 or more, and an average particle diameter. 1 to 50 nm, the average refractive index N1 of the metal compound particles and the matrix resin satisfies the following relationship with the refractive index N2 of the phosphor, and the metal compound particles are grafted: A phosphor composition.
0.20 ≧ | N1-N2 |.

Another feature of the present invention is a phosphor sheet containing a phosphor, a matrix resin, and metal compound particles, wherein the metal compound particles have a refractive index of 1.7 or more and an average particle diameter. Is 1 to 50 nm, the metal compound particles are grafted, and the average refractive index N1 of the metal compound particles and the matrix resin satisfies the following relationship (i) with the refractive index N2 of the phosphor: The phosphor sheet is characterized in that the viscoelastic behavior of the sheet satisfies the following relationships (ii), (iii), and (iv).
<Refractive index relationship>
(I) 0.20 ≧ | N1-N2 |
<Viscoelastic behavior>
(Ii) The storage elastic modulus G ′ is 1.0 × 10 ⁴ Pa ≦ G ′ ≦ 1.0 × 10 ⁶ Pa at a temperature of 25 ° C. and tan δ <1
(Iii) Storage modulus G ′ is 1.0 × 10 ² Pa ≦ G ′ <1.0 × 10 ⁴ Pa at a temperature of 100 ° C. and tan δ ≧ 1
(Iv) The storage elastic modulus G ′ is 1.0 × 10 ⁴ Pa ≦ G ′ ≦ 1.0 × 10 ⁶ Pa at a temperature of 200 ° C. and tan δ <1.

According to the present invention, an LED package with improved brightness can be provided by a simple process.

Cross-sectional SEM photograph (50,000 times magnification) of the cured film of the phosphor composition of Example 10 Cross-sectional SEM photograph of the cured film of the phosphor composition of Example 10 (magnification 100,000 times) Cross-sectional SEM photograph of the cured film of the phosphor composition of Comparative Example 8 (50,000 times magnification) Cross-sectional SEM photograph of the cured film of the phosphor composition of Comparative Example 8 (magnification of 100,000 times) Cross-sectional SEM photograph of the phosphor sheet of Example 19 (50,000 times magnification) Cross-sectional SEM photograph of the phosphor sheet of Example 19 (magnification 100,000 times) Cross-sectional SEM photograph of the phosphor sheet of Comparative Example 12 (magnification 50,000 times) Cross-sectional SEM photograph of the phosphor sheet of Comparative Example 13 (magnification 50,000 times) An example of the LED chip with a phosphor sheet using the phosphor sheet laminate of the present invention. An example of the LED package using the fluorescent substance sheet laminated body of this invention. An example of the LED package using the fluorescent substance sheet laminated body of this invention. The schematic diagram of an illumination intensity measurement system. An example of the LED package manufacturing method using the fluorescent substance composition of this invention. An example of the manufacturing method of the LED package using the fluorescent substance sheet laminated body of this invention. An example of the manufacturing method of the LED chip with a fluorescent substance sheet using the fluorescent substance sheet laminated body of this invention. An example of the manufacturing method of the LED chip with a fluorescent substance sheet using the fluorescent substance sheet laminated body of this invention. An example of the method for attaching the phosphor sheet laminate of the present invention An example of the method for attaching the phosphor sheet laminate of the present invention An example of the manufacturing method of the LED package using the fluorescent substance sheet laminated body of this invention. An example of the manufacturing method of the LED package using the fluorescent substance sheet laminated body of this invention.

<Phosphor composition>
A phosphor composition that is one feature of the present invention is a phosphor composition containing a phosphor, a matrix resin, and metal compound particles, and the refractive index of the metal compound particles is 1.7 or more. And the average particle diameter is 1 to 50 nm, the average refractive index N1 of the metal compound particles and the matrix resin satisfies the following relationship with the refractive index N2 of the phosphor, and the metal compound particles are grafted: It is characterized by.
0.20 ≧ | N1-N2 |.

In the present invention, the phosphor composition refers to a composition containing a phosphor, a matrix resin, and metal compound particles.

In the phosphor composition of the present invention, the average refractive index N1 of the metal compound particles and the matrix resin satisfies the following relationship with the refractive index N2 of the phosphor.
0.20 ≧ | N1-N2 |.

As a result, when the phosphor composition of the present invention is installed on the light emitting surface of the LED chip, the light extracted from the LED chip can be efficiently applied to the phosphor, and the light extraction performance of the LED chip is improved. As a result, the brightness of the LED package is improved.

The reason is presumed as follows. When the matrix resin contains the metal compound particles, the difference in refractive index between the mixed component and the phosphor can be reduced. Thereby, since reflection and scattering of light at the interface between the phosphor and the matrix resin containing metal compound particles can be suppressed, light incident on the phosphor composition from the LED chip efficiently hits the phosphor. Further, when the matrix resin contains the metal compound particles, the refractive index of the entire phosphor composition can be brought close to the refractive index of the LED chip. Therefore, total reflection inside the LED chip can also be suppressed, and light extraction from the LED chip is improved. As a result of these two effects, the brightness of the LED package can be improved.

In the present invention, a preferable upper limit value of the refractive index difference | N1-N2 | is 0.20, more preferably 0.10, and particularly preferably 0.05. By being below the upper limit value, the above effects can be obtained, and the brightness of the LED package can be improved. The smaller the refractive index difference | N1−N2 |, the greater the effect. Therefore, the lower limit is not particularly limited, but | N1−N2 | ≧ 0.02 is preferable.

The average refractive index N1 of the matrix resin containing metal compound particles is represented by the sum of the product of the refractive index and volume fraction of the metal compound particles and the product of the refractive index and volume fraction of the matrix resin.

The refractive index can be measured using a refractive index / film thickness measuring device “Prism Coupler Model 2010 / M” (manufactured by Metricon). Specifically, a transparent film of a composition in which metal compound particles are dispersed in a matrix resin is prepared, and the refractive index (TE) in the direction perpendicular to the film surface at 633 nm (using a He—Ne laser) is measured at a measurement temperature of 25 ° C. The average refractive index N1 can be obtained by measuring.

The refractive index N2 of the phosphor can be obtained by the Becke line method, the liquid immersion method, and the extrapolation method.

<Metal compound particles>
The metal compound particles used in the present invention have a refractive index of 1.7 or more and an average particle diameter of 1 to 50 nm. Hereinafter, such metal compound particles are referred to as “high refractive index nanoparticles”.

Since high refractive index nanoparticles are sufficiently smaller than the wavelength of visible light, they can be regarded as optically homogeneous by being dispersed in a matrix resin. In addition, since the refractive index of the high refractive index nanoparticles and the refractive index of the matrix resin are different, the average refractive index of the matrix resin containing metal compound particles having an average particle diameter of 1 to 50 nm is the refractive index and volume of the metal compound particles. It is expressed as the sum of the product of the fraction and the product of the refractive index and the volume fraction of the matrix resin. That is, if the metal compound particles have a refractive index larger than that of the matrix resin, the average refractive index can be increased.

(Particle size)
When the average particle diameter is smaller than 1 nm, the metal compound particles are difficult to exist as particles, and when the average particle diameter is larger than 50 nm, light is easily scattered and the light transmittance is lowered. From the viewpoint of suppressing light scattering, the average particle diameter is preferably 1 to 30 nm.

Here, the average particle diameter of the metal compound particles is an average value of particle diameters obtained by the following method. From the two-dimensional image obtained by observing the particles with a scanning electron microscope (SEM), the one that maximizes the distance between the two intersections of the straight line that intersects the outer edge of the particles at two points is calculated as the particle diameter. It is defined as Measurement is performed on 200 particles observed, and the average value of the obtained particle diameters is defined as the average particle diameter. For example, when measuring the particle size of metal compound particles present in the phosphor sheet, mechanical polishing method, microtome method, CP method (Cross-sect (I) on Pol (I) sher) and focused ion beam (F (I) B) Two-dimensional obtained by performing polishing so that the cross section of the phosphor sheet is observed by any of the processing methods, and then observing the obtained cross section with a scanning electron microscope (SEM) The average particle diameter can be calculated from the image.

(composition)
Metal compound particles include titania, zirconia, alumina, ceria, tin oxide, indium oxide, zircon, iron oxide, zinc oxide, niobium oxide, silicon nitride, boron nitride, aluminum nitride, silicon carbide, aluminum hydroxide, barium titanate Diamond etc. are mentioned, These may be used independently and may be used together 2 or more types. From the viewpoint of high refractive index and easy availability, at least one selected from the group consisting of aluminum compound particles, tin compound particles, titanium compound particles, zirconium compound particles, and niobium compound particles is preferably used. Specific examples include oxides, sulfides and hydroxides of aluminum, tin, titanium, or zirconium. Among these, from the viewpoint of adjusting the refractive index of the coating film and the cured film, zirconium oxide particles and / or Titanium oxide particles are preferably used.

If the metal compound particles have a high refractive index, the average refractive index when dispersed in the matrix resin can be increased, and as described above, the difference in refractive index from the LED chip is reduced to extract light from the LED chip. Efficiency can be improved. Commercially available metal compound particles include tin oxide-titanium oxide composite particles “OPTRAIK TR-502”, “OPTRAIK TR-504”, “OPTRAIK TR-520”, and silicon oxide-titanium oxide composite particles. "Optlake TR-503", "Optlake TR-527", "Optlake TR-528", "Optlake TR-529", "Optrake TR-513", "Optrake TR-505" of titanium oxide particles ”(Above, trade name, manufactured by Catalytic Chemical Industry Co., Ltd.), zirconium oxide particles (manufactured by Kojundo Chemical Laboratory Co., Ltd.), tin oxide-zirconium oxide composite particles (produced by Catalytic Chemical Industry Co., Ltd.), tin oxide And particles (manufactured by Kojundo Chemical Laboratory Co., Ltd.). These metal compound particles are preferably used after grafting to be described later in order to improve dispersibility with the matrix resin.

(Grafting)
In the present invention, the fact that the metal compound particles are grafted means that the polymer is chemically bonded (grafted) to the particle surface using hydroxyl groups present on the particle surface. By the grafting of the metal compound particles, a phosphor composition or a phosphor sheet having excellent adhesion to an LED chip or the like can be obtained.

The adhesion between the phosphor composition and the light emitting surface of the LED chip is an important factor for improving the brightness of the LED package. If the adhesiveness with the LED chip decreases due to the occurrence of voids or cracks such as air between the light emitting surface of the LED chip and the phosphor composition or phosphor sheet, the light extraction efficiency decreases.

When the metal compound particles are grafted, the dispersibility of the metal compound particles in the matrix resin is improved, and the compatibility between the metal compound particles and the matrix resin is improved. This makes it difficult for the interface between the matrix resin and the metal compound particles to occur. Therefore, when installing the phosphor composition or the phosphor sheet on the light emitting surface of the LED chip, it is possible to suppress voids or cracks that occur when the phosphor composition or the phosphor sheet is cured. Therefore, when they are installed on the light emitting surface of the LED chip, the adhesion between them and the light emitting surface is improved, the light extraction from the LED chip is improved, and as a result, the brightness of the LED package is improved.

Examples of the state where the interface between the matrix resin and the metal compound particles is not generated are shown in FIGS. 1 and 2, and examples of the state where the interface is generated are shown in FIGS. 1 and 2 are photographs obtained by cutting a cross section of a cured film of the phosphor composition of Example 10 described later and observing with a scanning electron microscope (SEM), and FIGS. 3 and 4 are comparative examples described later. It is the photograph which cut | disconnected the cross section of the cured film of the fluorescent substance composition of 8, and observed with SEM.

In the state where the interface between the matrix resin and the metal compound particles does not occur, as shown in FIGS. 1 and 2, the metal compound particles are uniformly dispersed in the matrix resin, and the boundary portion between the metal compound particles and the matrix resin is not present. It becomes clear. On the other hand, when the interface between the matrix resin and the metal compound particles is generated, as shown in FIGS. 3 and 4, the metal compound particles 102 form an aggregate in which the metal compound particles are aggregated. The boundary between the aggregate and the matrix resin 101 is clearly observed.

In addition, when a silicone fine particle is contained in a fluorescent substance composition, a mode different from this may be observed. This point will be described later.

In the present invention, the type of polymer used for grafting the metal compound particles is not particularly limited as long as it is chemically bonded to the surface of the metal compound particles. It may be a water-soluble polymer (for example, poly (N-isopropylacrylamide), polyethylene glycol, polyacrylamide, polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, initial condensate such as resole resin, urea resin, melamine resin, etc.) or water-insoluble. It may be a polymer (for example, polysiloxane, 1,4-cis-isoprene, isoprene elastomer, polystyrene, polybutadiene, polyisoprene, polymethyl methacrylate, poly n-butyl acrylate, polyvinyl chloride, polyacrylonitrile, polylactic acid, etc.). Particularly preferred is polysiloxane which is a condensate of alkoxysilane described later.

In the present invention, the presence or absence of grafting on the particle surface is observed with a scanning electron microscope (hereinafter referred to as SEM) or a transmission electron microscope (hereinafter referred to as TEM) at the boundary between the metal compound particles and the matrix resin. You can know by When grafted, the metal compound particles are uniformly dispersed in the matrix resin, and the boundary between the metal compound particles and the matrix resin becomes unclear, whereas when not grafted, the metal compound particles Since the particles are aggregated, the boundary portion between the metal compound particles and the matrix resin is clearly observed. As described above, when silicone fine particles are contained in the phosphor composition, a different situation may be observed.

The method of grafting the polymer onto the metal compound particle surface is not particularly limited, but it is desirable to graft the particle surface by condensation polymerization of a siloxane compound. Particularly preferred is a method in which an alkoxysilane compound is hydrolyzed with an acid catalyst in a solvent in the presence of metal compound particles, and then the hydrolyzate is subjected to a condensation reaction.

(Polysiloxane)
Polysiloxane is a condensate of alkoxysilane, which can be obtained by hydrolyzing an alkoxysilane compound in a solvent with an acid catalyst to form a silanol compound and then subjecting the silanol compound to a condensation reaction. As the alkoxysilane compound, one or more alkoxysilane compounds selected from the alkoxysilane compounds represented by the following general formulas (1) to (3) are preferable.

R ¹ Si (OR ⁴ ) ₃ (1)
R ¹ represents hydrogen, an alkyl group, an alkenyl group, an aryl group, or a substituted product thereof. From the viewpoint of crack resistance, it is preferable to use an alkoxysilane compound having a methyl group or a phenyl group as R ¹ . R ⁴ represents a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and may be the same or different. R ⁴ is more preferably a methyl group or an ethyl group.

R ² R ³ Si (OR ⁵ ) ₂ (2)
R ² and R ³ each represent hydrogen, an alkyl group, an alkenyl group, an aryl group, or a substituted product thereof. R ⁵ represents a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and may be the same or different. R5 is more preferably a methyl group or an ethyl group.

Si (OR ⁶ ) ₄ (3)
R ⁶ represents a methyl group or an ethyl group, and may be the same or different.

Specific examples of the alkoxysilane compounds represented by the general formulas (1) to (3) are shown below.

Examples of the trifunctional alkoxysilane compound represented by the general formula (1) include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, and ethyltrimethoxysilane. , Ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, 3-aminopropyltriethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, 3-glycidoxyship Pyrtrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N -Β- (aminoethyl) -γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α -Glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane Β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxy Sisilane, γ-glycidoxypropyl triisopropoxy silane, γ-glycidoxypropyl tributoxysilane, γ-glycidoxypropyltrimethoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxy Butyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxy Butyltrimethoxysilane, δ-glycidoxy Butyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltripropoxysilane, 2- (3 , 4-Epoxycyclohexyl) ethyltributoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) ) Propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, 4- (3,4-epoxycyclohexyl) butyltrimethoxysilane, 4- (3,4-epoxycyclohexyl) butyltriethoxysilane The Trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, perfluoropropylethyltrimethoxysilane, perfluoropropylethyltriethoxysilane, perfluoropentylethyltrimethoxy Silane, Perfluoropentylethyltriethoxysilane, Tridecafluorooctyltrimethoxysilane, Tridecafluorooctyltriethoxysilane, Tridecafluorooctyltripropoxysilane, Tridecafluorooctyltriisopropoxysilane, Heptadecafluorodecyltrimethoxysilane And heptadecafluorodecyltriethoxysilane. Of these, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane are preferable from the viewpoint of availability.

Examples of the bifunctional alkoxysilane compound represented by the general formula (2) include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, and methylvinyl. Diethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, γ- Methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxy Tilmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycyl Sidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, β-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethylmethoxyethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypro Ruethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylethyldimethoxysilane, tri Fluoropropylethyldiethoxysilane, trifluoropropylvinyldimethoxysilane, trifluoropropylvinyldiethoxysilane, heptadecafluorodecylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxy Examples thereof include silane and octadecylmethyldimethoxysilane. Of these, dimethyl dialkoxysilane is preferably used from the viewpoint of availability.

Examples of the tetrafunctional alkoxysilane compound represented by the general formula (3) include tetramethoxysilane and tetraethoxysilane.

These alkoxysilane compounds represented by the general formulas (1) to (3) may be used alone or in combination of two or more.

In the present invention, it is preferable to use a phenyl group-containing alkoxysilane compound and a methyl group-containing alkoxysilane compound. Thereby, when the matrix resin is a silicone resin, compatibility with the matrix resin is improved, and a phosphor composition and a phosphor sheet having excellent adhesion can be obtained.

In the present invention, it is desirable to use only a trifunctional alkoxysilane compound or a mixture of a trifunctional alkoxysilane compound and a bifunctional alkoxysilane compound. More specifically, the trifunctional alkoxysilane compound is preferably contained in an amount of 100 to 70 mol%, and the bifunctional alkoxysilane compound is preferably contained in an amount of 0 to 30 mol%. More preferably, it contains 10 to 20 mol% of a functional alkoxysilane compound. By carrying out like this, sclerosis | hardenability and hardness at the time of hardening the fluorescent substance composition containing a metal compound particle can be adjusted, and the handleability of the fluorescent substance sheet containing a metal compound particle can be improved.

Here, the handleability of the phosphor sheet indicates the ease of handling of the sheet when the sheet is attached to the LED chip. The handleability is correlated with the hardness of the phosphor sheet. If the sheet is too hard, the sheet may crack or break when the sheet is handled using tweezers or a thermocompression bonding tool. On the other hand, if the sheet is too soft, when the sheet is lifted with tweezers or a thermocompression bonding tool, the shape is deformed, or the sheet is stuck to the tweezers or thermocompression bonding tool, making it difficult to adhere to the LED chip.

The trifunctional alkoxysilane compound is preferably a trifunctional alkoxysilane compound represented by the general formula (1), and the bifunctional alkoxysilane compound is a bifunctional alkoxy compound represented by the general formula (2). It is preferable that it is a functional alkoxysilane compound.

In the hydrolysis reaction, an acid catalyst and water are added to the above alkoxysilane compound in a solvent in the presence of the metal compound particles over 1 to 180 minutes, and then reacted at room temperature to 110 ° C. for 1 to 180 minutes. preferable. By performing the hydrolysis reaction under such conditions, a rapid reaction can be suppressed. The reaction temperature is more preferably 40 to 105 ° C.

Further, after obtaining the silanol compound by the hydrolysis reaction, it is preferable to carry out the condensation reaction by heating the reaction solution as it is at 50 ° C. or higher and below the boiling point of the solvent for 1 to 100 hours. In order to increase the degree of polymerization of the polysiloxane, it is possible to reheat or add a base catalyst.

Various conditions in the hydrolysis can be obtained by considering the reaction scale, reaction vessel size, shape, etc., for example, by setting the acid concentration, reaction temperature, reaction time, etc., and obtaining physical properties suitable for the intended application. Can do.

Examples of the acid catalyst used in the hydrolysis reaction include acid catalysts such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acid or anhydrides thereof, and ion exchange resins. In particular, an acidic aqueous solution using formic acid, acetic acid or phosphoric acid is preferred.

A preferable content of these acid catalysts is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, preferably 100 parts by weight or more with respect to 100 parts by weight of the total alkoxysilane compound used in the hydrolysis reaction. Is 10 parts by weight or less, more preferably 5 parts by weight or less. Here, the total amount of the alkoxysilane compound means an amount including all of the alkoxysilane compound, its hydrolyzate and its condensate, and the same shall apply hereinafter. When the amount of the acid catalyst is 0.05 parts by weight or more, hydrolysis proceeds smoothly, and when the amount is 10 parts by weight or less, the hydrolysis reaction is easily controlled.

The solvent is appropriately selected in consideration of the dispersion stability of the metal compound particles. The solvent can be used not only as one type but also as a mixture of two or more types. Examples of the solvent include diacetone alcohol, propylene glycol monomethyl ether acetate, ethyl lactate, and γ-butyrolactone. Propylene glycol monomethyl ether acetate, γ-butyrolactone, and diacetone alcohol are particularly preferably used from the viewpoint of transmittance, ease of hydrolysis, and control of condensation reaction. Moreover, it is also preferable to adjust to a suitable density | concentration as a resin composition by adding a solvent after completion | finish of a hydrolysis reaction. Moreover, after hydrolysis according to the purpose, it is also possible to distill and remove a suitable amount of the produced alcohol under heating and / or reduced pressure, and then add a suitable solvent.

The amount of the solvent used in the hydrolysis reaction is preferably 50 parts by weight or more and more preferably 80 parts by weight or more with respect to 100 parts by weight of the total alkoxysilane compound. Moreover, 500 weight part or less is preferable and 200 weight part or less is more preferable. The production | generation of a gel can be suppressed by making the quantity of a solvent into 50 weight part or more. Moreover, a hydrolysis reaction advances rapidly by setting it as 500 parts weight or less.

Moreover, as the water used for the hydrolysis reaction, ion-exchanged water is preferable. The amount of water can be arbitrarily selected, but it is preferably used in the range of 1.0 to 4.0 mol with respect to 1 mol of the alkoxysilane compound.

<Phosphor>
The phosphor absorbs light emitted from the LED chip, performs wavelength conversion, and emits light having a wavelength different from that of the LED chip. Thereby, a part of the light emitted from the LED chip and a part of the light emitted from the phosphor can be mixed to produce a multicolor LED package containing white. Specifically, white light can be emitted by optically coupling a fluorescent material that emits a yellow light emission color with light from the LED chip to the blue LED chip. The phosphors as described above include various phosphors such as a phosphor that emits green light, a phosphor that emits blue light, a phosphor that emits yellow light, and a phosphor that emits red light.

The phosphor is not particularly limited as long as it can finally reproduce a predetermined color, and a known phosphor can be used. Examples of phosphors corresponding to blue LED chips include YAG phosphors, TAG phosphors, silicate phosphors, nitride phosphors, oxynitride phosphors, and the like.

<Matrix resin>
The matrix resin forms a continuous phase and is an epoxy resin, silicone resin (silicone rubber, silicone gel or other organopolysiloxane cured material as long as it is a material excellent in moldability, transparency, heat resistance, adhesiveness, etc. Products (including cross-linked products), urea resins, fluororesins, polycarbonate resins and the like can be used. By appropriately designing these resins, a resin useful for the phosphor composition of the present invention can be obtained.

It is also possible to add a dispersing agent or leveling agent for stabilizing the coating film as an additive, and an adhesion aid such as a silane coupling agent as a sheet surface modifier. It is also possible to add inorganic particles such as silica particles and silicone fine particles as a phosphor sedimentation inhibitor. In particular, a thermosetting or photocurable one is preferable. From the viewpoints of transparency and heat resistance, an epoxy resin, a silicone resin, or a mixture thereof can be suitably used.

The matrix resin is most preferably a silicone resin from the viewpoint of heat resistance. Among silicone resins, addition reaction curable silicone compositions are preferred. The addition reaction curable silicone composition is heated and cured at room temperature or 50 to 200 ° C., and is excellent in transparency, heat resistance, and adhesiveness. As the addition reaction curable silicone composition, a silicone having an alkenyl group bonded to a silicon atom, a silicone having a hydrogen atom bonded to a silicon atom, and a catalytic amount of a platinum-based catalyst can be used.

In the present invention, a silicone resin containing a silicon atom having a siloxane bond and having an aryl group directly bonded thereto is preferably used. In particular, a silicone resin having a siloxane bond and containing a silicon atom directly bonded to a naphthyl group is preferable because both a high refractive index and heat and light resistance can be achieved.

The silicone resin having a siloxane bond and containing a silicon atom directly bonded to an aryl group includes a silicone resin having a siloxane bond and containing a silicon atom directly bonded to a phenyl group, a siloxane bond, and a methyl resin. And a silicone resin containing a silicon atom in which a group and a phenyl group are directly connected.

Silicone resins having a siloxane bond and containing a silicon atom directly bonded to a naphthyl group include a silicone resin having a siloxane bond and a silicon atom directly bonded to a methyl group and a naphthyl group, and having a siloxane bond. And a silicone resin containing a silicon atom in which a methyl group, a phenyl group, and a naphthyl group are directly connected.

In addition, in a silicone resin containing a silicon atom in which a methyl group and a phenyl group are directly connected, a case in which a methyl group and a phenyl group are directly connected to one silicon atom, and a case where a silicon atom and a phenyl group in which a methyl group is directly connected Both cases where each has a directly-connected silicon atom are included. The same applies to a silicone resin containing a silicon atom in which a methyl group, a phenyl group and a naphthyl group are directly connected.

The silicone resin will be described in more detail. An addition reaction curable silicone composition containing a silicone having an alkenyl group bonded to a silicon atom, a silicone having a hydrogen atom bonded to a silicon atom, and a platinum-based catalyst as a hydrosilylation reaction catalyst is preferable. For example, sealing materials “OE6630” and “OE6636” manufactured by Toray Dow Corning Co., Ltd., “SCR-1012” and “SCR1016” manufactured by Shin-Etsu Chemical Co., Ltd. can be used. In particular, the matrix resin of the phosphor composition of the present invention is particularly preferably a crosslinked product obtained by hydrosilylation reaction of a crosslinkable silicone composition containing the compositions (A) to (D). This crosslinked product can be preferably used as a matrix resin for a phosphor sheet that does not require an adhesive because the storage elastic modulus decreases at 60 ° C. to 250 ° C. and a high adhesive force is obtained by heating. Hereinafter, this cross-linked product is referred to as a heat sealing resin.
(A) Average unit formula:
(R ¹ ₂ SiO _2/2 ) _a (R ¹ SiO _3/2 ) _b (R ² O _1/2 ) _c
(Wherein R ¹ is a phenyl group, an alkyl or cycloalkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms, provided that 65 to 75 mol% of R ¹ is phenyl. 10 to 20 mol% of R ¹ is an alkenyl group, R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and a, b, and c are 0.5 ≦ a ≦ 0. (6, 0.4 ≦ b ≦ 0.5, 0 ≦ c ≦ 0.1, and a + b = 1)
An organopolysiloxane represented by
(B) General formula:
R ³ ₃ SiO (R ³ ₂ SiO) _m SiR ³ ₃
(Wherein R ³ is a phenyl group, an alkyl or cycloalkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms, provided that 40 to 70 mol% of R ³ is phenyl. And at least one of R ³ is an alkenyl group, and m is an integer of 5 to 50.) {5 to 15 parts by weight relative to 100 parts by weight of component (A)}
(C) General formula:
(HR ⁴ ₂ SiO) ₂ SiR ⁴ ₂
(In the formula, R ⁴ is a phenyl group, or an alkyl group or cycloalkyl group having 1 to 6 carbon atoms, provided that 30 to 70 mol% of R ⁴ is phenyl.)
{Amount such that the molar ratio of silicon-bonded hydrogen atoms in this component to the total of alkenyl groups in component (A) and component (B) is 0.5 to 2}, and ( D) Catalyst for hydrosilylation reaction {Amount sufficient to promote hydrosilylation reaction between alkenyl group in component (A), component (B) and silicon atom-bonded hydrogen atom in component (C)}.

In the general formula of component (A), the values of a, b, and c are sufficient to obtain sufficient hardness at room temperature of the resulting crosslinked product, and softening at high temperature. In the general formula of the component (B), if the content of the phenyl group is less than the lower limit of the above range, the resulting crosslinked product is insufficiently softened at a high temperature. The resulting crosslinked product loses its transparency, and its mechanical strength also decreases. In the formula, at least one R ³ is an alkenyl group. This is because if the alkenyl group is not present, this component is not taken into the crosslinking reaction, and this component may bleed out from the resulting crosslinked product. In the formula, m is an integer in the range of 5 to 50, and this is a range in which handling workability is maintained while maintaining the mechanical strength of the resulting crosslinked product.

The content of the component (B) is within a range of 5 to 15 parts by weight with respect to 100 parts by weight of the component (A), and is a range for obtaining sufficient softening at a high temperature of the resulting crosslinked product. .

In the general formula of the component (C), R ⁴ is a phenyl group, or an alkyl group or cycloalkyl group having 1 to 6 carbon atoms. Examples of the alkyl group for R ⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a heptyl group. Examples of the cycloalkyl group for R ⁴ include a cyclopentyl group and a cycloheptyl group. Of R ⁴ , the phenyl group content is in the range of 30 to 70 mol%. This is a range in which the obtained crosslinked product can be sufficiently softened at a high temperature and can maintain transparency and mechanical strength.

The content of component (C) is such that the molar ratio of silicon-bonded hydrogen atoms in this component to the total of alkenyl groups in component (A) and component (B) is in the range of 0.5 to 2. This is a range in which sufficient hardness at room temperature of the resulting crosslinked product can be obtained.

The component (D) is a hydrosilylation catalyst for promoting the hydrosilylation reaction between the alkenyl group in the components (A) and (B) and the silicon atom-bonded hydrogen atom in the component (C). Examples of the component (D) include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts, and platinum-based catalysts are preferred because they can significantly accelerate the curing of the silicone composition. Examples of the platinum-based catalyst include platinum fine powder, chloroplatinic acid, alcohol solution of chloroplatinic acid, platinum-alkenylsiloxane complex, platinum-olefin complex, and platinum-carbonyl complex, particularly platinum-alkenylsiloxane complex. It is preferable. Examples of the alkenylsiloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, Examples thereof include alkenyl siloxanes in which part of the methyl groups of these alkenyl siloxanes are substituted with ethyl groups, phenyl groups, and the like, and alkenyl siloxanes in which the vinyl groups of these alkenyl siloxanes are substituted with allyl groups, hexenyl groups, and the like. In particular, 1,3-divinyl-1,1,3,3-toteramethyldisiloxane is preferred because the stability of the platinum-alkenylsiloxane complex is good. Further, since the stability of the platinum-alkenylsiloxane complex can be improved, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 1,3-diallyl-1,1 are added to this complex. , 3,3-tetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane, 1,3-divinyl-1,1,3,3-tetraphenyldisiloxane, It is preferable to add an alkenyl siloxane such as 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane or an organosiloxane oligomer such as a dimethylsiloxane oligomer. It is preferable.

The content of the component (D) is an amount sufficient to promote the hydrosilylation reaction between the alkenyl group in the components (A) and (B) and the silicon-bonded hydrogen atom in the component (C). Although not particularly limited, it is preferable that the amount of metal atoms in the present component is within a range of 0.01 to 500 ppm by mass unit with respect to the silicone composition, and more preferably 0.01 to 100 ppm. The amount is preferably in the range of 0.01 to 50 ppm, and particularly preferably in the range of 0.01 to 50 ppm. This is a range in which the obtained silicone composition is sufficiently crosslinked and does not cause problems such as coloring.

The silicone composition is composed of at least the above components (A) to (D), and other optional components include ethynylhexanol, 2-methyl-3-butyn-2-ol, and 3,5-dimethyl-1-hexyne. Alkyne alcohols such as 3-ol and 2-phenyl-3-butyn-2-ol; enyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-in 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane; Further, a reaction inhibitor such as benzotriazole may be contained. The content of the reaction inhibitor is not limited, but is preferably in the range of 1 to 5,000 ppm with respect to the weight of the silicone composition. By adjusting the content of the reaction inhibitor, the storage elastic modulus of the resulting cross-linked product can be adjusted.

<Silicon fine particles>
The phosphor composition of the present invention may contain silicone fine particles. By containing the silicone fine particles, it is possible to obtain a phosphor sheet having not only adhesiveness and workability but also good film thickness uniformity. In particular, by using silicone fine particles having an average particle size of 0.1 μm or more and 2.0 μm or less, it is possible to obtain a phosphor sheet that is excellent in dischargeability and excellent in film thickness uniformity when a slit die coater is used. it can.

Further, when silicone fine particles are present in the composition, the grafted metal compound particles cover the silicone fine particles. This further improves the compatibility between the matrix resin and the metal compound particles, so that the interface between them is less likely to occur. Therefore, since the adhesiveness with the light emitting surface of the LED chip is further improved, a further luminance improvement effect can be obtained. In addition, when the phosphor sheet is used, the storage elastic modulus (G ′) at 100 ° C. can be lowered and the adhesion to the LED chip can be improved.

Note that “the grafted metal compound particles cover the silicone fine particles” as used herein means a state in which the grafted metal compound particles uniformly cover the surfaces of the silicone fine particles. The state can be known by observing a cured product of the phosphor composition or a cross section of the phosphor sheet with SEM or TEM.

Examples of the state in which the grafted metal compound particles are coated with the silicone fine particles are shown in FIGS. 5 and 6, and examples of the uncoated state are shown in FIGS. 5 and 6 are photographs obtained by cutting a cross section of a phosphor sheet of Example 19 described later and observing with a scanning electron microscope (SEM), and FIGS. 7 and 8 are Comparative Examples 12 and 13 described later, respectively. It is the photograph which cut | disconnected the cross section of this phosphor sheet and observed with SEM.

In the state in which the grafted metal compound particles are coated with the silicone fine particles, as shown in FIGS. 5 and 6, the silicone fine particles 103 are uniformly dispersed in the matrix resin 101, and the surface of the silicone fine particles is grafted. It is observed that the converted metal compound particles 104 are covered. When the grafted metal compound particles do not cover the silicone fine particles, as shown in FIGS. 7 and 8, the phosphor 105 is present in the matrix resin 101, and the silicone fine particles 103, the metal compound particles It is observed that the 102s are aggregated to form an aggregate.

As shown in FIG. 5 and FIG. 6, the grafted metal compound particles are in a state in which the silicone fine particles are coated. The grafted metal compound particles and the silicone fine particles are weak in hydrogen bonds, van der Waals forces and the like. This is thought to be due to the fact that the connection is a pseudo connection.

The silicone fine particles are preferably fine particles made of silicone resin and / or silicone rubber. In particular, silicone fine particles obtained by a method of hydrolyzing organosilane such as organotrialkoxysilane, organodialkoxysilane, organotriacetoxysilane, organodiacetoxysilane, organotrioxime silane, organodioxime silane, and then condensing them. preferable.

Examples of the organotrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-proxysilane, methyltri-i-proxysilane, methyltri-n-butoxysilane, methyltri-i-butoxysilane, methyltri-s-butoxy Silane, methyltri-t-butoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, i-propyltrimethoxysilane, n-butyltributoxysilane, i-butyltributoxysilane, s-butyltrimethoxysilane, t -Butyltributoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane and the like are exemplified.

Organodialkoxysilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2- Aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminoisobutylmethyldimethoxysilane, N-ethylaminoisobutylmethyldiethoxysilane, (phenylaminomethyl) methyldimethoxysilane, vinylmethyl Examples include diethoxysilane.

Examples of organotriacetoxysilane include methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, and the like.

Examples of organodiacetoxysilane include dimethyldiacetoxysilane, methylethyldiacetoxysilane, vinylmethyldiacetoxysilane, and vinylethyldiacetoxysilane.

Examples of the organotrioxime silane include methyl trismethyl ethyl ketoxime silane, vinyl trismethyl ethyl ketoxime silane, and examples of the organodioxime silane include methyl ethyl bismethyl ethyl ketoxime silane.

Specifically, such silicone fine particles are reported in the method reported in JP-A-63-77940, the method reported in JP-A-62-248081, and reported in JP-A-2003-342370. For example, the method reported in JP-A-4-88022. In addition, organosilane such as organotrialkoxysilane, organodialkoxysilane, organotriacetoxysilane, organodiacetoxysilane, organotrioxime silane, organodioxime silane and / or a partial hydrolyzate thereof are added to an alkaline aqueous solution, Hydrolyzing and condensing to obtain silicone fine particles, or adding organosilane and / or a partial hydrolyzate thereof to water or an acidic solution to obtain a hydrolyzed partial condensate of the organosilane and / or the partial hydrolyzate thereof. After that, a method of obtaining an alkali fine particle by adding an alkali and proceeding a condensation reaction, an organosilane and / or a hydrolyzate thereof as an upper layer, an alkali or a mixed solution of an alkali and an organic solvent as a lower layer, the interface at these interfaces Organosilane and / or A hydrolyzate thereof by hydrolysis and polycondensation are also known a method of obtaining particles, In any of these methods, it is possible to obtain the silicone fine particles used in the present invention.

Among these, the reaction as reported in Japanese Patent Application Laid-Open No. 2003-342370 in producing spherical organopolysilsesquioxane fine particles by hydrolyzing and condensing organosilane and / or a partial hydrolyzate thereof. It is preferable to use silicone fine particles obtained by a method of adding a polymer dispersant in the solution.

In addition, in the production of silicone fine particles, organosilane and / or its partial hydrolyzate is hydrolyzed and condensed, and in the presence of a polymer dispersant and a salt that act as a protective colloid in a solvent in an acidic aqueous solution, Silicone fine particles produced by adding an organosilane and / or a hydrolyzate thereof to obtain a hydrolyzate and then adding an alkali to advance the condensation reaction can also be used.

The polymer dispersant is a water-soluble polymer, and any synthetic polymer or natural polymer can be used as long as it acts as a protective colloid in a solvent. Specifically, polyvinyl alcohol, polyvinyl pyrrolidone and the like can be used. It can be illustrated. As a method for adding the polymer dispersant, a method of adding in advance to the reaction initial solution, a method of adding organotrialkoxysilane and / or a partial hydrolyzate thereof simultaneously, an organotrialkoxysilane and / or a partial hydrolyzate thereof, The method of adding after hydrolyzing partial condensation can be illustrated, and any of these methods can be selected. Here, the addition amount of the polymer dispersant is preferably in the range of 5 × 10 ⁻⁷ to 10 ⁻² parts by weight with respect to 1 part by weight of the reaction solution, and in this range, aggregation of the silicone fine particles hardly occurs. .

The organic substituents contained in the silicone fine particles are preferably a methyl group and a phenyl group, and the refractive index of the silicone fine particles can be adjusted by the content of these substituents. For example, when the matrix resin is a silicone resin, in order not to reduce the brightness of the LED package, the difference in refractive index between the refractive index d1 of the silicone fine particles and the refractive index d2 due to components other than the silicone fine particles and the phosphor is reduced. Is preferred. The difference in refractive index between the refractive index d1 of the silicone fine particles and the refractive index d2 due to components other than the silicone fine particles and the phosphor is preferably less than 0.10, and more preferably 0.03 or less. By controlling the refractive index within such a range, reflection / scattering at the interface between the silicone fine particles and the silicone resin is reduced, high transparency and light transmittance are obtained, and the luminance of the LED package is not lowered. .

For the refractive index measurement, Abbe refractometer, Pulfrich refractometer, immersion type refractometer, immersion method, minimum declination method, etc. are used as the total reflection method, but Abbe refractometer is used to measure the refractive index of silicone resin. The immersion method is useful for measuring the refractive index of refractometers and silicone fine particles.

Further, as a means for controlling the refractive index difference, it can be adjusted by changing the amount ratio of the raw materials constituting the silicone fine particles. That is, for example, by adjusting the mixing ratio of methyltrialkoxysilane and phenyltrialkoxysilane, which are raw materials, and increasing the composition ratio of methyl groups, it is possible to achieve a refractive index close to 1.4. On the contrary, a relatively high refractive index can be achieved by increasing the constituent ratio of the phenyl group.

In the present invention, the average particle diameter of the silicone fine particles is represented by a median diameter (D50). The lower limit of the average particle diameter is preferably 0.1 μm or more, and more preferably 0.5 μm or more. The upper limit is preferably 2.0 μm or less, and more preferably 1.0 μm or less. Moreover, it is preferable to use monodispersed true spherical particles. In the present invention, the average particle diameter, that is, the median diameter (D50) and the particle size distribution of the silicone fine particles can be measured by SEM observation. A particle size distribution is obtained by performing image processing on a measurement image obtained by SEM, and in the particle size distribution obtained therefrom, the particle diameter of 50% of the accumulated portion from the small particle diameter side is obtained as the median diameter D50. If this method is used, the volume-based particle size obtained from the particle size distribution of the silicone fine particles is obtained by observing the cross-sectional SEM of the phosphor sheet and then calculating the average particle size of the silicone fine particles themselves. In the distribution, it is also possible to obtain a particle diameter of 50% accumulated from the small particle diameter side as the median diameter D50. In this case, the average particle size of the silicone fine particles determined from the cross-sectional SEM image of the phosphor sheet is theoretically 78.5% compared to the true average particle size, and is actually about 70% to 85%.

The content of the silicone fine particles is preferably 1 part by weight or more as a lower limit with respect to 100 parts by weight of the resin, and more preferably 10 parts by weight or more. Further, the upper limit is preferably 100 parts by weight or less, and more preferably 80 parts by weight or less. By containing 1 part by weight or more of silicone fine particles, a particularly good phosphor dispersion stabilizing effect can be obtained. On the other hand, by containing 80 parts by weight or less, the viscosity of the phosphor composition is not excessively increased.

<Solvent>
The phosphor composition of the present invention may contain a solvent. A solvent will not be specifically limited if the viscosity of resin of a fluid state can be adjusted. For example, toluene, methyl ethyl ketone, methyl isobutyl ketone, hexane, acetone, terpineol, texanol, methyl cellosolve, butyl carbitol, butyl carbitol acetate, propylene glycol monomethyl ether acetate and the like can be mentioned.

<Other ingredients>
The phosphor composition of the present invention contains a dispersing agent and a leveling agent for stabilizing the coating film, an adhesion assistant such as a silane coupling agent as a sheet surface modifier when the phosphor sheet is used. May be.

Moreover, in order to lower the storage elastic modulus (G ′) at 100 ° C., a silanol group-containing methylphenyl silicone resin may be contained as a heating adhesive. The structure of the silanol group-containing methylphenyl silicone resin is particularly preferably the following general formula (E).
(E) the general ^{_{formula: (R 5 SiO 3) d}} (PhSiO 3) e (R 5 OHSiO 2) f (PhOHSiO 2) g (R 6 SiO 2) h
In the formula, R ⁵ and R ⁶ are each an alkyl group or cycloalkyl group having 1 to 6 carbon atoms, Ph is a phenyl group, and d, e, f, g, and h are 20 ≦ d ≦ 40, 20 ≦ e ≦ 40, 5 ≦ f ≦ 15, 5 ≦ g ≦ 15, 20 ≦ h ≦ 40, and d + e + f + g + h = 100.

<Phosphor sheet laminate>
In the present invention, the phosphor sheet laminate refers to a laminate containing a substrate and a phosphor sheet formed by applying a phosphor composition onto the substrate.

(Base material)
As a base material, a well-known metal, a film, glass, a ceramic, paper, etc. can be used without a restriction | limiting in particular. Specifically, metal plates and foils such as aluminum (including aluminum alloys), zinc, copper, iron, cellulose acetate, polyethylene terephthalate (PET), polyethylene, polyester, polyamide, polyimide, polyphenylene sulfide, polystyrene, polypropylene, polycarbonate , Polyvinyl acetal, aramid, silicone, polyolefin, thermoplastic fluororesin, plastic film such as tetrafluoroethylene and ethylene copolymer (ETFE), α-polyolefin resin, polycaprolactone resin, acrylic resin, silicone resin and these A plastic film made of a copolymer resin of ethylene and ethylene, paper laminated with the plastic, or paper coated with the plastic, front Paper metal is laminated or deposited, the metals and plastic film laminated or deposited. Moreover, when the base material is a metal plate, the surface may be subjected to plating treatment or ceramic treatment such as chromium or nickel.

Among these, glass and resin films are preferably used because of the ease of producing the phosphor sheet and the ease of individualizing the phosphor sheet. In particular, the base material is preferably a flexible film because of the adhesion when the phosphor sheet is attached to the LED chip. Further, a film having a high strength is preferred so that there is no fear of breakage when handling a film-like substrate. Resin films are preferred in terms of their required characteristics and economy, and among these, plastic films selected from the group consisting of PET, polyphenylene sulfide, and polypropylene are preferred in terms of economy and handleability. Moreover, when drying a fluorescent substance sheet, or when attaching a fluorescent substance sheet to a LED chip, when a high temperature of 200 degreeC or more is required, a polyimide film is preferable at a heat resistant surface. The surface of the base material may be subjected to a mold release treatment in advance for ease of peeling of the sheet.

The thickness of the substrate is not particularly limited, but the lower limit is preferably 25 μm or more, and more preferably 38 μm or more. Moreover, as an upper limit, 5000 micrometers or less are preferable and 3000 micrometers or less are more preferable.

(Phosphor sheet)
In the present invention, the phosphor sheet refers to a sheet containing a phosphor inside. A phosphor sheet which is one feature of the present invention is a phosphor sheet containing a phosphor, a matrix resin, and metal compound particles, wherein the metal compound particles have a refractive index of 1.7 or more, and The average particle diameter is 1 to 50 nm, the metal compound particles are grafted, and the average refractive index N1 of the metal compound particles and the matrix resin is related to the refractive index N2 of the phosphor as follows: And the viscoelastic behavior of the sheet satisfies the following relationships (ii), (iii) and (iv).
<Refractive index relationship>
(I) 0.20 ≧ | N1-N2 |
<Viscoelastic behavior>
(Ii) The storage elastic modulus G ′ is 1.0 × 10 ⁴ Pa ≦ G ′ ≦ 1.0 × 10 ⁶ Pa at a temperature of 25 ° C. and tan δ <1
(Iii) Storage modulus G ′ is 1.0 × 10 ² Pa ≦ G ′ <1.0 × 10 ⁴ Pa at a temperature of 100 ° C. and tan δ ≧ 1
(Iv) The storage elastic modulus G ′ is 1.0 × 10 ⁴ Pa ≦ G ′ ≦ 1.0 × 10 ⁶ Pa at a temperature of 200 ° C. and tan δ <1.

Details of the phosphor, matrix resin, metal compound particles and grafting thereof, and other preferable components contained in the phosphor sheet are the same as those in the phosphor composition described above. Further, the explanation regarding the average refractive indexes N1, N2 and the relational expression (i) showing the relationship therebetween is also common to the above-described phosphor composition.

Next, the viscoelastic behavior of the phosphor sheet of the present invention will be described. The phosphor sheet of the present invention preferably has high elasticity near room temperature from the viewpoints of storage properties, transportability, and processability. On the other hand, from the viewpoint of deforming to follow the shape of the LED chip and in close contact with the light extraction surface of the LED chip, the elasticity becomes low under certain temperature conditions, and the flexibility, adhesion, and fluidity are expressed. It is preferable. In particular, the phosphor sheet of the present invention preferably exhibits fluidity when heated at 60 ° C. or higher. It is important that the phosphor sheet of the present invention has high adhesion to the light extraction surface of the LED chip, and this greatly improves the light extraction from the LED chip. Therefore, it is necessary for the viscoelastic behavior of the phosphor sheet to satisfy the above (ii) to (iv).

Here, the storage elastic modulus (G ′) of the phosphor sheet is a storage elastic modulus (G ′) when the dynamic viscoelasticity measurement (temperature dependence) of the phosphor sheet is performed by a rheometer. Dynamic viscoelasticity means that when shear strain is applied to a material at a sinusoidal frequency, the shear stress that appears when a steady state is reached is divided into a component (elastic component) whose strain and phase match, and the strain and phase are This is a technique for analyzing the dynamic mechanical properties of a material by decomposing it into components (viscous components) delayed by 90 °.

Dynamic viscoelasticity measurement (temperature dependency) can be measured using a general viscosity / viscoelasticity measuring device. In this invention, it is set as the value at the time of measuring on the following conditions.

Measuring device: Viscosity and viscoelasticity measuring device HAAKE MARSIII
(Thermo Fisher SCIENTIFIC made)
Measurement conditions: OSC temperature-dependent measurement Geometry: Parallel disk type (20mm)
Measurement time: 1980 seconds Angular frequency: 1 Hz
Angular velocity: 6.2832 rad / sec Temperature range: 25 to 200 ° C (with low temperature control function)
Temperature increase rate: 0.08333 ° C./sec Sample shape: Circular (diameter 18 mm).

Here, the storage elastic modulus (G ′) is obtained by dividing the stress component whose phase coincides with the shear strain by the shear strain. Since the storage elastic modulus (G ′) represents the elasticity of the material against dynamic strain at each temperature, it is closely related to the hardness of the phosphor sheet, that is, the processability.

On the other hand, the loss elastic modulus (G ″) is obtained by dividing the shear strain and the stress component whose phase is delayed by 90 ° by the shear strain. The loss elastic modulus represents the viscosity of the material. That is, it is closely related to adhesion.

Further, the loss tangent (tan δ) obtained by dividing the loss elastic modulus (G ″) by the storage elastic modulus (G ′) is an index indicating the state in which the material is placed. On the other hand, elasticity is dominant and it is in a solid state, whereas if tan δ is 1 or more, viscosity is dominant and it indicates a liquid state.

The phosphor sheet in the present invention is sufficiently elastic at room temperature (25 ° C.) because 1.0 × 10 ⁴ Pa ≦ G ′ ≦ 1.0 × 10 ⁶ Pa at 25 ° C. and tan δ <1. It is. For this reason, the sheet is cut without deformation of the surroundings even with a high shear stress such as a cutting process with a blade, and processability with high dimensional accuracy is obtained. The storage elastic modulus at 25 ° C. of the phosphor sheet is more preferably 9.0 × 10 ⁵ Pa or less from the viewpoint of crack prevention during handling and workability.

Tan δ at room temperature is more preferably 0.7 or less from the viewpoint of lowering the attaching temperature. Moreover, there is no restriction | limiting in particular as a minimum, However, It is preferable that it is 0.1 or more, It is more preferable that it is 0.2 or more, It is further more preferable that it is 0.25 or more.

Further, since the phosphor sheet satisfies 1.0 × 10 ² Pa ≦ G ′ <1.0 × 10 ⁴ Pa at 100 ° C. and tan δ ≧ 1, the sheet is sufficiently viscous at 100 ° C. High fluidity. Therefore, if the phosphor sheet having this physical property is heated to 100 ° C. or higher and attached to the LED chip, the phosphor sheet quickly flows and deforms according to the shape of the light emitting surface of the LED chip, and is high. Adhesion can be obtained. Thereby, the light extraction property from the LED chip is improved, and the luminance is improved. The storage elastic modulus at 100 ° C. of the phosphor sheet is more preferably 9.0 × 10 ³ Pa or less from the viewpoint of lowering the attaching temperature.

Tan δ at 100 ° C. is more preferably 1.6 or more from the viewpoint of adhesion. The upper limit is not particularly limited, but is preferably 4.0 or less, more preferably 3.6 or less, and even more preferably 3.3 or less.

Furthermore, when the phosphor sheet satisfies 1.0 × 10 ⁴ Pa ≦ G ′ ≦ 1.0 × 10 ⁶ Pa and tan δ <1 at 200 ° C., the LED chip can finally operate stably. Can be made. If the phosphor sheet is heated at 200 ° C. or higher, complete curing of the sheet is completed and the entire resin is integrated, so that it is not affected by thermal factors such as heat when the LED chip is lit. The storage elastic modulus (G ′) at 200 ° C. of the phosphor sheet is more preferably 9.0 × 10 ⁵ Pa or less from the viewpoint of preventing cracks.

Tan δ at 200 ° C. is more preferably tan δ ≦ 0.08 from the viewpoint of thermal stability. The lower limit is not particularly limited, but is preferably 0.01 or more, more preferably 0.02 or more, and further preferably 0.03 or more.

If the above storage elastic modulus (G ′) is obtained as the phosphor sheet, the resin contained therein may be in an uncured state. In consideration of the handleability and storage stability of the sheet, it is preferable that the resin contained is not completely cured as a whole but is cured to some extent. As an example, it is preferable that the curing has progressed to such an extent that the storage elastic modulus (G ′) does not change for a long period of time of 1 month or longer after storage at room temperature.

<Method for producing phosphor sheet>
The phosphor sheet of the present invention can be obtained from the phosphor composition described above. Details of the manufacturing method will be described later.

The thickness of the phosphor sheet of the present invention is not particularly limited, but is preferably 10 to 1000 μm. If it is smaller than 10 μm, it is difficult to form a uniform sheet because of unevenness caused by the phosphor particles. If it exceeds 1000 μm, cracks tend to occur and sheet molding is difficult. More preferably, it is 30 to 100 μm.

On the other hand, from the viewpoint of increasing the heat resistance of the sheet, the thickness of the sheet is preferably 200 μm or less, more preferably 100 μm or less, and even more preferably 50 μm or less.

The film thickness of the sheet in the present invention is the film thickness (average film thickness) measured based on JIS K7130 (1999) Plastic-Film and Sheet-Thickness Measuring Method A Method for Measuring Thickness by Mechanical Scanning. That means.

Heat resistance refers to resistance to heat generated in the LED package. The heat resistance can be evaluated by comparing the luminance when the LED package emits light at room temperature and when the LED package emits light at a high temperature, and measuring how much the luminance at the high temperature decreases.

The LED chip is in an environment where a large amount of heat is generated in a small space, and particularly in the case of a high power LED, heat generation is significant. Due to such heat generation, the temperature of the phosphor rises and the brightness of the LED package decreases. Therefore, it is important how efficiently the generated heat is radiated. In this invention, the sheet | seat excellent in heat resistance can be obtained by making a sheet | seat film thickness into the said range. Moreover, if the sheet thickness varies, the amount of phosphor varies for each LED package, and as a result, the emission spectrum varies. Therefore, the variation in sheet thickness is preferably within ± 5%, more preferably within ± 3%. The film thickness variation referred to here is a thickness measurement method based on the thickness measurement method A by mechanical scanning in JIS K7130 (1999) plastic-film and sheet-thickness measurement method, and is shown below. Calculated by the formula.

More specifically, it is obtained by measuring the film thickness using a micrometer such as a commercially available contact-type thickness meter using the measurement conditions of the method A of measuring the thickness by mechanical scanning. The difference between the maximum value or the minimum value of the film thickness and the average film thickness is calculated, and this value is divided by the average film thickness, and the value expressed in 100 minutes is the film thickness variation B (%).
Film thickness variation B (%) = (maximum film thickness deviation value * −average film thickness) / average film thickness × 100
* For the maximum film thickness deviation value, the one with the larger difference from the average film thickness is selected from the maximum value or the minimum value.

<Method for producing phosphor composition>
Below, an example of the manufacturing method of the fluorescent substance composition of this invention is demonstrated. A predetermined amount of the aforementioned metal compound particles, matrix resin, phosphor, silicone fine particles, solvent and the like are mixed. After mixing the above components to a predetermined composition, the phosphor composition is uniformly mixed and dispersed with an agitator / kneader such as a homogenizer, a self-revolving stirrer, a 3-roller, a ball mill, a planetary ball mill, or a bead mill. Things are obtained. Defoaming is preferably carried out under vacuum or reduced pressure conditions after mixing or dispersing. Further, a specific component may be mixed in advance or a process such as aging may be performed. It is also possible to remove the solvent with an evaporator to obtain a desired solid content concentration.

<Method for producing phosphor sheet laminate>
Below, an example of the manufacturing method of the fluorescent substance composition of this invention is demonstrated. The phosphor composition produced by the method described above is applied onto a substrate and dried to produce a phosphor sheet laminate. Application is reverse roll coater, blade coater, slit die coater, direct gravure coater, offset gravure coater, kiss coater, natural roll coater, air knife coater, roll blade coater, varibar roll blade coater, two stream coater, rod coater, wire A bar coater, an applicator, a dip coater, a curtain coater, a spin coater, a knife coater or the like can be used. In order to obtain the film thickness uniformity of the phosphor sheet, it is preferably applied by a slit die coater.

The phosphor sheet can be dried using a general heating device such as a hot air dryer or an infrared dryer. For heating the phosphor sheet, a general heating device such as a hot air dryer or an infrared dryer is used. In this case, the heating conditions are usually 40 to 250 ° C. for 1 minute to 5 hours, preferably 60 ° C. to 200 ° C. for 2 minutes to 4 hours. It is also possible to perform heat curing stepwise such as step cure.

The concentration of the metal compound particles in the phosphor sheet of the present invention can be changed depending on the viscosity of the phosphor composition and the drying conditions (speed) after coating. When the viscosity of the phosphor composition is high, the metal compound particles hardly flow, and it is difficult to obtain a constant concentration region and a concentration change region. Therefore, it is preferable to prepare a phosphor composition containing a solvent. The viscosity of the paste is preferably 3000 to 100,000 mPa · s. Further, even if the drying temperature is increased and the drying speed is increased, the metal compound particles are less likely to flow, so that it is difficult to obtain a constant concentration region and a concentration changing region. Preferred drying conditions are as described above.

It is also possible to change the substrate as necessary after preparing the phosphor sheet laminate. In particular, when a surface with a high concentration of high refractive index nanoparticles is attached to the light emitting surface of the LED chip, it is preferable to change the base material to adjust the attachment surface. In this case, examples of a simple method include a method of performing replacement using a hot plate, a method of using a vacuum laminator and a dry film laminator, and the like, but are not limited thereto. The same method can also be used when the surface with the higher concentration of the high refractive index nanoparticles is made to face the light emitting surface of the LED chip.

<Application example of phosphor sheet>
The phosphor sheet laminate of the present invention is preferably a fluorescent material in which a phosphor sheet is laminated on the surface of an LED chip by being attached to a light emitting surface of an LED chip having a general structure such as lateral, vertical, and Philip chip. An LED chip with a body sheet can be formed, and can be suitably used for a vertical or flip chip type LED chip having a large light emitting area. The light emitting surface is a surface from which light from the LED chip is extracted.

Here, the light emitting surface from the LED chip may be a single plane or not a single plane. In the case of a single plane, there are mainly those having only the upper light emitting surface. Specifically, a vertical type LED chip, an LED chip whose side surface is covered with a reflective layer and light is extracted only from the upper surface are exemplified. On the other hand, when it is not a single plane, an LED chip having an upper light emitting surface and a side light emitting surface and an LED chip having a curved light emitting surface can be mentioned.

It is preferable that the light emitting surface is not a single plane because the light emitted from the side can be used and brightened. In particular, a flip chip type LED chip having an upper light emitting surface and a side light emitting surface is preferable because the light emitting area can be increased and the chip manufacturing process is easy. Further, the light emitting surface may be processed into a texture or the like based on an optical design in order to improve the light emission efficiency.

The phosphor sheet laminate of the present invention can be pasted using an adhesive such as a transparent resin without being directly pasted on the LED chip. On the other hand, it is preferable to directly cover the LED chip with the phosphor sheet because the light from the LED chip can be directly incident on the phosphor sheet as the wavelength conversion layer without being lost due to reflection or the like. Thereby, uniform white light with little color variation and high efficiency can be obtained. The wavelength conversion layer here refers to a layer that absorbs light emitted from the LED chip, converts the wavelength, and emits light having a wavelength different from that of the LED chip.

The LED chip with a phosphor sheet obtained by these methods is packaged with metal wiring and sealing, and then incorporated into a module to illuminate various LEDs including various types of lighting, liquid crystal backlights, and headlamps. It can be used suitably for an apparatus.

FIG. 9 shows a suitable example of an LED chip with a phosphor sheet. (A) is one in which a phosphor sheet is attached to the upper surface of the LED chip. (B) is one in which the phosphor sheet 2 is attached not only to the upper surface but also to the side surface of the LED chip 1. The wavelength conversion is also possible for light emission from the side surface, which is preferable. (C) uses a flip chip type LED, and the phosphor sheet 2 covers the upper and side surfaces, which are light emitting surfaces. (D) attaches the surface where the density | concentration of a high refractive index nanoparticle is large to the light emission surface of a LED chip.

10A to 10B show suitable examples of LED packages. (A) is the one in which the phosphor composition 4 is injected into the mounting substrate 7 with the reflector 5 on which the LED chip 1 is installed and then sealed with the transparent sealing material 6. (B) is one in which the phosphor sheet 2 is pasted on the LED chip 1 installed on the mounting substrate 7 with the reflector 5, and then sealed with the transparent sealing material 6. (C) is the one in which the phosphor sheet 2 is attached not only to the upper surface but also to the side surface of the LED chip 1 and is preferable because the wavelength can be converted even for light emission from the side surface. Further, a lens made of a transparent sealing material 6 is also attached.

(D) is the same as (b) except that the reflector 5 is not used and the lens molded body of the transparent sealing material 6 is used for sealing. (E) is the same as (c) except that the reflector 5 is not used.

(F) is the same as (c) except that a flip-chip type LED is used and the upper surface and side surfaces, which are light emitting surfaces, are covered with the phosphor sheet 2. When the side surface of the LED chip 1 is covered with the phosphor sheet 2, the phosphor sheet 2 may extend to the upper surface of the mounting substrate 7 as shown in FIG. (G) is the same as (e) except that the reflector 5 is not used and the lens is molded by the lens molding of the transparent sealing material 6. (H) is obtained by pasting the LED chip 1 and the phosphor sheet 2 with the transparent adhesive 9, and otherwise the same as (b). (I) is the same as (h) except that the phosphor sheet 2 with the base material 10 prepared in advance is used and the base material 10 is used without being peeled from the phosphor sheet 2. As the material of the substrate 10, glass is preferable.

The LED package to which the present invention can be applied is not limited to these. For example, the transparent sealing material 6 in (b) may have a shape as shown in (c), and the phosphor sheet 2 may be attached not only to the upper surface but also to the side surface of the LED chip 1. . As described above, the structures of the parts exemplified in (a) to (i) can be appropriately combined. Moreover, you may substitute or combine with well-known parts other than these.

Here, the transparent sealing material is an epoxy resin, silicone resin (cured organopolysiloxane (crosslinked product) such as silicone rubber, silicone gel, etc.) as long as it is a material excellent in moldability, transparency, heat resistance, adhesiveness, etc. And other known resins such as urea resins, fluororesins, and polycarbonate resins can be used. Moreover, the transparent sealing material mentioned above can be used for a transparent adhesive agent.

<Application example to LED package manufacturing method>
A method for producing an LED package using the phosphor composition of the present invention will be described. Although the suitable example of a manufacturing method of the LED chip which uses the fluorescent substance composition is shown in FIG. 12, it is not limited to this method. As a manufacturing method using the phosphor composition of the present invention, particularly preferably, (A) a step of injecting the phosphor composition into a package frame, and (B) a package is sealed with a sealing material after that step. It is a manufacturing method of the LED package including the process to perform.

First, (a) a mounting substrate 7 with a reflector 5 is prepared as a package frame 18. (B) The LED chip 1 is mounted on the mounting substrate 7 and installed.

Next, (c) a desired amount of the phosphor composition of the present invention is injected into the package frame 18 on which the LED chip 1 is installed. Examples of the injection method at this time include injection molding, compression molding, cast molding, transfer molding, coating, potting (dispensing), printing, transfer, and the like, but are not limited thereto. Particularly preferably, potting (dispensing) can be used.

After the injection, the phosphor composition can be placed on the LED chip in a form suitable for the package by heating and curing the phosphor composition. Heat curing can be performed using a general heating device such as a hot air dryer or an infrared dryer. The heat curing conditions are usually 40 to 250 ° C. for 1 minute to 5 hours, preferably 60 ° C. to 200 ° C. for 2 minutes to 4 hours. In this case, it is possible to perform heat curing stepwise such as step cure.

Thereafter, (d) the transparent sealing material 6 is injected and heat-cured to seal the LED chip 1. The injection method and heating conditions at this time conform to the conditions of the phosphor composition described above. The LED package 19 is manufactured by the above process. You may install an overcoat layer, a lens, etc. by transparent resin as needed.

Next, an LED package manufacturing method using the phosphor sheet laminate of the present invention will be described. As will be described later, a typical method for producing an LED package using the phosphor sheet laminate of the present invention is as follows: (1) A method of cutting a phosphor sheet into individual pieces and attaching them to individual LED chips, (2) There is a method in which dicing of the wafer and cutting of the phosphor sheet are collectively performed by pasting the wafer on which the LED chip before dicing has been fabricated, but it is not limited thereto. Particularly preferably (A) an alignment step in which one section of the phosphor sheet opposes the light emitting surface of one LED chip, and (B) pressurizing while heating with a thermocompression bonding tool. It is an LED package manufacturing method including at least a bonding step of bonding a partition and a light emitting surface of the one LED chip. Further, the step (A) is an alignment step in which the surface of the phosphor sheet having the higher concentration of inorganic particles among the upper and lower surfaces of one section of the phosphor sheet is opposed to the light emitting surface of the one LED chip. It is preferable that it is a manufacturing method of an LED package.

The phosphor sheet laminate of the present invention can be adhered using an adhesive such as a transparent resin without being directly adhered to the LED chip, but a phosphor using a heat-sealing resin as a matrix resin. The use of a sheet is preferable because it can be easily attached to the LED chip without an adhesive.

When the phosphor sheet is affixed to the LED chip, the phosphor sheet is affixed by applying pressure while heating at a desired temperature. The heating temperature is preferably 60 ° C. or higher and 250 ° C. or lower, and more preferably 60 ° C. or higher and 160 ° C. or lower. By setting the temperature to 60 ° C. or higher, the resin design for increasing the difference in elastic modulus between the room temperature and the attaching temperature becomes easy. Moreover, since the thermal expansion and thermal shrinkage of the base material and the phosphor sheet can be reduced by setting the temperature to 250 ° C. or lower, the accuracy of pasting can be increased. In particular, when the phosphor sheet is pre-perforated and aligned with a predetermined portion on the LED chip, the position accuracy of pasting is important. In order to increase the accuracy of pasting, it is more preferable to paste at 160 ° C. or lower.

As a method for attaching the phosphor sheet to the LED chip surface, any existing apparatus can be used as long as it can be bonded at a desired temperature, and a thermocompression bonding tool such as a mounter or a flip chip bonder can be used. Further, when affixing to the wafer level LED chips at once, it can be affixed using a vacuum laminator or a thermocompression bonding tool having a heating portion of about 100 to 200 mm square. In either case, the phosphor sheet is pressure-bonded to the LED chip at a desired temperature and thermally fused, and then allowed to cool to room temperature, and the substrate is peeled off. By providing the relationship between the temperature and the elastic modulus as in the present invention, the phosphor sheet after being allowed to cool to room temperature after heat fusion can be easily peeled off from the substrate while firmly adhering to the LED chip. It becomes possible.

The method for cutting the phosphor sheet will be described. The phosphor sheet is pre-cut into individual pieces before being attached to the LED chip, and then attached to individual LED chips, and the phosphor sheet is attached to the wafer level LED chip and then simultaneously with wafer dicing. Then, there is a method of cutting the phosphor sheet. In the case of cutting in advance before sticking, the uniformly formed phosphor sheet is processed into a predetermined shape by laser processing or cutting with a blade and divided. Since processing with a laser gives high energy, it is very difficult to avoid scorching of the resin and deterioration of the phosphor, and cutting with a blade is desirable. As a cutting method with a blade, there are a method of pushing and cutting a simple blade and a method of cutting with a rotary blade, both of which can be suitably used. As an apparatus for cutting with a rotary blade, an apparatus used for cutting (dicing) a semiconductor substrate (wafer) called a dicer into individual chips can be suitably used. If the dicer is used, the width of the dividing line can be precisely controlled by the thickness of the rotary blade and the condition setting, so that higher processing accuracy can be obtained than when cutting with a simple cutting tool.

When the phosphor sheet in a state of being laminated with the base material is cut, the whole base material may be singulated, or the phosphor sheet may be singulated and the base material may not be cut. Alternatively, the substrate may be a so-called half cut in which a cut line that does not penetrate is entered. The phosphor sheet thus separated is thermally fused on the light emitting surface of each individual LED chip. FIG. 13 shows an example of individualization, LED chip application, and dicing steps when the phosphor sheet is divided into individual substrates. The process of FIG. 13 includes a step of cutting the phosphor sheet into individual pieces, and a step of pressing the phosphor sheet cut into the individual pieces at a desired temperature and attaching them to the LED chip. FIG. 13A shows a state where the phosphor sheet 2 laminated with the base material 20 is fixed to the temporarily fixing sheet 21. In the process shown in FIG. 13, since both the phosphor sheet 2 and the base material 20 are separated, they are fixed to the temporarily fixing sheet 21 so as to be easy to handle. Next, as shown in (b), the phosphor sheet 2 and the substrate 20 are cut into individual pieces. Subsequently, as shown in (c), the separated phosphor sheet 2 and the base material 20 are aligned on the LED chip 1 mounted on the mounting substrate 7 and heated as shown in (d). Crimping is performed at a desired temperature using the crimping tool 22. At this time, it is preferable to perform the pressure bonding step under vacuum or reduced pressure so that air is not caught between the phosphor sheet 2 and the LED chip 1. After crimping, the substrate is allowed to cool to room temperature, and the substrate 20 is peeled off as shown in FIG. Here, when the base material 20 is glass or the like, the base material may be used as it is as shown in FIG.

In addition, when the phosphor sheets are separated into individual pieces with the base material being continuous, they may be heat-sealed to the wafer level LED chips before dicing as they are. FIG. 14 shows an example of individualization, LED chip attachment, and dicing steps when the phosphor sheet is separated into individual pieces while the base material is continuous. The process of FIG. 14 also includes a step of cutting the phosphor sheet into individual pieces and a step of heating the phosphor sheet cut into the individual pieces and attaching them to the LED chip. In the example of the process shown in FIG. 14, first, when the phosphor sheet 2 is separated into pieces in the process shown in (b), the base material 20 is not separated. In FIG. 14B, the substrate 20 is not cut at all, but may be partially cut as long as the substrate 20 is continuous. Next, as shown in (c), the phosphor sheet 2 that has been separated into pieces is opposed to the wafer 23 on which the LED chips before dicing are formed, and alignment is performed. In the step shown in (d), the wafer 23 on the surface of which the phosphor sheet 2 and the LED chip before dicing are formed is crimped at a desired temperature using the thermocompression bonding tool 22. At this time, it is preferable that the pressure bonding process is performed under vacuum or under reduced pressure so that air is not caught between the wafer 23 having the phosphor sheet 2 and the LED chip 1 formed on the surface. After the pressure bonding, the substrate is allowed to cool to room temperature. After the substrate 20 is peeled off as shown in (e), the wafer is diced into individual pieces, and the LED chips with phosphor sheets separated into individual pieces as shown in (f) Get 24.

When the phosphor sheet is thermally fused to the wafer level LED chips before dicing, the phosphor sheet can be cut together with the dicing of the LED chip wafer after pasting. FIG. 15 shows an example of a process in the case where the phosphor sheet and the wafer are diced together after being attached. The process of FIG. 15 includes a process of pressing and bonding a phosphor sheet to a plurality of LED chips at a desired temperature and a process of dicing the phosphor sheet and the LED chip together. In the process of FIG. 15, the phosphor sheet 2 is not cut in advance, and the phosphor sheet 2 side is made to face the wafer 23 on which the LED chips before dicing are formed as shown in FIG. Align. Next, as shown in (b), the wafer 23 on which the phosphor sheet 2 and the LED chip before dicing are formed on the surface is crimped by a thermocompression bonding tool 22 at a desired temperature. In this case, it is preferable to perform the pressure bonding step under vacuum or under reduced pressure so that air is not caught between the phosphor sheet 2 and the wafer 23 on which the LED chips are formed. After the pressure bonding, it is allowed to cool to room temperature, and after peeling the substrate 20 as shown in (c), the wafer is diced, and at the same time, the phosphor sheet 2 is cut into individual pieces, as shown in (d). An LED chip 24 with a phosphor sheet is obtained. In addition, as shown in (b), after the wafer 23 having the phosphor sheet 2 and the LED chip before dicing formed on the surface thereof is crimped at a desired temperature with a thermocompression bonding tool as shown in (b), 20 does not peel off, and the substrate is cut into individual pieces together with the phosphor sheet, and the LED chip 24 with the phosphor sheet with the substrate is obtained as shown in (f). In this case, when the base material 20 is glass or the like, it may be used as it is without peeling. In the case of a plastic film other than glass, an LED chip with a phosphor sheet with a base material separated into pieces is used as a substrate. After mounting, the substrate may be peeled off.

In any of the steps shown in FIGS. 13 to 15, when the phosphor sheet is attached to the LED chip having the electrode on the upper surface, the phosphor sheet is not attached to the electrode portion in order to remove the phosphor sheet. It is desirable to make a hole in the part in advance. Although known methods such as laser processing and die punching can be suitably used for drilling, laser processing causes burning of the resin and deterioration of the phosphor, so punching with a die is more desirable. When punching is performed, punching cannot be performed after the phosphor sheet is attached to the LED chip. Therefore, it is essential to perform punching before attaching the phosphor sheet. In the punching process using a mold, a hole having an arbitrary shape or size can be formed depending on the electrode shape of the LED chip to be attached. Any size and shape of the hole can be formed by designing the mold, but the electrode joint portion on the LED chip inside and outside the 1 mm square is preferably 500 μm or less in order not to reduce the area of the light emitting surface. The hole is formed with a size of 500 μm or less in accordance with its size. In addition, an electrode for performing wire bonding or the like needs to have a certain size and is at least about 50 μm. Therefore, the hole is about 50 μm in accordance with the size. If the size of the hole is too larger than the electrode, the light emitting surface is exposed, light leakage occurs, and the color characteristics of the LED package deteriorate. On the other hand, if it is too small than the electrode, the wire touches at the time of wire bonding, resulting in poor bonding. Therefore, in the drilling process, it is necessary to process small holes of 50 μm or more and 500 μm or less with high accuracy within ± 10%. In order to improve punching accuracy, the storage elastic modulus of the phosphor sheet at 25 ° C. It is very important that G ′ is 1.0 × 10 ⁴ Pa ≦ G ′ ≦ 1.0 × 10 ⁶ Pa and tan δ <1.

When a phosphor sheet that has been cut and perforated is aligned and adhered to a predetermined portion of the LED chip, an affixing device having an optical alignment (alignment) mechanism is required. At this time, it is difficult to align the phosphor sheet and the LED chip in terms of work, and in practice, the alignment is often performed in a state where the phosphor sheet and the LED chip are lightly contacted. At this time, if the phosphor sheet has adhesiveness, it is very difficult to move it in contact with the LED chip. If the phosphor sheet laminate of the present invention is aligned at room temperature, it is not sticky, so that it is easy to align the phosphor sheet and the LED chip with light contact.

The mass production method of the LED chip with the phosphor sheet and the LED package using the phosphor sheet laminate of the present invention will be described. First, a method for manufacturing an LED chip with a phosphor sheet will be described. As a method of attaching the phosphor sheet to the LED chip, as shown in FIG. 16, a method of attaching one by one using the phosphor sheet laminate 26 separated for each LED chip, and as shown in FIG. In addition, there is a method in which the phosphor sheet 2 is collectively coated on a plurality of LED chips, and then cut and individualized. Any method may be used.

The phosphor sheet is attached by pressing in a state where the base material softens and flows. In particular, when a heat-sealable phosphor sheet is used, the sticking temperature is preferably 60 ° C. or higher, and more preferably 80 ° C. or higher, from the viewpoint of enhancing adhesiveness. Further, the heat-fusible resin used for the phosphor sheet has a property that the viscosity is temporarily lowered by heating, and is further cured by heating. Therefore, the temperature of the attaching step is preferably 150 ° C. or lower from the viewpoint of maintaining adhesiveness, and more preferably 120 ° C. or lower from the viewpoint of maintaining the shape of the phosphor sheet at a certain level or higher. . Moreover, in order to prevent the remaining of an air pocket, it is preferable to stick on under reduced pressure of 0.01 MPa or less.

Examples of the manufacturing apparatus for performing such affixing include vacuum affixing machines such as a vacuum diaphragm laminator, a vacuum roll laminator, a vacuum hydraulic press, a vacuum servo press, a vacuum electric press, and a TOM molding machine. Among these, a vacuum diaphragm muraminator is preferable because a large number of treatments can be performed at one time, and pressure can be applied without deviation from directly above.

Next, two methods will be exemplified for the manufacturing method of the LED package using the phosphor sheet. The LED package manufacturing method is not limited to these examples.

The first manufacturing example is shown in FIG. (A) The LED chip 1 is temporarily fixed on the base 30 via the double-sided adhesive tape 29. (B) The phosphor sheet laminate 26 is laminated so that the phosphor sheet 2 is in contact with the LED chip 1. (C) After the laminate of (b) is placed in the lower chamber 32 of the vacuum diaphragm muraminator 35, the upper chamber 31 and the lower chamber 32 are depressurized while being heated. After heating under reduced pressure until the base material 25 flows, the diaphragm 33 is expanded by sucking the air into the upper chamber 31 through the air inlet 34, pressing the phosphor sheet 2 through the base material 25, and the LED chip 1. Paste to follow the light emitting surface. (D) After returning the upper and lower chambers to atmospheric pressure, the laminate is taken out from the vacuum diaphragm muraminator 33, and the substrate 25 is peeled off after being allowed to cool. Subsequently, the LED chip space 36 is cut with a dicing cutter or the like to produce an individual LED chip 37 with a phosphor sheet. (E) The LED chip 37 with the phosphor sheet is bonded to the package electrode 28 on the mounting substrate 27 via the gold bumps 8. (F) The LED package 38 is manufactured by the above process. If necessary, install an overcoat layer or lens with a transparent resin.

FIG. 19 shows a second manufacturing example. (A) The LED chip 1 is bonded to the package electrode 28 on the mounting substrate 27 via the gold bumps 8. (B) The phosphor sheet laminate 26 is laminated so that the phosphor sheet 2 is in contact with the LED chip 1. (C) After the laminate of (b) is placed in the lower chamber 32 of the vacuum diaphragm muraminator 33, the phosphor sheet 2 is attached to the light emitting surface of the LED chip 1 by the same method as in the manufacturing example of FIG. (D) After returning the upper and lower chambers to atmospheric pressure, the laminate is taken out from the vacuum diaphragm muraminator 33, and the substrate 25 is peeled off after being allowed to cool. Subsequently, the LED package 36 is cut into individual pieces. (E) The LED package 39 is manufactured through the above steps. If necessary, install an overcoat layer or lens with a transparent resin.

Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these.

<Metal compound particles>
Nanoparticle 1: Titanium oxide “Optlake TR-527” (manufactured by Catalyst Kasei Kogyo Co., Ltd. Composition: average particle diameter 15 nm, refractive index 2.50, titanium oxide particles 20% by weight)
Nanoparticle 2: Titanium oxide “Optlake TR-520” (manufactured by Catalyst Kasei Kogyo Co., Ltd. Composition: average particle diameter 15 nm, refractive index 2.50, titanium oxide particles 30% by weight)
Nanoparticle 3: Titanium oxide “Optlake TR-521” (manufactured by Catalytic Chemical Industry Co., Ltd. Composition: average particle diameter 15 nm, refractive index 2.50, titanium oxide particles 30% by weight)
Nanoparticle 4: Tin oxide particle “SN1” (average particle diameter 19 nm, refractive index 2.38)
Nanoparticle 5: Aluminum oxide particle “SA1” (average particle diameter 34 nm, refractive index 1.76)
Nanoparticle 6: Cerium oxide particle “CS1” (average particle diameter 34 nm, refractive index 2.20)
Nanoparticle 7: Zirconia oxide “ZS1” (average particle diameter 15 nm, refractive index 2.40, zirconia oxide particle 20% by weight)
Nanoparticle 8: Magnesium oxide particle “MS1” (average particle diameter 44 nm, refractive index 1.76)
Nanoparticle 9: Zinc oxide particle “AS1” (average particle diameter 94 nm, refractive index 1.95)
Nanoparticle 10: Titanium oxide particles “TS1” (average particle diameter 30 nm, refractive index 2.50, titanium oxide particles 20% by weight)
Nanoparticle 11: Titanium oxide particles “TS2” (average particle diameter 50 nm, refractive index 2.50, titanium oxide particles 20% by weight)
Nanoparticle 12: Titanium oxide particles “TS3” (average particle diameter 70 nm, refractive index 2.50, titanium oxide particles 20% by weight)
Nanoparticle 13: Titanium oxide particles “TS4” (average particle diameter 80 nm, refractive index 2.50, titanium oxide particles 20% by weight)
Nanoparticle 14: Zirconia oxide “ZS2” (average particle diameter 20 nm, refractive index 2.40, zirconia oxide particles 20% by weight)
Nanoparticle 15: Zirconia oxide particles “ZS3” (average particle size 30 nm, refractive index 2.40, zirconia oxide particles 20% by weight)
Nanoparticle 16: Zirconia oxide particles “ZS4” (average particle diameter 50 nm, refractive index 2.40, zirconia oxide particles 20% by weight)
Nanoparticle 17: Zirconia oxide particle “ZS5” (average particle size 70 nm, refractive index 2.40, zirconia oxide particle 20% by weight)
Nanoparticle 18: Zirconia oxide particles “ZS6” (average particle diameter 80 nm, refractive index 2.40, zirconia oxide particles 20% by weight)
Nanoparticle 19: Niobium oxide particles “NS1” (average particle diameter 15 nm, refractive index 2.30, niobium oxide particles 20% by weight).

(Grafting of metal compound particles)
<Grafting example 1>
16.6 g of methyltrimethoxysilane, 56.2 g of phenyltrimethoxysilane, “Optlake TR-527” having a number average particle diameter of 15 nm (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) Composition: 20% by weight of titanium oxide particles, methanol 80 wt%) 194 g and propylene glycol monomethyl ether acetate 126.9 g were put into a reaction vessel, and 21.9 g of water and 0.36 g of phosphoric acid were added to this solution while stirring so that the reaction temperature did not exceed 40 ° C. It was dripped. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 115 ° C. for 2 hours and then cooled to room temperature to obtain titanium oxide particles grafted with polysiloxane.

<Grafting example 2>
20.4 g of methyltrimethoxysilane, 69.4 g of phenyltrimethoxysilane, “OPTRAIK TR-520” having a number average particle diameter of 15 nm (trade name, manufactured by Catalyst Chemical Industry Co., Ltd., composition: 30% by weight of titanium oxide particles, γ 70.6 g of butyrolactone (70 wt%) and 44.1 g of γ-butyrolactone were placed in a reaction vessel, and 30.6 g of water and 0.48 g of phosphoric acid were added to this solution while stirring, and the reaction temperature did not exceed 40 ° C. Was dropped. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 130 ° C. for 2 hours and then cooled to room temperature to obtain titanium oxide particles grafted with polysiloxane.

<Grafting example 3>
8.2 g of methyltrimethoxysilane, 55.5 g of phenyltrimethoxysilane, 7.2 g of dimethyldimethoxysilane, “OPTRAIK TR-521” having a number average particle diameter of 15 nm (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd., composition: oxidation 71.1 g of titanium particles (70 wt% of titanium particles, 70 wt% of diacetone alcohol) and 23.9 g of γ-butyrolactone were placed in a reaction vessel, and 34.5 g of water and 1.0 g of phosphoric acid were added to this solution while stirring. The solution was added dropwise so that the temperature did not exceed 40 ° C. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 130 ° C. for 2 hours and then cooled to room temperature to obtain titanium oxide particles grafted with polysiloxane.

<Grafting example 4>
3-Glycidoxypropyltrimethoxysilane 28.78 g, phenyltrimethoxysilane 56.4 g, number-average particle diameter 15 nm “Optlake TR-527” (trade name, manufactured by Catalyst Chemical Industries, Ltd. Composition: titanium oxide particles 194 g of 20 wt% methanol 80 wt%) and 253.3 g of propylene glycol monomethyl ether acetate were placed in a reaction vessel. To this solution, 21.9 g of water and 0.36 g of phosphoric acid were stirred while the reaction temperature was 40 ° C. It was dripped so that it might not exceed. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 115 ° C. for 2 hours and then cooled to room temperature to obtain titanium oxide particles grafted with polysiloxane.

<Grafting example 5>
18.1 g of vinyltrimethoxysilane, 67.2 g of 3-glycidoxypropyltrimethoxysilane, “OPTRAIK TR-527” having a number average particle diameter of 15 nm (trade name, manufactured by Catalyst Chemical Industries, Ltd. Composition: titanium oxide particles 194 g of 20 wt% methanol 80 wt%) and 253.6 g of propylene glycol monomethyl ether acetate were placed in a reaction vessel. To this solution, 21.9 g of water and 0.36 g of phosphoric acid were stirred while the reaction temperature was 40 ° C. It was dripped so that it might not exceed. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 115 ° C. for 2 hours and then cooled to room temperature to obtain titanium oxide particles grafted with polysiloxane.

<Grafting example 6>
18.05 g of vinyltrimethoxysilane, 56.36 g of phenyltrimethoxysilane, “Optlake TR-527” having a number average particle diameter of 15 nm (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) Composition: 20% by weight of titanium oxide particles, methanol 805.7%) 205.7 g and propylene glycol monomethyl ether acetate 131.3 g were put in a reaction vessel. To this solution, 21.9 g of water and 0.36 g of phosphoric acid were stirred and the reaction temperature did not exceed 40 ° C. Was dropped. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 115 ° C. for 2 hours and then cooled to room temperature to obtain titanium oxide particles grafted with polysiloxane.

<Grafting example 7>
16.6 g of methyltrimethoxysilane, 56.2 g of phenyltrimethoxysilane, “Optlake TR-527” having a number average particle diameter of 15 nm (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) Composition: 20% by weight of titanium oxide particles, methanol 80 wt%) 194 g and propylene glycol monomethyl ether acetate 126.9 g were put into a reaction vessel, and 21.9 g of water and 0.36 g of phosphoric acid were added to this solution while stirring so that the reaction temperature did not exceed 40 ° C. It was dripped. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 1 hour, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 115 ° C. for 1 hour, and then cooled to room temperature to obtain titanium oxide particles grafted with polysiloxane.

<Grafting example 8>
16.6 g of methyltrimethoxysilane, 56.2 g of phenyltrimethoxysilane, “Optlake TR-527” having a number average particle diameter of 15 nm (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) Composition: 20% by weight of titanium oxide particles, methanol 80 wt%) 194 g and propylene glycol monomethyl ether acetate 126.9 g were put into a reaction vessel, and 21.9 g of water and 0.36 g of phosphoric acid were added to this solution while stirring so that the reaction temperature did not exceed 40 ° C. It was dripped. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 1 hour, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 115 ° C. for 15 minutes and then cooled to room temperature to obtain titanium oxide particles grafted with polysiloxane.

<Grafting example 9>
In a glove box from which oxygen and moisture have been removed, powdered titanium oxide particles “TKP-102” (trade name, manufactured by Teika Co., Ltd.) are spread thinly on a glass petri dish, and the petri dish is made into a plasma etcher (Meiwa Forsys, SEDE). ) And plasma treatment was performed for 15 minutes. The plasma-treated particles were transferred to a capped test tube, and a 9.6

mM

2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) styrene solution prepared in advance was placed in the test tube and sealed with a cap. Thereafter, it was inserted into an aluminum block heater heated to 125 ° C., and radical polymerization was performed. After 12 hours, the test tube was taken out of the heater and the glove box, and oxygen bubbled chloroform was added to completely stop the polymerization. After the titanium oxide particles and the solvent were separated by centrifugation, the titanium oxide particles were taken out. The titanium oxide particles were washed with acetone to obtain grafted titanium oxide particles.

<Grafting Example 10>
5.59 g of methyltrimethoxysilane, 19.0 g of phenyltrimethoxysilane, “OPTRAIK TR-527” (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) having a number average particle diameter of 15 nm, composition: 20% by weight of titanium oxide particles, methanol 804.6%) (264.6 g) and propylene glycol monomethyl ether acetate (103.3 g) were placed in a reaction vessel. To this solution, 7.39 g of water and 0.12 g of phosphoric acid were stirred and the reaction temperature did not exceed 40 ° C. Was dropped. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 115 ° C. for 2 hours and then cooled to room temperature to obtain titanium oxide particles grafted with polysiloxane.

<Grafting Example 11>
4.88 g of dimethyldimethoxysilane, 72.46 g of phenyltrimethoxysilane, “OPTRAIK TR-527” (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) having a number average particle diameter of 15 nm, composition: 20% by weight of titanium oxide particles, methanol 80 (% By weight) 213.4 g and 139.6 g of propylene glycol monomethyl ether acetate were put into a reaction vessel, and 21.9 g of water and 0.37 g of phosphoric acid were added to this solution while stirring so that the reaction temperature did not exceed 40 ° C. It was dripped. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 115 ° C. for 2 hours and then cooled to room temperature to obtain titanium oxide particles grafted with polysiloxane.

<Grafting example 12>
9.76 g of dimethyldimethoxysilane, 64.41 g of phenyltrimethoxysilane, “Optlake TR-527” having a number average particle diameter of 15 nm (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) Composition: 20% by weight of titanium oxide particles, methanol 80 (% By weight) 199.65 g and 130.6 g of propylene glycol monomethyl ether acetate were put in a reaction vessel, and 21.9 g of water and 0.37 g of phosphoric acid were added to this solution while stirring so that the reaction temperature did not exceed 40 ° C. It was dripped in. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 115 ° C. for 2 hours and then cooled to room temperature to obtain titanium oxide particles grafted with polysiloxane.

<Grafting example 13>
14.64 g of dimethyldimethoxysilane, 56.36 g of phenyltrimethoxysilane, “OPTRAIK TR-527” having a number average particle diameter of 15 nm (trade name, manufactured by Catalyst Chemical Industry Co., Ltd.) Composition: 20% by weight of titanium oxide particles, methanol 80 (Weight%) 185.94 g and 121.7 g of propylene glycol monomethyl ether acetate are put in a reaction vessel, and 21.9 g of water and 0.36 g of phosphoric acid are added to this solution while stirring so that the reaction temperature does not exceed 40 ° C. It was dripped. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 115 ° C. for 2 hours and then cooled to room temperature to obtain titanium oxide particles grafted with polysiloxane.

<Grafting Example 14>
19.52 g of dimethyldimethoxysilane, 48.31 g of phenyltrimethoxysilane, “OPTRAIK TR-527” (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) having a number average particle diameter of 15 nm, composition: 20% by weight of titanium oxide particles, 80 of methanol (Weight%) 172.22 g and propylene glycol monomethyl ether acetate 112.7 g were put into a reaction vessel, and 21.9 g of water and 0.35 g of phosphoric acid were added to this solution while stirring so that the reaction temperature did not exceed 40 ° C. It was dripped. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 115 ° C. for 2 hours and then cooled to room temperature to obtain titanium oxide particles grafted with polysiloxane.

<Grafting Example 15>
24.40 g of dimethyldimethoxysilane, 40.25 g of phenyltrimethoxysilane, “Optlake TR-527” having a number average particle diameter of 15 nm (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) Composition: 20% by weight of titanium oxide particles, methanol 80 (Weight%) 158.50 g and 103.7 g of propylene glycol monomethyl ether acetate are put in a reaction vessel, and 21.9 g of water and 0.33 g of phosphoric acid are added to this solution while stirring so that the reaction temperature does not exceed 40 ° C. It was dripped in. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 115 ° C. for 2 hours and then cooled to room temperature to obtain titanium oxide particles grafted with polysiloxane.

<Grafting Example 16>
29.28 g of dimethyldimethoxysilane, 32.20 g of phenyltrimethoxysilane, “OPTRAIK TR-527” having a number average particle diameter of 15 nm (trade name, manufactured by Catalyst Chemical Industry Co., Ltd.) composition: 20% by weight of titanium oxide particles, methanol 80 (% By weight) 144.79 g and 94.73 g of propylene glycol monomethyl ether acetate were put in a reaction vessel, and 21.9 g of water and 0.31 g of phosphoric acid were added to this solution while stirring so that the reaction temperature did not exceed 40 ° C. It was dripped. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 115 ° C. for 2 hours and then cooled to room temperature to obtain titanium oxide particles grafted with polysiloxane.

<Grafting Example 17>
34.16 g of dimethyldimethoxysilane, 24.15 g of phenyltrimethoxysilane, “Optlake TR-527” having a number average particle diameter of 15 nm (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) Composition: 20% by weight of titanium oxide particles, methanol 80 (% By weight) 131.07 g and propylene glycol monomethyl ether acetate 85.75 g were put into a reaction vessel, and 21.9 g of water and 0.30 g of phosphoric acid were added to this solution while stirring so that the reaction temperature did not exceed 40 ° C. It was dripped in. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 115 ° C. for 2 hours and then cooled to room temperature to obtain titanium oxide particles grafted with polysiloxane.

<Grafting Example 18>
39.04 g of dimethyldimethoxysilane, 16.10 g of phenyltrimethoxysilane, “Optlake TR-527” having a number average particle diameter of 15 nm (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) Composition: 20% by weight of titanium oxide particles, methanol 80 (% By weight) 117.35 g and propylene glycol monomethyl ether acetate 76.78 g were put in a reaction vessel, and 21.9 g of water and 0.28 g of phosphoric acid were added to this solution while stirring so that the reaction temperature did not exceed 40 ° C. It was dripped. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 115 ° C. for 2 hours and then cooled to room temperature to obtain titanium oxide particles grafted with polysiloxane.

<Grafting example 19>
43.92 g of dimethyldimethoxysilane, 8.05 g of phenyltrimethoxysilane, “Optlake TR-527” having a number average particle diameter of 15 nm (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) Composition: 20% by weight of titanium oxide particles, methanol 80 (% By weight) 103.64 g and 67.81 g of propylene glycol monomethyl ether acetate were put in a reaction vessel, and 21.9 g of water and 0.27 g of phosphoric acid were added to this solution while stirring so that the reaction temperature did not exceed 40 ° C. It was dripped in. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 115 ° C. for 2 hours and then cooled to room temperature to obtain titanium oxide particles grafted with polysiloxane.

<Grafting Example 20>
14.64 g of dimethyldimethoxysilane, 35.24 g of diphenyldimethoxysilane, “OPTRAIK TR-527” (trade name, manufactured by Catalyst Chemical Industry Co., Ltd.) having a number average particle diameter of 15 nm, composition: titanium oxide particles 20% by weight, methanol 80% by weight %) 94.59 g and 61.89 g of propylene glycol monomethyl ether acetate were put in a reaction vessel, and 21.9 g of water and 0.25 g of phosphoric acid were added to this solution while stirring so that the reaction temperature did not exceed 40 ° C. It was dripped. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 115 ° C. for 2 hours and then cooled to room temperature to obtain titanium oxide particles grafted with polysiloxane.
(Surface treatment of metal compound particles)
<Surface treatment example 1>
Put 24.5 g of methyltrimethoxysilane, 83.3 g of phenyltrimethoxysilane, and 124.0 g of γ-butyrolactone in a reaction vessel and stir while stirring with 38 g of water and 0.57 g of phosphoric acid so that the reaction temperature does not exceed 30 ° C. It was dripped in. After the dropwise addition, a distillation apparatus was attached to the flask, and the resulting solution was heated and stirred at a bath temperature of 105 ° C. for 2.5 hours, and reacted while distilling off methanol produced by hydrolysis. Thereafter, the solution was further heated and stirred at a bath temperature of 130 ° C. for 2 hours, and then cooled to room temperature to obtain a polymer solution. 10.0 g of the obtained polymer solution was taken, and 13.3 g of “OPTRAIK TR-527” (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd .: titanium oxide particles 20 wt%, methanol 80 wt%) and propylene Glycol monomethyl ether acetate was added and stirred to obtain a siloxane composition.

<Surface treatment example 2>
400 mL of “Optlake TR-527” (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd., composition: titanium oxide particles 20% by weight, methanol 80% by weight) was put in a reaction container, and phenyltrimethoxysilane 5.2 g (manufactured by Gelest) ) And heated at 60 ° C. for 2 hours, a white precipitate was formed. Next, when the supernatant was removed and 100 mL of acetone was added to the white precipitate, the affinity for the solvent was improved by introduction of the phenyl group, and the precipitate was almost dissolved. After removing a small amount of insoluble matter by filtration, the solvent was distilled off from the acetone solution and dried under reduced pressure at 80 ° C. for 10 hours to obtain titania particles surface-modified with phenyltrimethoxysilane.

<Solvent>
PGMEA: propylene glycol monomethyl ether acetate γBL: γ-butyrolactone DAA: diacetone alcohol PGME: propylene glycol monomethyl ether acetate: ethyl acetate <Substrate>
BX9: Release-treated polyethylene terephthalate (polyethylene terephthalate film) “Therapel” BX9 (manufactured by Toray Film Processing Co., Ltd., average film thickness 50 μm)
Glass: Glass (blue plate glass, plate thickness: 0.3 mm)
HP2: Release-treated polyethylene terephthalate (polyethylene terephthalate film) “Therapy HP2” (manufactured by Toray Film Processing Co., Ltd., average film thickness 50 μm)
PPS: Polyphenylene sulfide (polyphenylene sulfide film)
“Torelina 3000” (Toray Industries, Inc., average film thickness 50 μm)
PP: Polypropylene (polypropylene film)
“Trephan” (Toray Industries, Inc., average film thickness 50 μm)
PI: Polyimide (Polyimide film)
“Kapton 200H / V” (manufactured by Toray DuPont Co., Ltd., average film thickness 50 μm)
PO: Polyolefin (Polyolefin film)
"Opylan X-44B" (Mitsui Chemicals, Inc., manufactured by Tosero Co., Ltd., average film thickness 50μm)
AL: Aluminum (aluminum substrate plate thickness: 0.24 mm).

<Silicon fine particles>
Attach stirrer, thermometer, reflux tube and dropping funnel to 2L four-necked round bottom flask. Put 2L of 2.5% ammonia water containing 1ppm of polyether-modified siloxane "BYK333" as a surfactant into the flask. The temperature was raised in an oil bath while stirring at. When the internal temperature reached 50 ° C., 200 g of a mixture of methyltrimethoxysilane and phenyltrimethoxysilane (23/77 mol%) was dropped from the dropping funnel over 30 minutes. Stirring was continued for 60 minutes at the same temperature, then about 5 g of acetic acid (special grade reagent) was added, mixed with stirring, and then filtered. The product particles on the filter were added with 600 mL of water twice and 200 mL of methanol once, followed by filtration and washing. The cake on the filter was taken out, crushed, and freeze-dried over 10 hours to obtain 60 g of white powder. The obtained particles were monodisperse spherical fine particles as observed by SEM. As a result of measuring the refractive index of this fine particle by the immersion method, it was 1.54. As a result of observing the particles with a cross-sectional TEM, it was confirmed that the particles had a single structure.

<Phosphor>
Phosphor: “YAG81003” (YAG phosphor, median diameter (D ₅₀ ): 8.6 μm, refractive index: 1.8) manufactured by Nemoto Lumi Material Co., Ltd.

<Matrix resin>
Ingredients for compounding silicone resin Resin main component (MeViSiO _2/2 ) _0.25 (Ph ₂ SiO _2/2 ) _0.3 (PhSiO _3/2 ) _0.45 (HO _1/2 ) _0.03 (average composition, (A) Applicable)
Hardness modifier ViMe ₂ SiO (MePhSiO) _17.5 SiMe ₂ Vi (average composition, corresponding to component (B))
Crosslinking agent (HMe ₂ SiO) ₂ SiPh ₂ (corresponds to component (C).)
* However, Me: Methyl group, Vi: Vinyl group, Ph: Phenyl group Reaction inhibitor 1-Ethynylhexanol Platinum catalyst Platinum complex (1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution) Contains platinum Amount 5% by weight.

Silicone resins

1 and 7 to 19 used for preparing the phosphor composition were blended with the above silicone components to prepare a matrix resin. For the silicone resins 2 to 6, commercially available products (two-component mixed products) were used, and in some cases, the mixing ratio (A / B ratio) of the liquid A and the liquid B was changed to produce a matrix resin.

・ Silicone resin 1:
Resin main component 16.7 parts by weight, hardness adjusting agent 16.7 parts by weight, cross-linking agent 66.7 parts by weight,
0.025 weight part of reaction inhibitor, 0.03 weight part of platinum catalyst Silicone resin 2: “OE6630 (A liquid, B liquid)” (manufactured by Dow Corning Toray)
A / B ratio 1/4
Silicone resin 3: “OE6336 (liquid A, liquid B)” (manufactured by Dow Corning Toray)
A / B ratio 1/1
Silicone resin 4: “KER6075 (A liquid, B liquid)” (manufactured by Shin-Etsu Chemical)
A / B ratio 1/1
Silicone resin 5: “KER6075 (A liquid, B liquid)” (manufactured by Shin-Etsu Chemical)
A / B ratio 1 / 1.14
Silicone resin 6: “KER6075 (A liquid, B liquid)” (manufactured by Shin-Etsu Chemical)
A / B ratio 0.5 / 1
-Silicone resin 7:
Resin main component 16.7 parts by weight, hardness adjusting agent 20.0 parts by weight, cross-linking agent 66.7 parts by weight,
Reaction inhibitor 0.025 parts by weight, platinum catalyst 0.03 parts by weight Silicone resin 8:
Resin main component 18.2 parts by weight, hardness adjusting agent 18.2 parts by weight, cross-linking agent 63.6 parts by weight,
Reaction inhibitor 0.025 parts by weight, platinum catalyst 0.03 parts by weight Silicone resin 9:
15.4 parts by weight of a resin main component, 15.4 parts by weight of a hardness adjusting agent, 69.2 parts by weight of a crosslinking agent,
Reaction inhibitor 0.025 parts by weight, platinum catalyst 0.03 parts by weight Silicone resin 10:
25.0 parts by weight of resin main component, 20.0 parts by weight of hardness adjusting agent, 50.0 parts by weight of crosslinking agent,
Reaction inhibitor 0.025 parts by weight, platinum catalyst 0.03 parts by weight Silicone resin 11:
25.0 parts by weight of resin main component, 25.0 parts by weight of hardness adjusting agent, 50.0 parts by weight of crosslinking agent,
Reaction inhibitor 0.025 parts by weight, platinum catalyst 0.03 parts by weight Silicone resin 12:
Resin main component 41.7 parts by weight, hardness adjusting agent 9.1 parts by weight, cross-linking agent 41.7 parts by weight,
Reaction inhibitor 0.025 parts by weight, platinum catalyst 0.03 parts by weight Silicone resin 13:
33.3 parts by weight of resin main component, 43.3 parts by weight of hardness adjusting agent, 23.3 parts by weight of crosslinking agent,
Reaction inhibitor 0.025 parts by weight, platinum catalyst 0.03 parts by weight Silicone resin 14:
33.3 parts by weight of resin main component, 33.3 parts by weight of hardness adjusting agent, 33.3 parts by weight of crosslinking agent,
Reaction inhibitor 0.025 parts by weight, platinum catalyst 0.03 parts by weight Silicone resin 15:
Resin main component 41.7 parts by weight, hardness adjusting agent 18.2 parts by weight, cross-linking agent 41.7 parts by weight,
Reaction inhibitor 0.025 parts by weight, platinum catalyst 0.03 parts by weight Silicone resin 16:
Resin main component 16.7 parts by weight, hardness adjusting agent 4.3 parts by weight, cross-linking agent 70.7 parts by weight,
Reaction inhibitor 0.025 parts by weight, platinum catalyst 0.03 parts by weight Silicone resin 17:
23.3 parts by weight of a resin main component, 53.3 parts by weight of a hardness adjusting agent, 23.3 parts by weight of a crosslinking agent,
0.025 part by weight of reaction inhibitor, 0.03 part by weight of platinum catalyst Silicone resin 18:
33.3 parts by weight of a resin main component, 5.0 parts by weight of a hardness adjusting agent, 33.3 parts by weight of a crosslinking agent,
Reaction inhibitor 0.025 parts by weight, platinum catalyst 0.03 parts by weight Silicone resin 19:
18.9 parts by weight of a resin main component, 5.6 parts by weight of a hardness adjusting agent, 75.5 parts by weight of a crosslinking agent,
0.025 weight part of reaction inhibitor, 0.03 weight part of platinum catalyst.

<Refractive index measurement>
Using the refractive index / film thickness measuring device “Prism Coupler Model 2010 / M” (made by Metricon), the refractive index of the refractive index measurement sample was measured to measure the average refractive index N1 of the metal compound particles and the matrix resin. . The refractive index N2 of the phosphor was introduced into the following formula, and the refractive index difference was calculated | N1-N2 |.

<Preparation of refractive index measurement sample>
Metal compound particles were mixed in the matrix resin, and the dispersion was prepared by stirring and defoaming for 10 minutes at 1,000 rpm using a planetary stirring deaerator “Mazerustar KK-400” manufactured by Kurabo Industries. After 5 cc of the dispersion was dropped onto the film substrate, the sample was heated in an oven at 150 ° C. for 1 hour to prepare an average refractive index N1 measurement sample. If necessary, the solvent may be removed by an evaporator after preparing the liquid.

<Transparency test>
A sample for transparency evaluation was prepared by dispersing metal compound particles in a matrix resin, and the transparency was evaluated by observing the sample with an optical microscope.
A: There is no defect due to aggregation of nanoparticles, and a transparent film is formed.
B: Although there is a defect due to aggregation of nanoparticles, a relatively transparent film is formed.
C: White turbidity due to aggregation of nanoparticles (light is not transmitted).

<Preparation of sample for transparency evaluation>
Metal compound particles were mixed in the matrix resin, and the dispersion was prepared by stirring and defoaming for 10 minutes at 1,000 rpm using a planetary stirring deaerator “Mazerustar KK-400” manufactured by Kurabo Industries. A coating film was prepared on a glass substrate using an applicator, and then heated in an oven at 150 ° C. for 1 hour to prepare a transparency evaluation sample (75 μm). If necessary, the solvent may be removed by an evaporator after preparing the liquid.

<Ejection evaluation>
When the phosphor compositions prepared in each Example and Comparative Example were applied by a slit die coater, the ease of discharging the resin from the die when the discharge pressure was 0.1 Pa was evaluated.
Very good: Resin is discharged within 3 seconds after starting discharge.
Good: Resin is discharged within 10 seconds over 3 seconds after the start of discharge.
Poor: Resin is discharged after 10 seconds from the start of discharge.

<Evaluation of film thickness uniformity>
The surface of the phosphor sheet produced based on the examples was observed with an optical microscope, and defects such as repelling were confirmed to evaluate the ease of forming a sheet film.
A: There is no defect such as repelling, and a uniform film is formed. Very good film thickness uniformity.
B: The number of defects such as repellency is within 10 and a relatively uniform film is formed. The film thickness uniformity is practically no problem.
C: There are 11 or more repellents, and a uniform film is not formed. The film thickness uniformity is poor.

<Illuminance measurement of phosphor sheet>
In Examples 19 to 96 and Comparative Examples 11 to 36, the phosphor sheets were measured for illuminance by preparing samples in the following manner.

As shown in FIG. 11, a diffusion sheet 13 (Stock Co., Ltd.) cut so as to cover the LED light source 17 on the LED light source 17 (“MS-LED-460” manufactured by Prizmatix, wavelength: 460 nm, output:> 50 mW). ) "LSD-60x1PC10-F12" manufactured by Optical Solutions Co., Ltd.), black metal shading plate 16 with a hole with a diameter of 1 mm, and a surface with a high refractive index of the phosphor sheet is affixed so that bubbles do not enter the GaN substrate. Measure the illuminance (lx) of the measurement sample 12 by placing the light receiving part of the sample (measurement sample) 12, the light shielding cylinder 15 made of black metal, and the illuminance meter 11 (color illuminance meter “CL-200A” manufactured by Konica Minolta, Inc.) in this order. did. If measurement is always performed at a constant distance and a fixed angle, the illuminance is proportional to the luminance. The illuminance of Comparative Example 11 was set to 100, and the relative value of illuminance relative to this was shown.
(Rounded to the first decimal place)
A: The value of the relative value is 116 or more The brightness improvement effect is very large B: The value of the relative value is 110 or more and 115 or less The brightness improvement effect is large C: The value of the relative value is 104 or more and 109 or less The brightness improvement effect D: Relative value is 101 or more and 103 or less Some effect of improving brightness E: Relative value is 100 or less There is no effect of improving brightness.

<Preparation of sample for illuminance measurement>
A GaN substrate (plate thickness 0.5 mm) is set on the hot plate, the temperature of the hot plate is set to 130 ° C., and then the phosphor sheet is placed on the GaN substrate so that the phosphor sheet surface is in contact with the GaN substrate surface. The laminate was stacked. Thereafter, the base material (base film) side of the phosphor sheet laminate was squeezed for 60 seconds using a rubber roller, and the phosphor sheet was attached to the GaN substrate.
After moving the GaN substrate sample from the hot plate and returning to room temperature, the base material was peeled off to produce a sample substrate.

<Adhesion test>
Eleven parallel scratches were made on the surface of the sample substrate with an NT cutter at intervals of 1 mm in length and width to produce 100 squares. A polyester film adhesive tape (“Circuit Tape No. 647” manufactured by Teraoka Seisakusho) is strongly bonded to this, and then the end of the tape is peeled off at an angle of 45 °, and the phosphor sheet remains without peeling. The number of cells was visually confirmed to evaluate the adhesion.
S: Number of remaining cells 100 A: Number of remaining cells 95 to 99 B: Number of remaining cells 90 to 94 C: Number of remaining cells 85 to 89 D: The number of remaining squares is 84 or less.

<Sample preparation for adhesion test>
A GaN substrate (plate thickness 0.5 mm) is set on the hot plate, the temperature of the hot plate is set to 130 ° C., and then the phosphor sheet is placed on the GaN substrate so that the phosphor sheet surface is in contact with the GaN substrate surface. The laminate was stacked. Thereafter, the base material (base film) side of the phosphor sheet laminate was squeezed for 60 seconds using a rubber roller, and the phosphor sheet was attached to the GaN substrate.
After moving the GaN substrate sample from the hot plate and returning to room temperature, the base material was peeled off to produce a sample substrate.

<Dynamic elastic modulus measurement>
Measuring device: Viscosity / viscoelasticity measuring device HAAKE MARS III
(Thermo Fisher SCIENTIFIC made)
Measurement conditions: OSC temperature-dependent measurement Geometry: Parallel disk type (20mm)
Measurement time: 1980 seconds Angular frequency: 1 Hz
Angular velocity: 6.2832 rad / sec Temperature range: 25 to 200 ° C (with low temperature control function)
Temperature increase rate: 0.08333 ° C./sec Sample shape: Circular (diameter 18 mm).

<Measurement sample preparation for dynamic viscoelasticity measurement>
After the phosphor sheet laminate produced based on the examples and comparative examples was cut out into a circular shape with a diameter of 18 mm, the film was peeled off to obtain a phosphor sheet alone as a measurement sample. Tables 34, 36, 38, and 40 show the viscoelastic behavior of each phosphor sheet.

<Heat resistance test>
The LED chip is turned on by applying an electric current to the LED package using the phosphor sheet so that the surface temperature of the package is from room temperature (25 ° C.) to 170 ° C. Was used to measure the luminance. The luminance at room temperature (25 ° C.) and 170 ° C. was measured, and the heat retention was evaluated by calculating the luminance retention rate according to the following formula. It shows that it is excellent in heat resistance, so that a luminance retention is high. If the rating is B or more, there is no practical problem, and if the rating is A or more, it is practically excellent.
Luminance retention ratio I (%) = (luminance at 170 ° C./luminance at room temperature (25 ° C.)) × 100
(Rounded to the first decimal place)
S: Retention rate 90% or more Heat resistance is very good A: Retention rate 81-89% Good heat resistance B: Retention rate 51-80% Heat resistance is practically no problem C: Retention rate 50% or less bad.

<Hardness measurement and handling evaluation>
Hardness measurement was carried out as an index of handleability when using a phosphor sheet (such as cracking during handling, soft shape breaking). Measurement of rubber / plastic soft hardness tester “Durometer Type D” (Product No .: GSD-720J manufactured by Teclock Co., Ltd.) based on JIS K6253 (2012) Durometer Hardness Test Method Used as an apparatus, the hardness of the sheet at room temperature (25 ° C.) was measured. Based on the experience so far, there is a correlation between the hardness of the phosphor sheet and the ease of handling. Therefore, the handleability was evaluated based on the hardness. If the rating is B or more, there is no practical problem, and if the rating is A or more, it is practically excellent.
S: Hardness 60-79 Very easy to handle A: Hardness 80-89 or 50-59 Good handleability B: Hardness 40-49 Tweezers are shaped but handleability is practically acceptable C: Hardness 90 More than or less than 39 Handling is poor.

<Production of LED package and brightness evaluation>
The LED packages in Examples 1 to 18 and Comparative Examples 1 to 10 were produced as follows. The obtained phosphor composition was placed on a package frame (Enomoto's frame “TOP LED BASE”) on which an LED chip (“GM2QT450G” manufactured by Showa Denko KK, average wavelength: 453.4 nm) was mounted. An LED package was manufactured by casting using “MPP-1” manufactured by Musashino Engineering Co., Ltd. and curing at 80 ° C. for 1 hour and 150 ° C. for 2 hours. The manufactured LED package was turned on by passing a current of 20 mA, and the luminance immediately after the start of the test was measured using an instantaneous multi-metering system (“MCPD-7700” manufactured by Otsuka Electronics Co., Ltd.). It was. The illuminance of Comparative Example 1 was set to 100, and the relative value of illuminance relative to this was shown.
(Rounded to the first decimal place)
A: The value of the relative value is 116 or more The brightness improvement effect is very large B: The value of the relative value is 110 or more and 115 or less The brightness improvement effect is large C: The value of the relative value is 104 or more and 109 or less The brightness improvement effect D: Relative value is 101 or more and 103 or less Some effect of improving brightness E: Relative value is 100 or less There is no effect of improving brightness.

Example 1 (with silicone fine particles, effect of grafting)
<Preparation of phosphor composition>
Using a planetary stirring and degassing apparatus “Mazerustar KK-400” (manufactured by Kurabo Industries), 6.0 g of silicone resin 1 is added to and mixed with 3.0 g of titanium oxide particles obtained by the method of grafting example 1, The mixture was stirred and degassed at 1000 rpm for 10 minutes. After leaving for a desired time, the solvent was removed by an evaporator to prepare a sample having a solid content concentration of 80 wt%, and then a sample for refractive index measurement and a sample for transparency evaluation were prepared. As a result of the refractive index evaluation, the average refractive index N1 was 1.60. Further, the transparency was very good.

Next, 15.0 g of silicone resin 1 is added to and mixed with 30.0 g of the titanium oxide particles obtained by the method of Grafting Example 1 using a planetary stirring and defoaming device, and the mixture is stirred and removed at 1000 rpm for 3 minutes. Foamed. After leaving for a desired time, the solvent was removed by an evaporator to prepare a sample having a solid content concentration of 80 wt%. Next, 6.67 g of silicone fine particles, 26.67 g of phosphor, and 2.35 g of butyl carbitol were added and mixed. Thereafter, using a planetary stirring / defoaming apparatus, stirring and defoaming was performed at 1000 rpm for 5 minutes, and then mixed and dispersed six times with three rolls to prepare phosphor composition 1. The refractive index difference | N1−N2 | was 0.20. As a result of conducting a discharge property test using this phosphor composition 1, resin was discharged from the die simultaneously with the start of discharge, and good discharge property was confirmed. As a result of fabricating the LED package and measuring the luminance, relative illuminance was 110 with respect to Comparative Example 1, and the luminance improvement effect was obtained.

Comparative Example 1 (with silicone fine particles, influence of graft)
A phosphor composition was produced in the same manner as in Example 1 except that no metal compound particles were added. Then, the LED package by the same operation as Example 1 was produced and evaluated. The results are shown in Tables 3 and 4.

Comparative Example 2 (with silicone fine particles, graft effect)
A phosphor composition was produced in the same manner as in Example 1 except that the powder was changed to powdered titanium oxide particles “TKP-102” (trade name, manufactured by TEIKA CORPORATION) as the metal compound particles. Then, the LED package by the same operation as Example 1 was produced and evaluated. The results are shown in Tables 3 and 4. Since the dispersibility in the matrix resin was poor and agglomerated, the phosphor composition could not be produced.

Comparative Example 3 (with silicone fine particles, graft effect)
The same operation as in Example 1 except that the metal compound particles were changed to "Optlake TR-527" (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd., composition: titanium oxide particles 20 wt%, methanol 80 wt%). A phosphor composition was prepared. Then, the LED package by the same operation as Example 1 was produced and evaluated. The results are shown in Tables 3 and 4. Compared to Comparative Example 1, the luminance further decreased.

Examples 2 to 9, Comparative Examples 4 and 5 (with silicone fine particles, effect of grafting)
A phosphor composition was prepared in the same manner as in Example 1 except that the compositions shown in Tables 1 and 3 were changed. Then, the LED package by the same operation as Example 1 was produced, and evaluation was performed. The results are shown in Tables 1 to 4. From these examples, it was found that the brightness was greatly improved with the phosphor composition of the present invention. In Comparative Examples 4 and 5, the luminance was not improved.

Examples 10 to 18 and Comparative Examples 6 to 10 (no silicone fine particles, effect of grafting)
A phosphor composition was prepared in the same manner as in Example 1, except that the silicone fine particles were not added and the compositions shown in Tables 5 and 7 were changed. Then, the LED package by the same operation as Example 1 was produced, and evaluation was performed. The results are shown in Tables 5-8. From these examples, it was found that the luminance was improved with the phosphor composition of the present invention. In Comparative Examples 6 to 10, the luminance was not improved.

Example 19 (with silicone fine particles, graft effect, phosphor sheet)
<Preparation of phosphor composition>
Using a planetary stirring and degassing apparatus “Mazerustar KK-400” (manufactured by Kurabo Industries), 6.0 g of silicone resin 1 is added to and mixed with 3.0 g of titanium oxide particles obtained by the method of grafting example 1, The mixture was stirred and degassed at 1000 rpm for 3 minutes. After leaving for a desired time, the solvent was removed by an evaporator to prepare a sample having a solid content concentration of 80 wt%, and then a sample for refractive index measurement and a sample for transparency evaluation were prepared. As a result of the refractive index evaluation, the average refractive index N1 was 1.60. Further, the transparency was very good.

Next, 15.0 g of silicone resin 1 is added to and mixed with 30.0 g of the titanium oxide particles obtained by the method of Grafting Example 1 using a planetary stirring and defoaming device, and the mixture is stirred and removed at 1000 rpm for 3 minutes. Foamed. After leaving for a desired time, the solvent was removed by an evaporator to prepare a sample having a solid content concentration of 80 wt%. Next, 6.67 g of silicone fine particles, 26.67 g of phosphor, and 2.35 g of butyl carbitol were added and mixed. Thereafter, using a planetary stirring / defoaming apparatus, stirring and defoaming was performed at 1000 rpm for 5 minutes, and then mixed and dispersed six times with three rolls to prepare phosphor composition 1. The refractive index difference | N1−N2 | was 0.20. As a result of conducting a discharge property test using this phosphor composition 1, resin was discharged from the die simultaneously with the start of discharge, and good discharge property was confirmed.

<Preparation of phosphor sheet laminate>
Using a slit die coater, “Therapy” BX9 with phosphor composition 1 as a base material
It apply | coated on the mold release process surface (Toray Film Processing Co., Ltd. product, average film thickness of 50 micrometers), and it heated and dried at 120 degreeC for 30 minutes, and obtained the fluorescent substance sheet laminated body of 80 micrometers and a 100 mm square. Then, the fluorescent sheet was replaced using a dry film laminator, and the base film was changed to a polyphenylene sulfide film “Torelina 3000” (manufactured by Toray Industries, Inc., average film thickness 50 μm). As a result of the illuminance measurement, relative illuminance was 110 compared to Comparative Example 11, and an effect of improving luminance was obtained.

Examples 20 to 27, Comparative Examples 11 to 15 (with silicone fine particles, graft effect, phosphor sheet)
A phosphor composition was prepared in the same manner as in Example 19 except that the compositions described in Tables 9 and 11 were changed. Then, the fluorescent substance sheet laminated body by the operation similar to Example 19 was produced, and evaluation was performed. The results are shown in Tables 9-12. From these examples, it was found that a phosphor sheet obtained by forming the phosphor composition of the present invention into a sheet has good film thickness uniformity and greatly improved luminance. In Comparative Examples 10 to 14, the film thickness uniformity was poor and the luminance was not improved.

Examples 28 to 36, Comparative Examples 16 to 20 (no silicone fine particles, graft effect, phosphor sheet)
A phosphor composition was prepared in the same manner as in Example 19 except that the silicone fine particles were not added and the compositions shown in Tables 13 and 15 were changed. Then, the fluorescent substance sheet laminated body by the operation similar to Example 19 was produced, and evaluation was performed. The results are shown in Tables 13-16. From these examples, it was found that if the phosphor sheet is formed by forming the phosphor composition of the present invention into a sheet shape, the film thickness uniformity is within the practical range and the luminance is also improved. In Comparative Examples 16 to 20, the film thickness uniformity was poor and the luminance was not improved.

Example 37 (refractive index effect, phosphor sheet)

<Preparation of phosphor composition>
Using a planetary stirring and defoaming device “Mazerustar KK-400” (manufactured by Kurabo Industries), 1.58 g of silicone resin 1 is added to 9.52 g of titanium oxide particles obtained by the method of grafting example 1, and mixed. The mixture was stirred and degassed at 1000 rpm for 3 minutes. After leaving for a desired time, the solvent was removed by an evaporator to prepare a sample having a solid content concentration of 80 wt%, and then a sample for refractive index measurement and a sample for transparency evaluation were prepared. As a result of the refractive index evaluation, the average refractive index N1 was 1.63. Further, the transparency was very good.

Next, 7.93 g of silicone resin 1 was added to 47.57 g of titanium oxide particles obtained by the method of grafting example 1 using a planetary stirring and defoaming apparatus “Mazerustar KK-400” (manufactured by Kurabo Industries). The mixture was mixed and stirred and degassed at 1000 rpm for 3 minutes. After leaving for a desired time, the solvent was removed by an evaporator to prepare a sample having a solid content concentration of 80 wt%. Next, 6.67 g of silicone fine particles, 26.67 g of phosphor, and 2.66 g of butyl carbitol were added and mixed. Then, using a planetary stirring and defoaming device “Mazerustar KK-400” (manufactured by Kurabo Industries), stirring and defoaming at 1000 rpm for 5 minutes, mixing and dispersing 6 times with 3 rolls, phosphor composition 29 Produced. The refractive index difference | N1−N2 | was 0.17. As a result of conducting a dischargeability test using this phosphor composition 29, resin was discharged from the die simultaneously with the start of discharge, and good dischargeability was confirmed.

<Preparation of phosphor sheet laminate>
Using a slit die coater, the phosphor composition 29 as a base material was coated on a release treatment surface of “Therapy” BX9 (manufactured by Toray Film Processing Co., Ltd., average film thickness 50 μm), and heated at 120 ° C. for 30 minutes. It dried and obtained the fluorescent substance sheet laminated body of 80 micrometers and a 100 square mm. Then, the fluorescent sheet was replaced using a dry film laminator, and the base film was changed to a polyphenylene sulfide film “Torelina 3000” (manufactured by Toray Industries, Inc., average film thickness 50 μm). As a result of the illuminance measurement, relative illuminance was 111 with respect to Comparative Example 11, and a large luminance improvement effect was obtained.

Example 38 (refractive index effect, phosphor sheet)
<Preparation of phosphor composition>
Using a planetary stirring and defoaming device “Mazerustar KK-400” (manufactured by Kurabo Industries Co., Ltd.), 0.6 g of silicone resin 1 is added to 12.0 g of titanium oxide particles obtained by the method of grafting example 1 and mixed. The mixture was stirred and degassed at 1000 rpm for 3 minutes. After leaving for a desired time, the solvent was removed by an evaporator to prepare a sample having a solid content concentration of 80 wt%, and then a sample for refractive index measurement and a sample for transparency evaluation were prepared. As a result of the refractive index evaluation, the average refractive index N1 was 1.70. Further, the transparency was very good.

Next, 3.0 g of silicone resin 1 is added to and mixed with 60.0 g of titanium oxide particles obtained by the method of Grafting Example 1 using a planetary agitation / deaeration apparatus, and the mixture is agitated and removed at 1000 rpm for 3 minutes. Foamed. After leaving for a desired time, the solvent was removed by an evaporator to prepare a sample having a solid content concentration of 80 wt%. Next, 6.67 g of silicone fine particles, 26.67 g of phosphor, and 2.89 g of butyl carbitol were added and mixed. Thereafter, using a planetary stirring / defoaming apparatus, stirring and defoaming was performed at 1000 rpm for 5 minutes, and then mixed and dispersed six times with three rolls to prepare a phosphor composition 30. The refractive index difference | N1-N2 | was 0.10. As a result of conducting a dischargeability test using this phosphor composition 30, resin was discharged from the die simultaneously with the start of discharge, and good dischargeability was confirmed.

<Preparation of phosphor sheet laminate>
"Serapeel" BX9 using phosphor composition 30 as a base material using a slit die coater
It apply | coated on the mold release process surface (Toray Film Processing Co., Ltd. product, average film thickness of 50 micrometers), and it heated and dried at 120 degreeC for 30 minutes, and obtained the fluorescent substance sheet laminated body of 80 micrometers and a 100 mm square. Then, the fluorescent sheet was replaced using a dry film laminator, and the base film was changed to a polyphenylene sulfide film “Torelina 3000” (manufactured by Toray Industries, Inc., average film thickness 50 μm). As a result of the illuminance measurement, relative illuminance was 115 with respect to Comparative Example 11, and a large luminance improvement effect was obtained.

Example 39 (refractive index effect, phosphor sheet)
<Preparation of phosphor composition>
Using a planetary stirring and defoaming apparatus “Mazerustar KK-400” (manufactured by Kurabo Industries), 2.26 g of silicone resin 1 was added to 7.94 g of the titanium oxide particles obtained by the method of grafting Example 10 and mixed. The mixture was stirred and degassed at 1000 rpm for 3 minutes. After leaving for a desired time, the solvent was removed by an evaporator to prepare a sample having a solid content concentration of 80 wt%, and then a sample for refractive index measurement and a sample for transparency evaluation were prepared. As a result of the refractive index evaluation, the average refractive index N1 was 1.73. Further, the transparency was very good.

Next, 11.33 g of silicone resin 1 was added to 39.67 g of titanium oxide particles obtained by the method of grafting example 5 using a planetary stirring and defoaming apparatus “Mazerustar KK-400” (manufactured by Kurabo Industries). The mixture was mixed and stirred and degassed at 1000 rpm for 3 minutes. After leaving for a desired time, the solvent was removed by an evaporator to prepare a sample having a solid content concentration of 80 wt%. Next, 6.67 g of silicone fine particles, 26.67 g of phosphor, and 2.53 g of butyl carbitol were added and mixed. Then, using a planetary stirring and defoaming device “Mazerustar KK-400” (manufactured by Kurabo Industries), stirring and defoaming at 1000 rpm for 5 minutes, mixing and dispersing 6 times with three rolls, and phosphor composition 31 Produced. The refractive index difference | N1-N2 | was 0.07. As a result of conducting a discharge property test using this phosphor composition 31, resin was discharged from the die simultaneously with the start of discharge, and good discharge property was confirmed.

<Preparation of phosphor sheet laminate>
"Serapeel" BX9 using phosphor composition 31 as a base material using a slit die coater
It apply | coated on the mold release process surface (Toray Film Processing Co., Ltd. product, average film thickness of 50 micrometers), and it heated and dried at 120 degreeC for 30 minutes, and obtained the fluorescent substance sheet laminated body of 80 micrometers and a 100 mm square. Then, the fluorescent sheet was replaced using a dry film laminator, and the base film was changed to a polyphenylene sulfide film “Torelina 3000” (manufactured by Toray Industries, Inc., average film thickness 50 μm). As a result of the illuminance measurement, relative illuminance was 117 with respect to Comparative Example 11, and a very large luminance improvement effect was obtained.

Example 40 (refractive index effect, phosphor sheet)
<Preparation of phosphor composition>
Using a planetary stirring and defoaming device “Mazerustar KK-400” (manufactured by Kurabo Industries), 2.08 g of silicone resin 1 was added to 8.32 g of the titanium oxide particles obtained by the method of grafting Example 10 and mixed. The mixture was stirred and degassed at 1000 rpm for 3 minutes. After leaving for a desired time, the solvent was removed by an evaporator to prepare a sample having a solid content concentration of 80 wt%, and then a sample for refractive index measurement and a sample for transparency evaluation were prepared. As a result of the refractive index evaluation, the average refractive index N1 was 1.75. Further, the transparency was very good.

Next, 10.40 g of silicone resin 1 was added to 41.60 g of titanium oxide particles obtained by the method of grafting example 5 using a planetary stirring and defoaming apparatus “Mazerustar KK-400” (manufactured by Kurabo Industries). The mixture was mixed and stirred and degassed at 1000 rpm for 3 minutes. After leaving for a desired time, the solvent was removed by an evaporator to prepare a sample having a solid content concentration of 80 wt%. Next, 6.67 g of silicone fine particles, 26.67 g of phosphor, and 2.56 g of butyl carbitol were added and mixed. Then, using a planetary stirring and defoaming device “Mazerustar KK-400” (manufactured by Kurabo Industries), stirring and defoaming at 1000 rpm for 5 minutes, mixing and dispersing six times with three rolls, the phosphor composition 32 is obtained. Produced. The refractive index difference | N1-N2 | was 0.05. As a result of a discharge property test using this phosphor composition 32, resin was discharged from the die simultaneously with the start of discharge, and good discharge property was confirmed.

<Preparation of phosphor sheet laminate>
“Serapeel” BX9 using phosphor composition 32 as a base material using a slit die coater
It apply | coated on the mold release process surface (Toray Film Processing Co., Ltd. product, average film thickness of 50 micrometers), and it heated and dried at 120 degreeC for 30 minutes, and obtained the fluorescent substance sheet laminated body of 80 micrometers and a 100 mm square. Then, the fluorescent sheet was replaced using a dry film laminator, and the base film was changed to a polyphenylene sulfide film “Torelina 3000” (manufactured by Toray Industries, Inc., average film thickness 50 μm). As a result of the illuminance measurement, relative illuminance was 119 with respect to Comparative Example 11, and a very large luminance improvement effect was obtained.

Example 41 (refractive index effect, phosphor sheet)
<Preparation of phosphor composition>
Using a planetary stirring and defoaming apparatus “Mazerustar KK-400” (manufactured by Kurabo Industries), 1.58 g of silicone resin 1 was added to 9.52 g of titanium oxide particles obtained by the method of grafting Example 10 and mixed. The mixture was stirred and degassed at 1000 rpm for 3 minutes. After leaving for a desired time, the solvent was removed by an evaporator to prepare a sample having a solid content concentration of 80 wt%, and then a sample for refractive index measurement and a sample for transparency evaluation were prepared. As a result of the refractive index evaluation, the average refractive index N1 was 1.78. Further, the transparency was very good.

Next, 7.93 g of silicone resin 1 was added to 47.57 g of titanium oxide particles obtained by the method of grafting example 1 using a planetary stirring and defoaming apparatus “Mazerustar KK-400” (manufactured by Kurabo Industries). The mixture was mixed and stirred and degassed at 1000 rpm for 3 minutes. After leaving for a desired time, the solvent was removed by an evaporator to prepare a sample having a solid content concentration of 80 wt%. Next, 6.67 g of silicone fine particles, 26.67 g of phosphor, and 2.66 g of butyl carbitol were added and mixed. Then, using a planetary stirring and defoaming device “Mazerustar KK-400” (manufactured by Kurabo Industries), stirring and defoaming at 1000 rpm for 5 minutes, mixing and dispersing six times with three rolls, the phosphor composition 33 is obtained. Produced. The refractive index difference | N1−N2 | was 0.02. As a result of conducting a dischargeability test using this phosphor composition 33, resin was discharged from the die simultaneously with the start of discharge, and good dischargeability was confirmed.

<Preparation of phosphor sheet laminate>
“Serapeel” BX9 using phosphor composition 33 as a base material using a slit die coater
It apply | coated on the mold release process surface (Toray Film Processing Co., Ltd. product, average film thickness of 50 micrometers), and it heated and dried at 120 degreeC for 30 minutes, and obtained the fluorescent substance sheet laminated body of 80 micrometers and a 100 mm square. Then, the fluorescent sheet was replaced using a dry film laminator, and the base film was changed to a polyphenylene sulfide film “Torelina 3000” (manufactured by Toray Industries, Inc., average film thickness 50 μm). As a result of the illuminance measurement, relative illuminance was 122 with respect to Comparative Example 11, and a very large luminance improvement effect was obtained.

Comparative Example 21 (refractive index effect, phosphor sheet)
<Preparation of phosphor composition>
Using silicone resin 2, a sample for refractive index measurement and a sample for transparency evaluation were prepared without using metal compound particles. As a result of the refractive index evaluation, the average refractive index N1 was 1.54. Further, the transparency was very good.

Next, 26.67 g of silicone resin 2 was taken out, 6.67 g of silicone fine particles, 26.67 g of phosphor, and 1.8 g of butyl carbitol were added and mixed. Then, using a planetary stirring and defoaming device “Mazerustar KK-400” (manufactured by Kurabo Industries), stirring and defoaming at 1000 rpm for 5 minutes, mixing and dispersing six times with three rolls, the phosphor composition 34 is obtained. Produced. The refractive index difference | N1−N2 | was 0.26. As a result of conducting a dischargeability test using this phosphor composition 34, resin was discharged from the die simultaneously with the start of discharge, and good dischargeability was confirmed.

<Preparation of phosphor sheet laminate>
"Serapeel" BX9 using phosphor composition 34 as a base material using a slit die coater
It apply | coated on the mold release process surface (Toray Film Processing Co., Ltd. product, average film thickness of 50 micrometers), and it heated and dried at 120 degreeC for 30 minutes, and obtained the fluorescent substance sheet laminated body of 80 micrometers and a 100 mm square. As a result of the illuminance measurement, the relative illuminance was 90 with respect to Comparative Example 11, and the luminance improvement effect was not obtained.

Comparative Example 22 (refractive index effect, phosphor sheet)
<Preparation of phosphor composition>
Using a planetary stirring and defoaming device “Mazerustar KK-400” (manufactured by Kurabo Industries), 3.8 g of silicone resin 1 is added to and mixed with titanium oxide particles 3.88 obtained by the method of grafting example 1, The mixture was stirred and degassed at 1000 rpm for 3 minutes. After leaving for a desired time, the solvent was removed by an evaporator to prepare a sample having a solid content concentration of 80 wt%, and then a sample for refractive index measurement and a sample for transparency evaluation were prepared. As a result of the refractive index evaluation, the average refractive index N1 was 1.58. Further, the transparency was very good.

Next, 19.0 g of silicone resin 1 was added to 19.0 g of the titanium oxide particles obtained by the method of grafting example 1 using a planetary stirring and defoaming apparatus “Mazerustar KK-400” (manufactured by Kurabo Industries). The mixture was mixed and stirred and degassed at 1000 rpm for 3 minutes. After leaving for a desired time, the solvent was removed by an evaporator to prepare a sample having a solid content concentration of 80 wt%. Next, 6.67 g of silicone fine particles, 26.67 g of phosphor, and 2.14 g of butyl carbitol were added and mixed. Then, using a planetary stirring and defoaming device “Mazerustar KK-400” (manufactured by Kurabo Industries), stirring and defoaming at 1000 rpm for 5 minutes, mixing and dispersing 6 times with 3 rolls, phosphor composition 35 Produced. The refractive index difference | N1-N2 | was 0.22. As a result of conducting a dischargeability test using this phosphor composition 35, resin was discharged from the die simultaneously with the start of discharge, and good dischargeability was confirmed.

<Preparation of phosphor sheet laminate>
"Serapeel" BX9 using phosphor composition 35 as a base material using a slit die coater
It apply | coated on the mold release process surface (Toray Film Processing Co., Ltd. product, average film thickness of 50 micrometers), and it heated and dried at 120 degreeC for 30 minutes, and obtained the fluorescent substance sheet laminated body of 80 micrometers and a 100 mm square. Then, the fluorescent sheet was replaced using a dry film laminator, and the base film was changed to a polyphenylene sulfide film “Torelina 3000” (manufactured by Toray Industries, Inc., average film thickness 50 μm). As a result of the illuminance measurement, relative illuminance was 100 with respect to Comparative Example 11, and the luminance enhancement effect was not obtained.

Comparative Example 23 (refractive index effect, phosphor sheet)
<Preparation of phosphor composition>
Using silicone resin 3, a sample for refractive index measurement and a sample for transparency evaluation were prepared without using metal compound particles. As a result of the refractive index evaluation, the average refractive index N1 was 1.40. Further, the transparency was very good.

Next, 26.67 g of silicone resin 3 was taken out, 6.67 g of silicone fine particles, 26.67 g of phosphor, and 1.8 g of butyl carbitol were added and mixed. Added and mixed. Then, using a planetary stirring and defoaming device “Mazerustar KK-400” (manufactured by Kurabo Industries), stirring and defoaming at 1000 rpm for 5 minutes, mixing and dispersing six times with three rolls, the phosphor composition 36 is obtained. Produced. The refractive index difference | N1−N2 | was 0.40. As a result of conducting a discharge property test using this phosphor composition 36, resin was discharged from the die simultaneously with the start of discharge, and good discharge property was confirmed.

<Preparation of phosphor sheet>
“Serapeel” BX9 using phosphor composition 36 as a base material using a slit die coater
It apply | coated on the mold release process surface (Toray Film Processing Co., Ltd. product, average film thickness of 50 micrometers), and it heated and dried at 120 degreeC for 30 minutes, and obtained the fluorescent substance sheet laminated body of 80 micrometers and a 100 mm square. As a result of the illuminance measurement, the relative illuminance was 80 with respect to Comparative Example 11, and the luminance enhancement effect was not obtained.

Examples 42 to 47 (Solvent effect, phosphor sheet)
Grafted titanium oxide particles were obtained in the same manner as Grafting Example 1 except that the solvents listed in Table 19 were used. A phosphor composition was prepared in the same manner as in Example 19 except that this was used. Then, the fluorescent substance sheet laminated body by the operation similar to Example 19 was produced, and evaluation was performed. The results are shown in Tables 19 and 20. From these examples, it was found that a phosphor sheet formed by forming the phosphor composition of the present invention into a sheet shape has good paste transparency and improved luminance.

Examples 48 to 52, Comparative Example 24 (effect of high refractive index nanoparticles, phosphor sheet)
Grafted nanoparticles were obtained in the same manner as Grafting Example 1 except that the metal compound particles listed in Table 22 were used. A phosphor composition was prepared in the same manner as in Example 19 except that this was used. Then, the fluorescent substance sheet laminated body by the operation similar to Example 19 was produced, and evaluation was performed. The results are shown in Tables 21 and 22. From these examples, it was found that the luminance was improved if the phosphor sheet was formed by forming the phosphor composition of the present invention into a sheet shape. In Comparative Example 24, the luminance was not improved.

Examples 19, 53 to 57, Comparative Examples 25 to 28 (Effect of particle size of high refractive index nanoparticles, phosphor sheet)
Grafted nanoparticles were obtained in the same manner as Grafting Example 1, except that the metal compound particles listed in Table 23 were used. A phosphor composition was prepared in the same manner as in Example 19 except that this was used. Then, the fluorescent substance sheet laminated body by the operation similar to Example 19 was produced, and evaluation was performed. The results are shown in Tables 23 and 24. From these examples, it was found that the luminance was improved if the phosphor sheet was formed by forming the phosphor composition of the present invention into a sheet shape. In Comparative Examples 25 to 28, the luminance was not improved.

Examples 58 to 64 (Effect of base material, phosphor sheet)
A phosphor composition was prepared in the same manner as in Example 19. Thereafter, a phosphor sheet laminate was prepared and evaluated in the same manner as in Example 19 except that the base material described in Table 25 was used. The results are shown in Table 25. In Examples 58 to 64, the film thickness uniformity was better than that of Comparative Example 11. In addition, as a result of the illuminance measurement, in comparison with Comparative Example 11, Examples 58 to 64 obtained an effect of improving luminance. From these results, it was found that changing the base material did not change the effect on luminance.

Examples 65 to 71 (Effect of phosphor sheet thickness, phosphor sheet)
A phosphor composition was prepared in the same manner as in Example 19. Thereafter, a phosphor sheet laminate was produced and evaluated in the same manner as in Example 19 except that the sheet thickness was changed to that shown in Table 26. The results are shown in Table 26. As a result of the heat resistance test, it was confirmed that the heat resistance tends to deteriorate as the film thickness increases. Further, as a result of the illuminance measurement, it was found that the luminance was improved in Examples 65 to 71 as compared with Comparative Example 11.

Example 72 (Effect of high refractive index nanoparticles, phosphor sheet)
Grafted nanoparticles were obtained in the same manner as Grafting Example 1, except that the metal compound particles listed in Table 19 were used. A phosphor composition was prepared in the same manner as in Example 19 except that this was used. Then, the fluorescent substance sheet laminated body by the operation similar to Example 19 was produced, and evaluation was performed. The results are shown in Table 28. From Example 72, it turned out that a brightness | luminance will improve if it is a fluorescent substance sheet formed by forming the fluorescent substance composition of this invention in a sheet form.

Examples 19, 73 to 82, Comparative Example 14 (Effect of molar ratio of alkoxysilane compound, phosphor sheet)
A phosphor composition was prepared in the same manner as in Example 19 except that the grafting method described in Tables 29 and 31 was used. Then, the fluorescent substance sheet laminated body by the operation similar to Example 19 was produced, and evaluation was performed. The results are shown in Tables 29-32. As a result of evaluating the handleability, Examples 19 and 73 to 82 obtained practically no problem with respect to Comparative Example 11, and Examples 19, 73 to 75 were particularly excellent in handleability. Further, as a result of the illuminance measurement, Examples 19, 73 to 82 showed a great brightness improvement effect as compared with Comparative Example 11.

Examples 19, 83 to 91, Comparative Examples 11, 13, 14, 29 to 35 (with silicone fine particles, viscoelastic behavior, phosphor sheet)
A phosphor composition was prepared in the same manner as in Example 19 except that the matrix resin described in Tables 33, 35, and 37 was used. Then, the fluorescent substance sheet laminated body by the same operation as Example 19 was produced, and viscoelastic behavior and various evaluation were performed. The results are shown in Tables 33-38. As a result of the adhesion test, Examples 19, 83 to 91, which are within the range of the viscoelastic behavior of the present invention, showed good adhesion, whereas Comparative Examples 11, 13, 14, 29 ~ 35 was the result of poor adhesion. Further, as a result of the illuminance measurement, the luminance improvement effect was obtained in Examples 19 and 83 to 91 with respect to Comparative Example 11. In Comparative Examples 11, 13, 14, and 29 to 35, the luminance improvement effect was not obtained. From these results, it was found that the brightness enhancement effect can be obtained with the phosphor sheet of the present invention.

Examples 28, 92 to 96, Comparative Examples 16, 18, 19, 36 (no silicone fine particles, viscoelastic behavior, phosphor sheet)
A phosphor composition was prepared in the same manner as in Example 19 except that the silicone fine particles were not added and the matrix resin described in Table 39 was used. Then, the fluorescent substance sheet laminated body by the same operation as Example 19 was produced, and viscoelastic behavior and various evaluation were performed. The results are shown in Tables 39 and 40. As a result of the adhesion test, Examples 28 and 92 to 96, which are within the range of the viscoelastic behavior of the present invention, showed good adhesion, whereas Comparative Examples 16, 18, 19, and 36. Was the result of poor adhesion. As a result of measuring the illuminance, the brightness improvement effect was obtained in Examples 28 and 92 to 96 with respect to Comparative Example 11. In Comparative Examples 16, 18, 19, and 36, the luminance improvement effect was not obtained. From these results, it was found that the brightness enhancement effect can be obtained with the phosphor sheet of the present invention.

DESCRIPTION OF SYMBOLS 1 LED chip 2 Phosphor sheet 3 Electrode 4 Phosphor composition 5 Reflector 6 Transparent sealing material 7 Mounting board 8 Gold bump 9 Transparent adhesive 10 Base material 11 Illuminometer 12 Measurement sample 13 Diffusion sheet 14 Stand 15 Light shielding cylinder 16 Light shielding Plate 17 LED light source 18 Package frame 19 LED package 20 Base material 21 Temporary fixing sheet 22 Thermocompression bonding tool 23 Wafer with LED chip formed on the surface 24 LED chip with phosphor sheet 25 Base material 26 Phosphor sheet laminate 27 Package substrate 28 Package electrode 29 Double-sided adhesive tape 30 Base 31 Upper chamber 32 Lower chamber 33 Diaphragm 35 Vacuum diaphragm muraminator 34 Intake / exhaust port 36 Cutting part 37 LED chip with

phosphor sheet

38, 39 LED pad Cage 101 Matrix resin 102 Metal compound particle 103 Silicone fine particle 104 Grafted metal compound particle 105 Phosphor

Claims

A phosphor composition containing a phosphor, a matrix resin, and metal compound particles, wherein the metal compound particles have a refractive index of 1.7 or more and an average particle diameter of 1 to 50 nm, The phosphor composition, wherein the average refractive index N1 of the metal compound particles and the matrix resin satisfies the following relationship with the refractive index N2 of the phosphor, and the metal compound particles are grafted.
0.20 ≧ | N1-N2 |
The phosphor composition according to claim 1, further comprising silicone fine particles.
The phosphor composition according to claim 2, wherein the surface of the silicone fine particles is coated with the grafted metal compound particles.
4. The phosphor composition according to claim 1, wherein the metal compound particles are grafted with an alkoxysilane condensate.
The phosphor composition according to any one of claims 1 to 4, wherein the metal compound particles are grafted with a condensate of alkoxysilane, and the alkoxysilane includes a phenyl group-containing alkoxysilane and a methyl group-containing alkoxysilane.
The metal compound particles are grafted by hydrolyzing an alkoxysilane compound in a solvent with an acid catalyst in the presence of the metal compound particles, and then subjecting the hydrolyzate to a condensation reaction. The phosphor composition according to any one of the above.
The phosphor composition according to claim 6, wherein the alkoxysilane compound contains 100 to 70 mol% of a trifunctional alkoxysilane compound and 0 to 30 mol% of a bifunctional alkoxysilane compound.
The fluorescence according to any one of claims 1 to 7, wherein the metal compound particles are at least one metal compound particle selected from the group consisting of aluminum compound particles, tin compound particles, titanium compound particles, zirconium compound particles and niobium compound particles. Body composition.
The phosphor composition according to any one of claims 1 to 8, wherein the matrix resin is a silicone resin.
The phosphor composition according to claim 9, wherein the matrix resin is a silicone resin having a siloxane bond and containing a silicon atom to which an aryl group is directly bonded.
The phosphor composition according to claim 10, wherein the matrix resin contains a silicon atom having a siloxane bond and having a naphthyl group directly bonded thereto.
A phosphor sheet formed by forming the phosphor composition according to any one of claims 1 to 11 into a sheet shape.
A phosphor sheet containing a phosphor, a matrix resin, and metal compound particles, wherein the metal compound particles have a refractive index of 1.7 or more and an average particle diameter of 1 to 50 nm. Compound particles are grafted, the average refractive index N1 of the metal compound particles and the matrix resin satisfies the following relationship (i) with the refractive index N2 of the phosphor, and the viscoelastic behavior of the sheet is A phosphor sheet characterized by satisfying (ii), (iii) and (iv).
<Refractive index relationship>
(I) 0.20 ≧ | N1-N2 |
<Viscoelastic behavior>
(Ii) The storage elastic modulus G ′ is 1.0 × 10 4 Pa ≦ G ′ ≦ 1.0 × 10 6 Pa at a temperature of 25 ° C. and tan δ <1
(Iii) Storage modulus G ′ is 1.0 × 10 2 Pa ≦ G ′ <1.0 × 10 4 Pa at a temperature of 100 ° C. and tan δ ≧ 1
(Iv) The storage elastic modulus G ′ is 1.0 × 10 4 Pa ≦ G ′ ≦ 1.0 × 10 6 Pa at a temperature of 200 ° C. and tan δ <1
The phosphor sheet according to claim 13, further comprising silicone fine particles.
The phosphor sheet according to claim 14, wherein the surface of the silicone fine particles is coated with the grafted metal compound particles.
The phosphor sheet according to any one of claims 13 to 15, wherein the metal compound particles are grafted with a condensate of alkoxysilane.
The phosphor sheet according to any one of claims 13 to 16, wherein the metal compound particles are grafted with a condensate of alkoxysilane, and the alkoxysilane includes a phenyl group-containing alkoxysilane and a methyl group-containing alkoxysilane.
The metal compound particles are grafted by hydrolyzing an alkoxysilane compound in a solvent with an acid catalyst in the presence of the metal compound particles and then subjecting the hydrolyzate to a condensation reaction. The phosphor sheet according to any one of the above.
The phosphor sheet according to claim 18, wherein the alkoxysilane compound contains 100 to 70 mol% of a trifunctional alkoxysilane compound and 0 to 30 mol% of a bifunctional alkoxysilane compound.
The fluorescence according to any one of claims 13 to 19, wherein the metal compound particles are at least one metal compound particle selected from the group consisting of aluminum compound particles, tin compound particles, titanium compound particles, zirconium compound particles and niobium compound particles. Body sheet.
The phosphor sheet according to any one of claims 13 to 20, wherein the matrix resin is a silicone resin.
The phosphor sheet according to claim 21, wherein the matrix resin contains a silicon atom having a siloxane bond and an aryl group directly bonded thereto.
The phosphor sheet according to claim 22, wherein the matrix resin contains a silicon atom having a siloxane bond and having a naphthyl group directly bonded thereto.
The phosphor sheet according to any one of claims 13 to 23, wherein the thickness of the sheet is 10 to 1000 µm.
A phosphor sheet laminate comprising a substrate and the phosphor sheet according to any one of claims 12 to 24.
The phosphor sheet laminate according to claim 25, wherein the substrate is glass.
The phosphor sheet laminate according to claim 25, wherein the substrate is a plastic film selected from the group consisting of polyethylene terephthalate (PET), polyphenylene sulfide (PPS), and polypropylene (PP).
An LED chip with a phosphor sheet comprising the phosphor sheet according to any one of claims 12 to 24 on a light emitting surface of the LED chip.
An LED package using the phosphor composition according to any one of claims 1 to 11.
An LED package using the phosphor sheet according to any one of claims 12 to 24.
A method for manufacturing an LED package using the phosphor composition according to any one of claims 1 to 11, comprising: (A) injecting the phosphor composition into a package frame; and (B) Then, the manufacturing method of an LED package including the process of sealing an LED package with a sealing material at least.
25. A method of manufacturing an LED package using the phosphor sheet according to any one of claims 12 to 24, wherein (A) a position where one section of the phosphor sheet faces a light emitting surface of one LED chip. An LED package manufacturing method including at least a bonding step, and (B) an adhesion step in which the one section of the sheet and the light emitting surface of the one LED chip are bonded while being heated by a thermocompression bonding tool.
The step (A) is an alignment step in which the surface on the higher concentration side of the high refractive index nanoparticles among the upper and lower surfaces of one section of the phosphor sheet is opposed to the light emitting surface of the one LED chip. 33. A method of manufacturing an LED package according to claim 32.
An LED package manufacturing method using the phosphor sheet according to any one of claims 12 to 24, comprising a step of covering a light emitting surface of an LED chip with the phosphor sheet.
The method for manufacturing an LED package according to any one of claims 32 to 34, wherein the light emitting surface of the LED chip is not a single plane.