JP6863367B2 - Fluorescent material sheet, LED chip and LED package using it, manufacturing method of LED package, and light emitting device including LED package, backlight unit and display - Google Patents

Description

The present invention relates to a phosphor sheet, an LED chip and an LED package using the same, a method for manufacturing an LED package, and a light emitting device including the LED package, a backlight unit, and a display.

Light emitting diodes (LEDs, Light Emitting Diodes) are used for the backlight of liquid crystal displays (LCD, Liquid Crystal Display) and have features such as low power consumption, long life, and design against the background of remarkable improvement in luminous efficiency. The market is rapidly expanding not only in the in-vehicle field such as car headlights, but also for general lighting. Since LEDs have a low environmental load, they are expected to form a huge market in the general lighting field in the future.

Since the emission spectrum of an LED depends on the semiconductor material forming the LED chip, its emission color is limited. Therefore, in order to obtain white light for LCD backlights and general lighting using LEDs, it is necessary to dispose an inorganic phosphor suitable for each chip on the LED chip and convert the emission wavelength. Specifically, a method of installing a yellow phosphor on an LED chip that emits blue light, a method of installing a red phosphor and a green phosphor on an LED chip that emits blue light, and the like have been proposed.

As one of the specific methods for installing the phosphor on the LED chip, a method of sticking a sheet containing the phosphor (hereinafter referred to as "fluorescent sheet") on the LED chip has been proposed (for example). , Patent Documents 1 to 4). In this method, the amount of the phosphor to be arranged on the LED chip is constant as compared with the method in which the phosphor composition in which the phosphor is dispersed in the resin is dispensed and cured on the LED chip, which has been put into practical use in the past. It is easy to make a quantity. As a result, it is excellent in that the color and brightness of the obtained white LED can be made uniform.

Japanese Unexamined Patent Publication No. 2009-235368 JP-A-2010-123802 Japanese Patent No. 2011-102004 Japanese Patent No. 5287935

When the method of attaching the fluorescent material sheet on the LED chip is used, it corresponds to the cutting process when the fluorescent material sheet is fragmented to the size of the LED chip, or the electrode portion on the LED chip in the fluorescent material sheet. It is necessary to make holes in the part. Therefore, a fluorescent material sheet having excellent processability is required.

On the other hand, the phosphor sheet is required to have adhesiveness for being attached on the LED chip. In Patent Document 4, by using a silicone composition containing a specific organopolysiloxane, the processability before sticking to the LED chip is excellent, and the adhesiveness at the time of sticking to the LED chip is also excellent. It is disclosed that a new phosphor sheet can be obtained. However, this fluorescent sheet has insufficient curability after being attached to the LED chip, so that satisfactory adhesiveness has not been obtained. As a result, the LED chip to which the phosphor sheet is attached has a problem that the brightness is lowered due to poor adhesiveness.

In order to solve such a problem, an object of the present invention is to provide a phosphor sheet having both processability such as cutting and adhesiveness to an LED chip.

That is, the present invention is a phosphor sheet containing a phosphor and a silicone resin, wherein the storage elastic modulus G'at 25 ° C. is 0.01 MPa or more and the storage elastic modulus G'at 100 ° C. is less than 0.01 MPa. Moreover, it is a phosphor sheet having a storage elastic modulus G'at 140 ° C. of 0.05 MPa or more.

According to the present invention, it is possible to provide a phosphor sheet having excellent processability such as cutting and good adhesiveness to an LED chip.

An example of an LED package using a phosphor sheet according to an embodiment of the present invention. An example of an LED package using a phosphor sheet according to an embodiment of the present invention. An example of a method for manufacturing an LED package using a phosphor sheet according to an embodiment of the present invention. An example of a method for attaching a phosphor sheet according to an embodiment of the present invention. An example of a method for attaching a phosphor sheet according to an embodiment of the present invention. An example of a method for attaching a phosphor sheet according to an embodiment of the present invention. An example of a method for manufacturing an LED package using a phosphor sheet according to an embodiment of the present invention. An example of a method for manufacturing an LED package using a phosphor sheet according to an embodiment of the present invention.

Hereinafter, a fluorescent material sheet according to the present invention, an LED chip and an LED package using the same, a method for manufacturing the LED package, and a preferred embodiment of a light emitting device including the LED package, a backlight unit, and a display will be described in detail. .. However, the present invention is not limited to the following embodiments, and can be variously modified and implemented according to an object and an application.

<Fluorescent sheet>
The phosphor sheet according to the embodiment of the present invention contains a phosphor and a silicone resin, has a storage elastic modulus G'at 25 ° C. of 0.01 MPa or more, and has a storage elastic modulus G'at 100 ° C. of less than 0.01 MPa. And the storage elastic modulus G'at 140 ° C. is 0.05 MPa or more.

The phosphor sheet according to the embodiment of the present invention is sufficiently elastic at room temperature (25 ° C.) because the storage elastic modulus G'at 25 ° C. is 0.01 MPa or more. Therefore, the phosphor sheet is cut without deformation around the cut portion against a fast shear stress such as cutting by a blade, and workability with high dimensional accuracy can be obtained.

The upper limit of the storage elastic modulus G'at 25 ° C. is not particularly limited, but is preferably 2.0 MPa or less from the viewpoint of ease of handling the sample.

The phosphor sheet according to the embodiment of the present invention has a storage elastic modulus G'at 100 ° C. of less than 0.01 MPa, so that the sheet is sufficiently viscous at 100 ° C. and has high fluidity. Therefore, by attaching the phosphor sheet having this physical property to the LED chip while heating it at 100 ° C. or higher, the phosphor sheet quickly flows and deforms according to the shape of the light emitting surface of the LED chip. High adhesion between the LED chip and the LED chip can be obtained. As a result, the light extraction property from the LED chip is improved, and the brightness is improved.

The lower limit of the storage elastic modulus G'at 100 ° C. is not particularly limited, but if the fluidity of the phosphor sheet is too high when it is heat-pasted on the LED chip, it is processed by cutting or drilling before pasting. The shape is preferably 0.005 MPa or more because the shape cannot be retained at the time of sticking.

In the phosphor sheet according to the embodiment of the present invention, the LED chip can be finally operated stably when the storage elastic modulus G'at 140 ° C. is 0.05 MPa or more. When the fluorescent sheet having these physical characteristics is heated at 140 ° C. or higher, the complete curing of the sheet is completed quickly and the entire resin is integrated, so that the adhesiveness between the fluorescent sheet and the LED chip is improved. This also improves the brightness of the LED package. Further, the interface between the LED chip and the phosphor sheet is less affected by the heat when the LED is lit, so that the peeling of the LED chip and the phosphor sheet is suppressed. Therefore, the reliability of the LED package is increased.

The storage elastic modulus G'here is the storage elastic modulus G'when the dynamic viscoelasticity measurement (temperature dependence) of the phosphor sheet is performed by a rheometer. Dynamic viscoelasticity is a component (elastic component) that matches the phase of the shear stress that appears when a steady state is reached when shear strain is applied to the material at a sine frequency, and the strain and phase are the same. This is a method of analyzing the dynamic mechanical properties of a material by decomposing it into a component (viscous component) delayed by 90 °.

The dynamic viscoelasticity measurement (temperature dependence) can be performed by using a general viscosity / viscoelasticity measuring device. In the present invention, it is a value when the measurement is performed under the following conditions.

Measuring device: Viscosity / viscoelasticity measuring device HAAKE MARSIII
(Made by Thermo Fisher SCIENTIFIC)
Measurement conditions: OSC temperature-dependent measurement Geometry: Parallel disk type (20 mm)
Measurement time: 1980 seconds Angular frequency: 1 Hz
Angular velocity: 6.2832 rad / sec Temperature range: 25 to 200 ° C (with low temperature temperature control function)
Temperature rise rate: 0.08333 ° C / sec Sample shape: Circular (diameter 18 mm)
Sample thickness: 50 μm or more.

When the thickness of the measurement sample is 50 μm or more, dynamic viscoelasticity measurement can be performed stably. When the sample thickness is less than 50 μm, several sheets can be stacked and heat-pressed on a hot plate at 100 ° C. to prepare an integrated film (sheet), and a sample having a desired thickness can be prepared.

The storage elastic modulus G'is obtained by dividing the stress component whose phase matches the shear strain by the shear strain. The storage modulus G'represents the elasticity of the material against dynamic strain at each temperature and is related to the hardness of the phosphor sheet. Therefore, the storage modulus G'at each measurement temperature affects the following properties of the phosphor sheet. For example, at 25 ° C, the storage elastic modulus G'affects the processability of the phosphor sheet, at 100 ° C, it affects the fluidity and adhesiveness of the phosphor sheet, and at 140 ° C, the phosphor sheet. Affects curability and adhesion.

The thickness of the phosphor sheet according to the embodiment of the present invention is not particularly limited, but is preferably 10 μm or more and 1000 μm or less. The lower limit is more preferably 30 μm or more. The upper limit is more preferably 200 μm or less, further preferably 100 μm or less, and further preferably 50 μm or less. When the thickness of the phosphor sheet is 1000 μm or less, the crack resistance is particularly excellent, and when the thickness is 200 μm or less, the heat resistance is particularly excellent.

The fluorescent material sheet according to the embodiment of the present invention may be a laminated body provided with another layer, if necessary. Examples of the other layer include a base material and a barrier layer.

(Silicone resin)
The fluorescent material sheet according to the embodiment of the present invention contains a silicone resin mainly from the viewpoint of transparency and heat resistance.

As the silicone resin used in the present invention, a curable silicone resin is preferable. The curable silicone resin may have either a one-component type or a two-component type (three-component type). The curable silicone resin includes a dealcohol type, a deoxime type, a deacetic acid type, a dehydroxylamine type, and the like as a type that causes a condensation reaction by moisture in the air or a catalyst. In addition, there is an addition reaction type in which a hydrosilylation reaction is caused by a catalyst. Any of these types of curable silicone resins may be used. In particular, the addition reaction type silicone resin is more preferable because it has no by-products associated with the curing reaction, has a small curing shrinkage, and can be easily cured by heating.

The addition reaction type silicone resin is formed, for example, by a hydrosilylation reaction between a compound containing an alkenyl group bonded to a silicon atom and a compound having a hydrogen atom bonded to a silicon atom.

Examples of the "compound containing an alkenyl group bonded to a silicon atom" include vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, propenyltrimethoxysilane, norbornenyltrimethoxysilane, and octenyltrimethoxysilane. And so on. Examples of the "compound having a hydrogen atom bonded to a silicon atom" include methylhydrogenpolysiloxane, dimethylpolysiloxane-CO-methylhydrogenpolysiloxane, ethylhydrogenpolysiloxane, and methylhydrogenpolysiloxane-CO-methyl. Examples include phenylpolysiloxane. Examples of the addition reaction type silicone rubber include those formed by the hydrosilylation reaction of such a material. Further, as the silicone resin, for example, a known one as described in JP-A-2010-159411 can be used.

In the present invention, the silicone resin is preferably a crosslinked product of a crosslinkable silicone composition (hereinafter referred to as "the present composition") containing at least the following components (A) to (D). Here, among the silicone resins, the crosslinked product of the present composition is preferably 20% by weight or more, more preferably 50% by weight or more, and further preferably 80% by weight or more.

(A) Average unit formula:

(In the average unit formula (1), R ¹ is a monovalent hydrocarbon group having 1 to 14 carbon atoms, at least one is an aryl group, and at least one is an alkenyl having 2 to 6 carbon atoms. The group. R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. A, b, c, d, and e are 0 ≦ a ≦ 0.1 and 0.2 ≦ b ≦ 0.9. , 0.1 ≦ c ≦ 0.6, 0 ≦ d ≦ 0.2, 0 ≦ e ≦ 0.1, and a + b + c + d + e = 1.
Organopolysiloxane having a branched structure represented by.

(B) Average unit formula:

(In the average unit formula (2), R ³ is a monovalent hydrocarbon group having 1 to 14 carbon atoms, at least one of which is an aryl group, and at least one of which is an alkenyl having 2 to 6 carbon atoms. The groups f, g and h are numbers that satisfy 0.1 <f ≦ 0.4, 0.2 ≦ g ≦ 0.5, 0.2 ≦ h ≦ 0.5, and f + g + h = 1. )
Organopolysiloxane having a branched structure represented by.

(C) An organopolysiloxane having at least two Si—H bonds in one molecule and 12 to 70 mol% of organic groups bonded to silicon atoms being aryl groups.

(D) Catalyst for hydrosilylation reaction.

By having an aryl group, the organopolysiloxane of the component (A) can improve the compatibility with the components (B) to (D). Further, the organopolysiloxane of the component (A) has an alkenyl group having 2 to 6 carbon atoms, so that a cross-linking reaction of the components (A) to (C) is caused. Further, since the organopolysiloxane of the component (A) has a branched structure, the curability is improved and good adhesiveness to the LED chip can be obtained.

The branched structure indicates a structure in which the basic structural unit has a T unit (RSiO _3/2 ) or a Q unit (SiO _4/2 ) in the average unit formula. Here, in the average unit formula, a trifunctional unit in which one organic substituent represented by R is attached to a silicon atom is a T unit, and a tetrafunctional unit in which an organic substituent represented by R is not attached to a silicon atom. The unit of sex is called the Q unit.

By incorporating a branched structure into the organopolysiloxane of the component (A), the cross-linking reaction rate is improved and good curability can be obtained in the phosphor sheet.

The existence of the branched structure in the organopolysiloxane can be confirmed by subjecting the organopolysiloxane to a treatment such as a methyl orthoformate decomposition method and then performing an NMR analysis or a GPC-MALS analysis.

In particular, in GPC-MALS analysis, the molecular weight distribution and turning radius of organopolysiloxane can be obtained. Therefore, the existence of the branched structure can be confirmed by specifying the organopolysiloxane having the same molecular weight component and having a small turning radius.

In the average unit formula (1), the values of a, b, c, d and e indicate that the obtained crosslinked product has sufficient hardness at room temperature and is softened at high temperature to carry out the present invention. It is a sufficient range.

The organopolysiloxane of the component (B) is compatible with the component (A) by having an aryl group. Thereby, the mechanical strength and transparency of the cured film of the phosphor sheet containing the silicone resin can be maintained. Further, the organopolysiloxane of the component (B) has an alkenyl group having 2 to 6 carbon atoms, so that a cross-linking reaction of the components (A) to (C) is caused. Further, since the organopolysiloxane of the component (B) has a branched structure, the curability is improved and good adhesiveness to the LED chip can be obtained.

Further, from the viewpoint of good handleability in sample preparation and the like, the organopolysiloxane of the component (B) preferably has a viscosity of 20 Pa · s or less at 25 ° C.

The content of the component (B) is preferably in the range of 10 parts by weight or more and 95 parts by weight or less with respect to 100 parts by weight of the component (A). This is the range for the resulting crosslinked product to be sufficiently softened at high temperatures.

The organopolysiloxane of the component (C) has at least two Si—H bonds in one molecule, thereby causing a cross-linking reaction of the components (A) to (C). Further, in the organopolysiloxane of the component (C), 12 to 70 mol% of the organic groups bonded to the silicon atom are aryl groups, so that the obtained crosslinked product is sufficiently softened at high temperature and crosslinked. Maintains the transparency and mechanical strength of objects.

In particular, in the present invention, the organopolysiloxane of the component (C) is
Average unit formula:

(In the average unit formula (3), R ⁴ is an aryl group, an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group. However, 12 to 70 mol% of ^{R 4 is an aryl group.)}
It is preferably an organopolysiloxane represented by.

In the average unit formula (3), R ⁴ is preferably a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group. Examples of the alkyl group of 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 of R ⁴ include a cyclopentyl group and a cycloheptyl group. Of the ^{R 4,} phenyl group content is preferably 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 the transparency and mechanical strength of the crosslinked product can be maintained.

The content of the component (C) is the molar ratio of the hydrogen atom bonded to the silicon atom in the component (C) to the total amount of the alkenyl group in the component (A) and the alkenyl group in the component (B). The amount is preferably in the range of 0.5 to 2. This is because the obtained crosslinked product has sufficient hardness at room temperature.

The catalyst for the hydrosilylation reaction of the component (D) promotes the hydrosilylation reaction between the alkenyl groups in the components (A) and (B) and the hydrogen atom bonded to the silicon atom in the component (C). Is a catalyst for. Examples of the component (D) include a platinum-based catalyst, a rhodium-based catalyst, and a palladium-based catalyst. Of these, a platinum-based catalyst is preferable because it can remarkably accelerate the curing of the present composition.

Examples of this platinum-based catalyst include platinum fine powder, platinum chloride acid, an alcohol solution of platinum chloride acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex, and a platinum-carbonyl complex. In particular, the platinum-based catalyst is preferably a platinum-alkenylsiloxane complex.

Examples of this alkenylsiloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane. Examples thereof include alkenylsiloxanes in which some of the methyl groups of these alkenylsiloxanes are substituted with ethyl groups, phenyl groups, etc., and alkenylsiloxanes in which the vinyl groups of these alkenylsiloxanes are substituted with allyl groups, hexenyl groups, etc. In particular, 1,3-divinyl-1,1,3,3-toteramethyldisiloxane is preferable because the stability of this platinum-alkenylsiloxane complex is good.

In addition, since the stability of this platinum-alkenylsiloxane complex can be improved, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-diallyl- 1,1,3,3-Tetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane, 1,3-divinyl-1,1,3,3-tetraphenyldisiloxane It is preferable to add an alkenylsiloxane such as siloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane or an organosiloxane oligomer such as a dimethylsiloxane oligomer. In particular, it is preferable to add alkenylsiloxane to this complex.

The content of the component (D) is sufficient to promote the hydrosilylation reaction between the alkenyl groups in the components (A) and (B) and the hydrogen atom bonded to the silicon atom in the component (C). The amount is not particularly limited. Preferably, the content of the component (D) is an amount in which the metal atom in the component (D) is in the range of 0.01 to 500 ppm in mass units with respect to the present composition. Further, the content of the component (D) is preferably an amount in which the metal atom is in the range of 0.01 to 100 ppm, and the content of the metal atom is preferably in the range of 0.01 to 50 ppm. , Especially preferable. This is a range in which the present composition is sufficiently crosslinked and problems such as coloring do not occur.

This composition contains ethynylhexanol, 2-methyl-3-butyne-2-ol, 3,5-dimethyl-1-hexin-3-ol, 2-phenyl-3-butyne-2-ol as any other components. Alkyne alcohols such as oars; enyne compounds such as 3-methyl-3-pentene-1-in, 3,5-dimethyl-3-hexene-1-in; 1,3,5,7-tetramethyl-1,3 , 5,7-Tetravinylcyclotetrasiloxane, 1,3,5,7-Tetramethyl-1,3,5,7-Tetrahexenylcyclotetrasiloxane, benzotriazole and the like may be contained. The content of this reaction inhibitor is not limited, but is preferably in the range of 1 to 5,000 ppm with respect to the weight of the present composition. By adjusting the content of the reaction inhibitor, the storage elastic modulus of the obtained silicone resin can also be adjusted.

In the phosphor sheet according to the embodiment of the present invention, the content of the silicone resin is preferably 10% by weight or more, more preferably 30% by weight or more of the entire fluorescent material sheet. The content of the silicone resin is preferably 90% by weight or less, more preferably 85% by weight or less, and even more preferably 70% by weight or less.

The fluorescent material sheet according to the embodiment of the present invention is particularly preferably used for LED surface coating applications, as will be described in detail later. At that time, when the content of the silicone resin in the phosphor sheet is in the above range, it is possible to obtain a light emitting device exhibiting excellent performance.

(Fluorescent material)
The phosphor absorbs the light emitted from the LED chip, converts the wavelength of the light, and emits light having a wavelength different from that of the LED chip. As a result, a part of the light emitted from the LED chip and a part of the light emitted from the phosphor are mixed to obtain a multicolor LED including white. Specifically, a single LED chip is used by optically combining a blue LED chip and a phosphor that absorbs the light emitted from the LED chip and emits a yellow emission color. It is possible to obtain white light emission.

The above-mentioned phosphors include various phosphors such as a fluorescent substance that emits green light, a fluorescent substance that emits blue light, a fluorescent substance that emits yellow light, and a phosphor that emits red light. Specific examples of the phosphor used in the present invention include known phosphors such as inorganic phosphors, organic phosphors, and quantum dots. As the phosphor, either a fluorescent pigment or a fluorescent dye can be used.

The inorganic phosphor is not particularly limited as long as it can finally reproduce a predetermined color, and known ones can be used.

As the organic phosphor, it is preferable that the emission spectrum has a peak in a wavelength region of 500 to 700 nm. Such a phosphor is excited by excitation light in the wavelength range of 400 to 500 nm and emits light in the wavelength region of 500 to 700 nm. Examples of the fluorescent substance as described above include a fluorescent substance that emits green light, a fluorescent substance that emits yellow light, and a phosphor that emits red light. Examples of the organic phosphor used in the present invention include pyrromethene compounds, coumarin dyes, phthalocyanine dyes, stilben dyes, cyanine dyes, polyphenylene dyes, rhodamine dyes, pyridine dyes, pyrromethene dyes, and porphyrin dyes. , Oxazine-based dyes, pyrazine-based dyes, allylsulfoamide / melamine formaldehyde cocondensation dyes, perylene-based phosphors and the like. From the viewpoint of color reproducibility, a pyrromethene compound is preferably used, and in particular, an organic compound represented by the general formula (4) described later is preferably used.

Quantum dots are semiconductor nanoparticles that are excited by excitation light and emit fluorescence.
As the quantum dots used in the present invention, core-shell type semiconductor nanoparticles are preferable from the viewpoint of improving durability. As the core, II-VI group semiconductor nanoparticles, III-V group semiconductor nanoparticles, multidimensional semiconductor nanoparticles and the like can be used. Specific examples thereof include, but are not limited to, CdSe, CdTe, CdS, ZnS, ZnSe, ZnTe, InP, InAs, InGaP and the like. Of these, CdSe, CdTe, InP, and InGaP are preferable from the viewpoint of emitting visible light with high efficiency. As the shell, CdS, ZnS, ZnO, GaAs, and a complex thereof can be used, but the shell is not limited thereto. The emission wavelength of the quantum dots can usually be adjusted by the composition and size of the particles.

A ligand having a Lewis basic coordinating group may be coordinated on the surface of the quantum dot. Examples of the Lewis basic coordinating group include an amino group, a carboxy group, a mercapto group, a phosphine group, a phosphine oxide group, and the like. Specifically, hexylamine, decylamine, hexadecylamine, octadecylamine, oleylamine, myristylamine, laurylamine, oleic acid, mercaptopropionic acid, trioctylphosphine, trioctylphosphine oxide and the like can be raised. Among them, hexadecylamine, trioctylphosphine, and trioctylphosphine oxide are preferable, and trioctylphosphine oxide is particularly preferable.

Quantum dots coordinated with these ligands can be produced by a known synthetic method. For example, C.I. B. Murray, D.M. J. Norris, M. et al. G. It can be synthesized by the method described in Bowendi, Journal of Physical Chemistry, 1993, 115 (19), pp8706-8715, or The Journal Physical Chemistry, 101, pp9463-9475, 1997. Further, as the quantum dot in which the ligand is coordinated, a commercially available quantum dot can be used without any limitation. For example, Lumidot (manufactured by Sigma-Aldrich) can be mentioned.

Examples of the fluorescent substance particularly preferably used in the present invention include an inorganic fluorescent substance. The inorganic phosphor used in the present invention will be described below.

(Inorganic phosphor)
The inorganic phosphor used in the present invention preferably has a peak in the emission spectrum in a wavelength region of 500 to 700 nm. Such a phosphor is excited by excitation light in the wavelength range of 400 to 500 nm and emits light in the wavelength region of 500 to 700 nm. Examples of the fluorescent substance as described above include a fluorescent substance that emits green light, a fluorescent substance that emits yellow light, and a phosphor that emits red light.

The shape of the inorganic phosphor is not particularly limited, and various shapes such as spherical and columnar can be used.

Examples of the inorganic phosphor used in the present invention include YAG-based phosphors, TAG-based phosphors, silicate phosphors, nitride-based phosphors, oxynitride-based phosphors, nitride phosphors, and oxynitride phosphors. , Mn-activated difluoride complex phosphor and the like. Preferred examples of the oxynitride phosphor include a β-sialone type phosphor.

Of these, nitride phosphors, oxynitride phosphors, and Mn-activated compound fluoride complex phosphors are preferably used, and β-type sialone phosphors and Mn-activated compound fluoride complex phosphors are more preferably used. By using these phosphors, a high-luminance phosphor sheet can be obtained.

Further, the fluorescent substance sheet according to the embodiment of the present invention preferably contains a β-type sialone phosphor and a Mn-activated difluoride complex phosphor.

(Β-type sialone phosphor)
The β-type sialon is a solid solution of β-type silicon nitride, in which Al is substituted at the Si position and O is substituted at the N position of the β-type silicon nitride crystal. Since there are two types of atoms in the unit cell (unit cell) of β-type sialon, Si _6-z Al _{z Oz} N _8-z is used as a general formula. Here, z is 0 to 4.2. The solid solution range of β-type sialon is very wide, and the molar ratio of (Si, Al) / (N, O) needs to be maintained at 3/4. A general method for producing β-type sialon is a method in which silicon oxide and aluminum nitride, or aluminum oxide and aluminum nitride are added and heated in addition to silicon nitride.

β-type sialone is a β-type sialon that is excited by blue light from ultraviolet rays by incorporating luminescent elements such as rare earths (Eu, Sr, Mn, Ce, etc.) into the crystal structure and exhibits green light emission with a wavelength of 520 to 550 nm. It becomes a phosphor.

The β-type sialone phosphor used in the present invention preferably has a peak in the emission spectrum in the wavelength region of 535 to 550 nm. Within such a range, when the phosphor sheet according to the embodiment of the present invention is applied to the LED package, good light emission characteristics can be obtained. The average particle size of the β-type sialon phosphor is preferably 1 μm or more, more preferably 10 μm or more, and even more preferably 16 μm or more. Further, 100 μm or less is preferable, 50 μm or less is more preferable, and 19 μm or less is further preferable. Within such a range, when the phosphor sheet according to the embodiment of the present invention is applied to the LED package, good light emission characteristics can be obtained.

(KSF phosphor)
The Mn-activated compound fluoride complex phosphor is a phosphor having Mn as an activator and a fluoride complex salt of an alkali metal or an alkaline earth metal as a parent crystal. In this Mn-activated compound fluoride complex phosphor, the coordination center of the fluoride complex forming the parent crystal is preferably a tetravalent metal (Si, Ti, Zr, Hf, Ge, Sn), and around it. The number of coordinating fluorine atoms is preferably 6.

The Mn-activated compound fluoride complex phosphor is _{selected from the group consisting of the general formula A 2} MF ₆ : Mn (where A is Li, Na, K, Rb and Cs, and contains at least Na and / or K 1). It is an alkali metal of one or more species, and M is one or more tetravalent elements selected from the group consisting of Si, Ti, Zr, Hf, Ge and Sn). _K 2 _SiF in the general formula 6: what is Mn of KSF phosphor. As the Mn-activated difluoride complex phosphor used in the present invention, this KSF phosphor is preferable.

The average particle size of the Mn-activated difluoride complex phosphor is preferably 1 μm or more, more preferably 10 μm or more, and preferably 20 μm or more. Further, 100 μm or less is preferable, 70 μm or less is more preferable, and 40 μm or less is further preferable. Within such a range, when the phosphor sheet according to the embodiment of the present invention is applied to the LED package, good light emission characteristics can be obtained.

In the present invention, the average particle size is the median diameter (D50). The average particle size can be measured by observing the phosphor sheet with a scanning electron microscope (SEM). From the two-dimensional image obtained by observing the cross section of the phosphor sheet, the maximum distance between the two intersections of the straight line intersecting the outer edge of the phosphor particles at the two points is calculated, and this is calculated as the phosphor. Defined as the individual particle size of the particles. The particle size is calculated for 200 of the observed phosphor particles by this method, and in the particle size distribution obtained from the particle size distribution, the particle size of 50% of the accumulated passages from the small particle size side is defined as D50.

When targeting an LED light emitting device equipped with a phosphor sheet, a mechanical polishing method, a microtome method, a CP method (Cross-sect (I) on Pol (I) sher) and a focused ion beam (F (I) B) After polishing so that the cross section of the phosphor sheet can be observed by any of the processing methods, the above average particle diameter is calculated from the two-dimensional image obtained by observing the obtained cross section with an SEM. Can be done.

In the present invention, the content of the inorganic phosphor in the phosphor sheet is preferably 35% by weight or more, more preferably 40% by weight or more, and more preferably 60% by weight or more of the entire phosphor sheet. More preferred. By setting the phosphor content in the phosphor sheet in such a range, the brightness of the phosphor sheet can be increased. Although the upper limit of the phosphor content is not particularly specified, the content of the phosphor in the phosphor sheet is 90% by weight or less of the entire phosphor sheet from the viewpoint that a phosphor sheet having excellent workability can be easily produced. It is more preferably 85% by weight or less, further preferably 80% by weight or less, and even more preferably 70% by weight or less.

Examples of the fluorescent substance particularly preferably used in the present invention include an organic compound represented by the general formula (4) as an organic phosphor. The organic compound represented by the general formula (4) used in the present invention will be described below.

(Organic compound represented by the general formula (4))

In the general formula (4) representing an organic compound in the present embodiment, R ⁵ , R ⁶ , Ar ^{1 to} Ar ⁵ and L may be the same or different, and may be the same or different, hydrogen, alkyl group, cycloalkyl group, aralkyl group. , Alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, mercapto group, alkoxy group, alkylthio group, arylether group, arylthioether group, aryl group, heteroaryl group, heterocyclic group, halogen, haloalkyl group, haloalkenyl group, A fused ring and an aliphatic ring formed between a haloalkynyl group, a cyano group, an aldehyde group, a carbonyl group, a carboxyl group, an ester group, a carbamoyl group, an amino group, a nitro group, a silyl group, a siloxanyl group, and an adjacent substituent. Selected from. M represents an m-valent metal and is at least one selected from boron, beryllium, magnesium, chromium, iron, nickel, copper, zinc and platinum. In all the above groups, the hydrogen may be deuterium. This also applies to the organic compounds described below or their partial structures.

Further, in the following description, for example, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms is an aryl group having all 6 to 40 carbon atoms including the number of carbon atoms contained in the substituent substituted with the aryl group. It is a group. The same applies to other substituents that specify the number of carbon atoms.

Further, in all the above groups, the substituents in the case of substitution include an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a hydroxyl group, a thiol group, an alkoxy group and an alkylthio group. , Aryl ether group, aryl thioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, nitro group, silyl group, siroxanyl group, boryl A group and a phosphine oxide group are preferable, and a specific substituent which is preferable in the description of each substituent is preferable. Further, these substituents may be further substituted with the above-mentioned substituents.

"Unsubstituted" in the case of "substituted or unsubstituted" means that a hydrogen atom or a deuterium atom has been substituted. The same applies to the case of "substituted or unsubstituted" in the organic compound or its partial structure described below.

Further, among all the above groups, the alkyl group is a saturated aliphatic group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group. Indicates a hydrocarbon group. This alkyl group may or may not further have a substituent. The additional substituent when substituted is not particularly limited, and examples thereof include an alkyl group, an aryl group, and a heteroaryl group, and this point is also common to the following description. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably in the range of 1 or more and 20 or less, more preferably 1 or more and 8 or less from the viewpoint of availability and cost.

The cycloalkyl group refers to a saturated alicyclic hydrocarbon group such as cyclopropyl, cyclohexyl, norbornyl, adamantyl, etc., which may or may not have a substituent. The number of carbon atoms in the alkyl group moiety is not particularly limited, but is preferably in the range of 3 or more and 20 or less.

The aralkyl group refers to an aromatic hydrocarbon group mediated by an aliphatic hydrocarbon such as a benzyl group or a phenylethyl group. Both of these aliphatic hydrocarbons and aromatic hydrocarbons may be unsubstituted or have a substituent.

The alkenyl group refers to an unsaturated aliphatic hydrocarbon group containing a double bond such as a vinyl group, an allyl group, or a butadienyl group, which may or may not have a substituent. The carbon number of the alkenyl group is not particularly limited, but is usually in the range of 2 or more and 20 or less.

The cycloalkenyl group refers to an unsaturated alicyclic hydrocarbon group containing a double bond such as a cyclopentenyl group, a cyclopentadienyl group, a cyclohexenyl group, etc., which may have a substituent. You don't have to.

The alkynyl group refers to an unsaturated aliphatic hydrocarbon group containing a triple bond such as an ethynyl group, which may or may not have a substituent. The carbon number of the alkynyl group is not particularly limited, but is usually in the range of 2 or more and 20 or less.

The alkoxy group refers to a functional group to which an aliphatic hydrocarbon group is bonded via an ether bond such as a methoxy group, an ethoxy group, or a propoxy group, and even if the aliphatic hydrocarbon group has a substituent. You do not have to have it. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably in the range of 1 or more and 20 or less.

The alkylthio group is one in which the oxygen atom of the ether bond of the alkoxy group is replaced with a sulfur atom. The hydrocarbon group of the alkylthio group may or may not have a substituent. The number of carbon atoms of the alkylthio group is not particularly limited, but is usually in the range of 1 or more and 20 or less.

The aryl ether group refers to a functional group in which an aromatic hydrocarbon group is bonded via an ether bond, for example, a phenoxy group, and the aromatic hydrocarbon group may or may not have a substituent. Good. The number of carbon atoms of the aryl ether group is not particularly limited, but is preferably in the range of 6 or more and 40 or less.

The arylthio ether group is one in which the oxygen atom of the ether bond of the aryl ether group is replaced with a sulfur atom. The aromatic hydrocarbon group in the aryl ether group may or may not have a substituent. The number of carbon atoms of the aryl ether group is not particularly limited, but is usually in the range of 6 or more and 40 or less.

The aryl group indicates, for example, an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, a phenanthryl group, a triphenylenyl group and a terphenyl group. The aryl group may or may not have a substituent. The number of carbon atoms of the aryl group is not particularly limited, but is preferably in the range of 6 or more and 40 or less.

A heteroaryl group is one or more non-carbon atoms such as a furanyl group, a thiophenyl group, a pyridyl group, a quinolinyl group, a pyrazinyl group, a pyrimidinyl group, a triazinyl group, a naphthylyl group, a benzofuranyl group, a benzothiophenyl group and an indolyl group. It indicates a cyclic aromatic group having in the individual ring, which may be unsubstituted or substituted. The number of carbon atoms of the heteroaryl group is not particularly limited, but is preferably in the range of 2 or more and 30 or less.

The heterocyclic group refers to an aliphatic ring having an atom other than carbon such as a pyran ring, a piperidine ring, and a cyclic amide in the ring, which may or may not have a substituent. .. The number of carbon atoms of the heterocyclic group is not particularly limited, but is usually in the range of 2 or more and 20 or less.

The carbonyl group, carboxyl group, and carbamoyl group may or may not have a substituent. Here, examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group and the like, and these substituents may be further substituted.

The amino group is a substituted or unsubstituted amino group. The amino group may or may not have a substituent, and examples of the substituent in the case of substitution include an aryl group, a heteroaryl group, a linear alkyl group, a branched alkyl group and the like. .. As the aryl group and heteroaryl group, a phenyl group, a naphthyl group, a pyridyl group and a quinolinyl group are preferable. These substituents may be further substituted. The number of carbon atoms is not particularly limited, but is preferably 2 or more and 50 or less, more preferably 6 or more and 40 or less, and particularly preferably 6 or more and 30 or less.

Halogen refers to fluorine, chlorine, bromine or iodine. The haloalkyl group, haloalkenyl group, and haloalkynyl group refer to those in which a part or all of the above-mentioned alkyl group, alkenyl group, and alkynyl group, such as a trifluoromethyl group, are substituted with the above-mentioned halogen, and the rest. The part of may be unchanged or substituted. In addition, aldehyde groups, carbonyl groups, ester groups, and carbamoyl groups include those substituted with aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, heterocycles, etc., and further include aliphatic hydrocarbons, Aliphatic hydrocarbons, aromatic hydrocarbons, and heterocycles may be unsubstituted or substituted.

The silyl group refers to a functional group having a bond to a silicon atom such as a trimethylsilyl group, which may or may not have a substituent. The number of carbon atoms of the silyl group is not particularly limited, but is usually in the range of 3 or more and 20 or less. The number of silicon is usually 1 or more and 6 or less.

The siloxanyl group refers to a silicon compound group via an ether bond such as a trimethylsiloxanyl group. Substituents on silicon may be further substituted.

The organic compound represented by the general formula (4) as described above exhibits a high fluorescence quantum yield and has a small peak half-value width of the emission spectrum, so that both efficient color conversion and high color purity are achieved. can do.

Among the metal complexes in the organic compound represented by the general formula (4), the complex in which M is boron is particularly preferable in that the fluorescence quantum yield is high. Further, a boron trifluoride complex in which L is fluorine or a fluorine-containing aryl group and m-1 is 2, is particularly preferable in terms of availability of materials and ease of synthesis.

Further, any adjacent disubstituted groups (for example, R ⁵ and Ar ² of the general formula (4)) may be bonded to each other to form a conjugated or non-conjugated fused ring. The constituent elements of such a fused ring may contain elements selected from nitrogen, oxygen, sulfur, phosphorus and silicon in addition to carbon. Further, the condensed ring may be condensed with yet another ring.

The organic compound represented by the general formula (4) as described above can be subjected to luminous efficiency, color purity, thermal stability, photostability, dispersibility, etc. by introducing an appropriate substituent at an appropriate position. Various properties and physical properties can be adjusted.

^{For example, the substituent Ar 5} has a great influence on the durability of the organic compound represented by the general formula (4), that is, the decrease in the emission intensity of the organic compound with time. Specifically, when Ar ⁵ is hydrogen, the reactivity of this hydrogen is high, so that the hydrogen easily reacts with water and oxygen in the air. This causes the decomposition of ^{Ar 5.} Further, when Ar ⁵ is a substituent having a large degree of freedom of movement of the molecular chain such as an alkyl group, the reactivity is certainly lowered, but the organic compounds aggregate with time in the sheet, resulting in the result. This causes a decrease in emission intensity due to concentration dimming. Therefore, Ar ⁵ is preferably a group that is rigid, has a small degree of freedom of movement, and does not easily cause aggregation. Specifically, it is a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. It is preferable that it is one of the above.

^{Ar 5} is preferably a substituted or unsubstituted aryl group from the viewpoint of giving a higher fluorescence quantum yield, being more difficult to pyrolyze, and photostability. As the aryl group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group and an anthrasenyl group are preferable from the viewpoint of not impairing the emission wavelength.

Further, in order to enhance the photostability of the organic compound, it is necessary to appropriately suppress the twist of the carbon-carbon bond between ^{Ar 5 and the pyrromethene skeleton.} This is because if the twist is excessively large, the reactivity with the excitation light is increased and the photostability is lowered. From this point of view, Ar ⁵ is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, or a substituted or unsubstituted naphthyl group, and is preferably substituted or unsubstituted. It is more preferably a phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted terphenyl group. Particularly preferred is a substituted or unsubstituted phenyl group.

Further, Ar ⁵ is preferably a moderately bulky substituent. By having Ar ⁵ having a certain bulk height, it is possible to prevent molecular aggregation. As a result, the luminous efficiency and durability of the organic compound are further improved.

A more preferable example of such a bulky substituent is the structure of ^{Ar 5 represented by the following general formula (5).}

That is, in the general formula (4) representing the organic compound, Ar ⁵ is preferably a group represented by the general formula (5). In the ^{general formula (5) representing Ar 5} , r is a hydrogen, an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a hydroxyl group, a thiol group, an alkoxy group, an alkylthio group and an aryl. Ether group, arylthioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl group, Selected from the group consisting of phosphine oxide groups. k is an integer of 1-3. When k is 2 or more, r may be the same or different.

Of these groups, for example, the oxycarbonyl group may or may not have a substituent. Examples of the substituent of the oxycarbonyl group include an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group and the like, and these substituents may be further substituted.

From the viewpoint of being able to give a higher fluorescence quantum yield, r is preferably a substituted or unsubstituted aryl group. Among these aryl groups, a phenyl group and a naphthyl group are particularly preferable examples. When r is an aryl group, k in the general formula (5) is preferably 1 or 2, and k is more preferably 2 from the viewpoint of further preventing molecular agglutination. Further, when k is 2 or more, it is preferable that at least one of r is substituted with an alkyl group. As the alkyl group in this case, a methyl group, an ethyl group and a tert-butyl group are particularly preferable examples from the viewpoint of thermal stability.

Further, from the viewpoint of controlling the fluorescence wavelength and absorption wavelength and enhancing the compatibility with the solvent, r is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group or a halogen. , Methyl group, ethyl group, tert-butyl group, methoxy group are more preferable. From the viewpoint of dispersibility, a tert-butyl group and a methoxy group are particularly preferable. The fact that r is a tert-butyl group or a methoxy group is more effective in preventing quenching due to aggregation of molecules.

Compared to the case where Ar ^{1 to} Ar ^{4 are all hydrogen, when at least one of Ar 1 to} Ar ⁴ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. It shows better thermal and photostability.

When ^{at least one of Ar 1 to} Ar ⁴ is a substituted or unsubstituted aryl group, the aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, or a naphthyl group, and more preferably a phenyl group or a biphenyl group. is there. Particularly preferably, it is a phenyl group.

When ^{at least one of Ar 1 to} Ar ⁴ is a substituted or unsubstituted heteroaryl group, the heteroaryl group is preferably a pyridyl group, a quinolinyl group, or a thiophenyl group, and more preferably a pyridyl group or a quinolinyl group. Particularly preferred is a pyridyl group.

Further, in the general formula (4) representing the organic compound, Ar ^{1 to} Ar ⁴ may all be the same or different, and are a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. Is preferable. This is because it exhibits better thermal and photostability. In the phosphor composition or the like according to the present embodiment, when the organic compound converts the light emitted from the light emitter into light having a longer wavelength than the inorganic phosphor combined with the organic compound, the general formula (5) ^{All of Ar 1 to Ar 4} represented by 1 may be the same or different, and are more preferably substituted or unsubstituted aryl groups, and particularly preferably phenyl groups. In this case, for example, if the emitted light from the illuminant is blue light, the inorganic phosphor converts the blue light into green light, and the organic compound converts the blue light into the color of the inorganic phosphor. Converts to light with a longer wavelength, that is, red light.

Further, in the general formula (4) representing the organic compound, ^{at least one of Ar 1 to} Ar ⁴ is preferably a substituent represented by the general formula (6). As a result, both high color purity and durability can be achieved.

In the general formula (6), R ⁷ is selected from the group consisting of an alkyl group, a cycloalkyl group, an alkoxy group and an alkylthio group. n is an integer of 1 to 3. When n is 2 or more, each R ⁷ may be the same or different.

In the aryl group represented by the general formula (6), when R ⁷ is an electron donating group, it mainly affects the color purity, and is therefore preferable. Examples of the electron donating group include an alkyl group, a cycloalkyl group, an alkoxy group and an alkylthio group. In particular, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an aryl group substituted with an alkylthio group having 1 to 8 carbon atoms is preferable. When R ⁷ is an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, a higher color purity can be obtained, which is more preferable. Further, as the aryl group that mainly affects the light emission efficiency, an aryl group having a bulky substituent such as a t-butyl group or an adamantyl group is preferable.

Further, from the viewpoint of heat resistance and color purity, ^{it is preferable that Ar 1} and Ar ⁴ and Ar ² and Ar ³ are aryl groups having the same structure, respectively. Further, from the viewpoint of dispersibility, ^{at least one of Ar 1 to} Ar ⁴ is a group represented by the general formula (6), and R ⁷ is an alkyl group or an alkoxy group having 4 or more carbon atoms. More preferred. Among them, a t-butyl group, a methoxy group or a t-butoxy group is particularly preferable as an example of at least one of ^{Ar 1 to} Ar ^4.

In the general formula (6), n is preferably an integer of 1 to 3, and more preferably 1 or 2 from the viewpoint of easiness of obtaining raw materials and synthesizing.

On the other hand, in the general formula (4) representing the organic compound, ^{it is particularly preferable that Ar 1} ≠ Ar ² or Ar ³ ≠ Ar ⁴ because the dispersibility in the film is improved and high-efficiency light emission can be obtained. .. Here, "≠" indicates that the bases have different structures. For example, Ar ¹ ≠ Ar ² indicates that Ar ¹ and Ar ² are groups of different structures. Ar ³ ≠ Ar ⁴ indicates that Ar ³ and Ar ⁴ are groups of different structures. In other words, ^{Ar 1} ≠ Ar ² or Ar ³ ≠ Ar ⁴ does not mean that ^{"Ar 1} = Ar ² and Ar ³ = Ar ^4". That is, ^{among any combinations of Ar 1 to} Ar ⁴ , (1) Ar ¹ = Ar ² = Ar ³ = Ar ⁴ and (2) Ar ¹ = Ar ² and Ar ³ = Ar ^4. , Ar ¹ ≠ Ar ³ is excluded.

The aryl group represented by the general formula (6) affects various properties and physical properties such as luminous efficiency, color purity, heat resistance and light resistance of the organic compound represented by the general formula (4). There are some aryl groups that improve several properties, but none of them show sufficient performance. In particular, it is difficult to achieve both high luminous efficiency and high color purity. Therefore, if a plurality of types of aryl groups can be introduced into the organic compound represented by the general formula (4), it is expected that an organic compound having a good balance in light emission characteristics and color purity can be obtained.

An ^{organic compound of Ar 1} = Ar ² = Ar ³ = Ar ⁴ can have only one type of aryl group. Further, ^{in an organic compound in which Ar 1} = Ar ² and Ar ³ = Ar ⁴ and Ar ¹ ≠ Ar ³ , the aryl group having a specific physical property is biased to one pyrrole ring. In this case, it is difficult to maximize the physical characteristics of each aryl group as described later in relation to the luminous efficiency and the color purity.

On the other hand, in the organic compound according to the embodiment of the present invention, substituents having certain physical properties can be arranged on the left and right pyrrole rings in a well-balanced manner, and therefore, as compared with the case where the substituent is biased to one pyrrole ring. Therefore, it is possible to maximize the physical properties.

This effect is particularly excellent in improving the luminous efficiency and the color purity in a well-balanced manner. It is preferable that one or more aryl groups that affect the color purity are present in each of the pyrrole rings on both sides, because the conjugated system is expanded and high color purity light emission can be obtained. However, ^{an organic compound in which Ar 1} = Ar ² and Ar ³ = Ar ⁴ and Ar ¹ ≠ Ar ³ is the other when, for example, an aryl group affecting color purity is introduced into one pyrrole ring. When an aryl group that affects the light emission efficiency is introduced into the pyrrole ring, the aryl group that affects the color purity is biased to the pyrrole ring on one side, so that the conjugated system is not sufficiently expanded and the color purity is not sufficiently improved. Further, if an aryl group having a different structure, which also affects the color purity, is introduced into the other pyrrole ring, the luminous efficiency cannot be improved.

On the other hand, in the organic compound according to the embodiment of the present invention, one or more aryl groups that affect the color purity are introduced into the pyrrole rings on both sides, and the aryl groups that affect the luminous efficiency at other positions. Can be introduced. Therefore, the organic compound according to the embodiment of the present invention is preferable because it can maximize the properties of both color purity and luminous efficiency. It is preferable to introduce an aryl group that affects the color purity at the positions of Ar ² and Ar ^{3 because the conjugated system is most expanded.}

When ^{at least one of Ar 1 to} Ar ⁴ is a substituted or unsubstituted alkyl group, the alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert. -Alkyl groups having 1 to 6 carbon atoms such as a butyl group, a pentyl group and a hexyl group are preferable. Further, as this alkyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group are preferable from the viewpoint of excellent thermal stability. Further, from the viewpoint of preventing concentration quenching and improving the emission quantum yield, the tert-butyl group having a high sterically bulk is more preferable as the alkyl group. On the other hand, a methyl group is also preferably used as the alkyl group from the viewpoint of easiness of synthesis and availability of raw materials.

On the other hand, in the general formula (4) representing the above organic compound, Ar ^{1 to} Ar ⁴ may all be the same or different, and when they are substituted or unsubstituted alkyl groups, they are soluble in a binder resin or a solvent. Is preferable because it is good. In this case, as the alkyl group, a methyl group is preferable from the viewpoint of easiness of synthesis and availability of raw materials. For example, in the phosphor composition according to the present embodiment, when the organic compound converts the emitted light from the illuminant into light having a shorter wavelength than the inorganic phosphor combined with the organic compound, the general formula ( all Ar ¹ to Ar ⁴ represented in 4), which may be the same or different and each a substituted or unsubstituted alkyl group, preferably a methyl group. Specifically, if the emitted light from the illuminant is blue light, the inorganic phosphor converts this blue light into red light, and the organic compound converts this blue light into color conversion of this inorganic phosphor. Converts to light with a shorter wavelength, that is, green light.

In the general formula (4) representing such an organic compound, at least one of ^{R 5} and R ^{6 is hydrogen.} That is, R ⁵ and R ⁶ are preferably any one of hydrogen, alkyl group, carbonyl group, oxycarbonyl group and aryl group, but are hydrogen or alkyl group from the viewpoint of thermal stability. Is preferable. ^{In particular, at least one of R 5} and R ⁶ is more preferably hydrogen, from the viewpoint that a narrow full width at half maximum can be easily obtained in the emission spectrum.

Further, L is preferably an alkyl group, an aryl group, a heteroaryl group, a fluorine, a fluorine-containing alkyl group, a fluorine-containing heteroaryl group or a fluorine-containing aryl group. In particular, L is more preferably a fluorine or a fluorine-containing aryl group because it is stable to excitation light and a higher fluorescence quantum yield can be obtained. Further, L is more preferably fluorine because of its ease of synthesis.

Here, the fluorine-containing aryl group is an aryl group containing fluorine, and examples thereof include a fluorophenyl group, a trifluoromethylphenyl group, and a pentafluorophenyl group. The fluorine-containing heteroaryl group is a fluorine-containing heteroaryl group, and examples thereof include a fluoropyridyl group, a trifluoromethylpyridyl group, and a trifluoropyridyl group. The fluorine-containing alkyl group is an alkyl group containing fluorine, and examples thereof include a trifluoromethyl group and a pentafluoroethyl group.

Further, as another embodiment of the organic compound represented by the general formula (4), it is preferable that at least one of ^{R 5} , R ⁶ , and Ar ^{1 to} Ar ^{5 is an electron-withdrawing group.} In particular, (1) ^{at least one of R 1} , R ² , Ar ^{1 to} Ar ⁴ is an electron-withdrawing group, (2) Ar ⁵ is an electron-withdrawing group, or (3) R ⁵ , R ⁶ , Ar ^{1 to} Ar ⁴ are preferably at least one electron-withdrawing group, and Ar ⁵ is preferably an electron-withdrawing group. By introducing an electron-withdrawing group into the pyrromethene skeleton of an organic compound in this way, the electron density of the pyrromethene skeleton can be significantly reduced. As a result, the stability of the organic compound with respect to oxygen is further improved, and as a result, the durability of the organic compound can be further improved.

An electron-withdrawing group is also called an electron-accepting group, and is an atomic group that attracts electrons from an atomic group substituted by an inductive effect or a resonance effect in organic electron theory. Examples of the electron-withdrawing group include those having a positive value as the substituent constant (σp (para)) of Hammett's law. The constant of the substituent of Hammett's rule (σp (para)) can be quoted from the 5th edition of the Basics of Chemistry Handbook (page II-380). The phenyl group also has an example of taking a positive value as described above, but in the present invention, the electron-withdrawing group does not contain a phenyl group.

Examples of electron-withdrawing groups include -F (σp: +0.06), -Cl (σp: +0.23), -Br (σp: +0.23), -I (σp: +0.18),- CO ₂ R ¹² (σp: ^{+0.45 when R 12} is an ethyl group), -CONH ² (σp: +0.38), ^{-COR 12} (σp: ^{+0.49 when R 12} is a methyl group), -CF _{Examples thereof include 3} (σp: +0.50), −SO ₂ R ¹² (σp: ^{+0.69 when R 12} is a methyl group), −NO ₂ (σp: +0.81) and the like. R ¹² is independently a hydrogen atom, an aromatic hydrocarbon group having 6 to 30 substituted or unsubstituted ring-forming atoms, a heterocyclic group having 5 to 30 substituted or unsubstituted ring-forming atoms, substituted or absent. It represents a substituted alkyl group having 1 to 30 carbon atoms and a substituted or unsubstituted cycloalkyl group having 1 to 30 carbon atoms. Specific examples of each of these groups include the same examples as described above.

Preferred electron-withdrawing groups include fluorine, a fluorine-containing aryl group, a fluorine-containing heteroaryl group, a fluorine-containing alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted ester group, a substituted or unsubstituted amide group, and a substituent. Alternatively, an unsubstituted sulfonyl group or a cyano group can be mentioned. This is because they are difficult to decompose chemically.

More preferred electron-withdrawing groups include a fluorine-containing alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted ester group or a cyano group. This is because they have the effect of preventing concentration quenching and improving the emission quantum yield. A particularly preferred electron-withdrawing group is a substituted or unsubstituted ester group.

In the general formula (4) representing the organic compound, ^{at least one of R 5} and R ⁶ is preferably an electron-withdrawing group. This is because the stability of the organic compound represented by the general formula (4) with respect to oxygen can be improved without impairing the luminous efficiency and the color purity, and as a result, the durability of the organic compound can be improved. Because it can be done.

Further, in the ^{general formula (5) representing Ar 5 of the} organic compound, r is more preferably an electron-withdrawing group. This is because the stability of the organic compound represented by the general formula (4) with respect to oxygen is further improved without impairing the luminous efficiency and the color purity, and as a result, the durability of the organic compound can be significantly improved. Because it can be done.

As one of the preferable examples of the organic compound represented by the general formula (4), Ar ^{1 to} Ar ⁴ may all be the same or different, and are substituted or unsubstituted alkyl groups, and further, Ar. ⁵ can be cited is a group represented by the general formula (5). In this case, ^{it is particularly preferable that Ar 5} is a group represented by the general formula (5) in which r is contained as a substituted or unsubstituted phenyl group.

Further, as another preferable example of the organic compound represented by the general formula (4), Ar ^{1 to} Ar ⁴ may all be the same or different, and are selected from the above general formula (6). Further, ^{there is a case where Ar 5} is a group represented by the general formula (5). In this case, Ar ⁵ is more preferably a group represented by the general formula (5) in which r is contained as a tert-butyl group or a methoxy group, and is represented by the general formula (5) in which r is contained as a methoxy group. It is particularly preferable that the group is to be used.

An example of the organic compound represented by the general formula (4) is shown below, but the organic compound according to the present embodiment is not limited thereto.

The organic compound represented by the general formula (4) can be produced, for example, by the method described in JP-A-8-509471 and JP-A-2000-208262. That is, the desired pyrromethene-based metal complex can be obtained by reacting the pyrromethene compound and the metal salt in the presence of a base.

Regarding the synthesis of the pyrromethene-boron trifluoride complex, J. et al. Org. Chem. , Vol. 64, No. 21, pp7813-7819 (1999), Angew. Chem. , Int. Ed. Engl. , Vol. 36, The organic compound represented by the general formula (4) can be produced with reference to the method described in pp1333-1335 (1997) and the like.

The fluorescent composition according to the embodiment of the present invention may appropriately contain other compounds in addition to the organic compound represented by the general formula (4), if necessary. For example, an assist dopant such as rubrene may be contained in order to further increase the energy transfer efficiency from the excitation light to the organic compound represented by the general formula (4). Further, when it is desired to add a luminescent color other than the luminescent color of the organic compound represented by the general formula (4), a desired organic luminescent material such as a coumarin-based pigment, a perylene-based dye, a phthalocyanine-based dye, or a stillben-based dye is used. Compounds such as cyanine pigments, polyphenylene pigments, rhodamine pigments, pyridine pigments, pyromethene pigments, porphyrin pigments, oxazine pigments, and pyrazine pigments can be added. In addition to these organic light emitting materials, known light emitting materials such as inorganic phosphors, fluorescent pigments, fluorescent dyes, and quantum dots can be added in combination.

The following is an example of an organic light emitting material other than the organic compound represented by the general formula (4), but the present invention is not particularly limited thereto.

The content of the organic compound represented by the general formula (4) in the phosphor composition according to the embodiment of the present invention is prepared by the molar absorption coefficient of the organic compound, the fluorescence quantum yield and the absorption intensity at the excitation wavelength. Depending on the thickness and permeability of the film, it is usually ^10-5 weight percent to 10 weight percent, and even ^10-4 weight percent to 5 weight percent, based on the total weight of the fluorophore composition. It is preferably ^10-3 weight percent to 2 weight percent, especially preferably.

(solvent)
The fluorescent material sheet according to the embodiment of the present invention may contain a solvent. The solvent is not particularly limited as long as the viscosity of the fluid resin can be adjusted. Examples of this solvent include toluene, methyl ethyl ketone, methyl isobutyl ketone, hexane, acetone, terpineol, texanol, methyl cellsolve, butyl carbitol, butyl carbitol acetate, propylene glycol monomethyl ether acetate and the like.

(Other ingredients)
The fluorescent material sheet according to the embodiment of the present invention contains a dispersant and a leveling agent for stabilizing the coating film, and an adhesion auxiliary agent such as a silane coupling agent as a modifier on the surface of the fluorescent material sheet. You may.

In addition, the fluorescent material sheet according to the embodiment of the present invention may contain fine particles. Examples of the fine particles include silicone fine particles, titania, silica, alumina, silicone, zirconia, ceria, aluminum nitride, silicon carbide, silicon nitride, barium titanate and the like. Further, the fluorescent material sheet according to the embodiment of the present invention may contain a silanol group-containing methylphenyl silicone resin as a heat adhesive in order to reduce the storage elastic modulus G'at 100 ° C. Silicone fine particles, silica fine particles, and alumina fine particles are preferably used from the viewpoint of easy availability, and silicone fine particles are particularly preferably used.

Since the phosphor sheet according to the embodiment of the present invention contains silicone fine particles, not only adhesiveness and processability but also film thickness uniformity is improved. In particular, by using silicone fine particles having an average particle size (median type: D50) of 0.1 μm or more and 2.0 μm or less, the ejection property is excellent when a slit die coater is used, and the film thickness uniformity is excellent. A phosphor sheet can be obtained.

The average particle size of the silicone fine particles can be measured by the above-mentioned method in the same manner as the average particle size of the phosphor. The average particle size of the silicone fine particles is more preferably 0.5 μm or more as the lower limit. Further, the upper limit is more preferably 1.0 μm or less.

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 and then condensing organosilanes such as organotrialkoxysilane, organodialkoxysilane, organotriacetoxysilane, organodiacetoxysilane, organotrioxymsilane, and organodioxymsilane. preferable. Among these, in producing spherical organopolysilsesquioxane fine particles by hydrolyzing and condensing organosilane and / or a partial hydrolyzate thereof, a reaction as reported in JP-A-2003-342370. It is preferable to use the silicone fine particles obtained by the method of adding the polymer dispersant into the solution.

Further, in producing silicone fine particles, an organosilane and / or a partial hydrolyzate thereof is hydrolyzed and condensed, and a polymer dispersant and a salt acting as a protective colloid in a solvent are present 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 allow the condensation reaction to proceed can also be used.

The content of the silicone fine particles in the phosphor sheet is preferably 0.5% by weight or more, and more preferably 1% by weight or more of the entire phosphor sheet. The upper limit of the content of the silicone fine particles in the phosphor sheet is not particularly specified, but from the viewpoint of good mechanical properties, it is preferably 20% by weight or less, more preferably 10% by weight or less of the entire phosphor sheet. ..

(Base material)
The base material is an example of a support for a fluorescent material sheet in the present invention. The base material is not particularly limited, and for example, known metals, films, glass, ceramics, paper and the like can be used. Specifically, plates and foils of metals such as aluminum (including aluminum alloys), zinc, copper, and iron; cellulose acetate, polyethylene terephthalate (PET), polyethylene, polyester, polyamide, polyimide, polyphenylene sulfide, polystyrene, polypropylene, Plastic films such as polycarbonate, polyvinyl acetal, aramid, silicone, polyolefin, thermoplastic fluororesin, 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 and ethylene; a paper on which the plastic is laminated, a paper coated with the plastic, a paper on which the metal is laminated or vapor-deposited, a plastic film on which the metal is laminated or vapor-deposited, and the like. Can be mentioned. When the base material is a metal plate, the surface of the metal plate may be plated or ceramic-treated with a chromium-based or nickel-based material.

Among these, glass and plastic 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 in the form of a flexible film from the viewpoint of adhesion when the phosphor sheet is attached to the LED chip. Further, a film having high strength is preferable so that there is no risk of breakage when handling the film-like base material. Plastic films are preferable in terms of their required characteristics and economic efficiency. Among the plastic films, a plastic film selected from the group consisting of PET, polyphenylene sulfide, and polypropylene is preferable in terms of economy and handleability. Further, when the fluorescent material sheet is dried or when a high temperature of 200 ° C. or higher is required when the fluorescent material sheet is attached to the LED chip, a polyimide film is preferable in terms of heat resistance. The surface of the base material may be mold-released in advance because the phosphor sheet can be easily peeled off from the base material.

The thickness of the base material is not particularly limited, but the lower limit is preferably 25 μm or more, more preferably 38 μm or more. The upper limit is preferably 5000 μm or less, more preferably 3000 μm or less.

(Other layers)
The fluorescent material sheet according to the embodiment of the present invention may include a barrier layer. The barrier layer is appropriately used when improving the gas barrier property with respect to the phosphor sheet.

Examples of the barrier layer having a barrier function against oxygen include silicon oxide, aluminum oxide, tin oxide, indium oxide, yttrium oxide, magnesium oxide, etc., or a mixture thereof, or metal oxidation obtained by adding other elements to these. A film made of a substance; or a film made of various resins such as nylon, polyvinylidene chloride, and a copolymer of ethylene and vinyl alcohol can be mentioned.

Examples of the barrier layer having a barrier function against moisture include various resins such as polyethylene, polypropylene, nylon, polyvinylidene chloride, vinylidene chloride and vinyl chloride, a copolymer of vinylidene chloride and acrylonitrile, and a fluororesin. Can be mentioned.

Further, the phosphor sheet according to the embodiment of the present invention has an antireflection function, an antiglare function, an antireflection antiglare function, a light diffusion function, and a hard coat function (anti-reflection function) according to the functions required for the phosphor sheet. An auxiliary layer having a friction function), an antistatic function, an antifouling function, an electromagnetic wave shielding function, an infrared ray blocking function, an ultraviolet ray blocking function, a polarizing function, and a toning function may be further provided.

<Method of producing fluorescent sheet>
Hereinafter, an example of a method for producing a fluorescent material sheet according to an embodiment of the present invention will be described. The production method described below is an example, and the production method of the phosphor sheet is not limited to this.

First, as a coating liquid for forming a fluorescent material sheet, a composition in which a fluorescent material is dispersed in a silicone resin (hereinafter referred to as "fluorescent material composition") is prepared. The above-mentioned silicone resin, phosphor, and if necessary, additives such as silicone fine particles and a solvent are mixed in a predetermined amount. After mixing the above components to a predetermined composition, the mixture is homogeneously mixed and dispersed by a stirrer / kneader such as a homogenizer, a self-revolving stirrer, a three-roller, a ball mill, a planetary ball mill, and a bead mill. , A phosphor composition is obtained.

Defoaming under vacuum or reduced pressure conditions is also preferably performed after mixing and dispersing, or in the process of mixing and dispersing. Further, a specific component may be mixed in advance, or the finished fluorescent composition may be subjected to a treatment such as aging. It is also possible to remove the solvent from the mixture after mixing and dispersing by an evaporator to obtain a desired solid content concentration.

The fluorescent composition prepared by the above method is applied onto a substrate and dried to prepare a fluorescent sheet. 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, toe stream coater, rod coater, wire bar coater, applicator, dip. It can be performed by a coater, a curtain coater, a spin coater, a knife coater, or the like. In order to obtain the film thickness uniformity of the phosphor sheet, it is preferable to apply it with 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. In this case, the drying 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 dry in stages such as step cure.

After preparing the phosphor sheet, it is possible to change the base material as needed. In this case, as a simple method, a method of reattaching the base material using a hot plate, a method of reattaching the base material using a vacuum laminator or a dry film laminator, and the like can be mentioned.

<Application example of fluorescent sheet>
By attaching the phosphor sheet according to the embodiment of the present invention or a cured product thereof to the light emitting surface of the LED chip, an LED chip with a phosphor sheet is formed in which the phosphor sheet is laminated on the surface of the LED chip. it can. The LED chip to which the phosphor sheet according to the embodiment of the present invention can be applied is not particularly limited, and examples thereof include LED chips having a general structure such as lateral, vertical, and Philip chips. As such LED chips, vertical type and flip chip type LED chips having a large light emitting area are particularly preferable. The light emitting surface of the LED chip means a surface from which the light from the LED chip is taken out.

Here, the light emitting surface of the LED chip may or may not be a single plane. Examples of a single plane include an LED chip having only an upper light emitting surface. Specific examples thereof include a vertical type LED chip and an LED chip in which the side surface of the LED chip is covered with a reflective layer so that light is extracted only from the upper surface. On the other hand, examples of the case where the surface is not a single plane include an LED chip having an upper light emitting surface and a side light emitting surface, an LED chip having a curved light emitting surface, and the like.

Among these LED chips, an LED chip whose light emitting surface is not a single plane is preferable because it can be brightened by utilizing light emission from the side portion. 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 manufacturing process of the LED chip is easy. Further, the surface of the light emitting surface may be textured based on the optical design for improving the luminous efficiency of the LED chip.

The phosphor sheet according to the embodiment of the present invention may be directly attached to the LED chip, or may be attached via an adhesive such as a transparent resin. A method of directly attaching the phosphor sheet according to the embodiment of the present invention to the LED chip from the viewpoint that the light from the LED chip can be directly incident on the phosphor sheet without loss due to reflection or the like. However, it is more preferable. As a result, it is possible to obtain highly efficient and uniform white light with little color variation.

An LED package can be manufactured by mounting the LED chip with a phosphor sheet obtained by these methods on a wiring board provided with metal wiring or the like and packaging the LED chip. After that, by incorporating it into a module, it can be suitably used for various light emitting devices such as various types of lighting, liquid crystal backlights, and headlamps.

FIG. 1 shows a suitable example of the LED package according to the embodiment of the present invention. In FIG. 1A, the LED chip 1 to which the phosphor sheet 2 is attached is installed on the mounting substrate 5 provided with the reflector 4, and the upper surface portion of the LED chip 1 is sealed by the transparent sealing material 3. It is a thing.

In FIG. 1B, the LED chip 1 to which the phosphor sheet 2 is attached is installed on the mounting substrate 5 provided with the reflector 4, and the upper surface portion and the side surface portion of the LED chip 1 are sealed by the transparent sealing material 3. It was stopped.

In FIG. 1 (c), in the configuration shown in FIG. 1 (b), the phosphor sheet 2 is attached not only to the upper surface but also to the side surface of the LED chip 1. In this embodiment, the emission wavelength can be converted by the phosphor sheet 2 even for light emission from the side surface of the LED chip, which is preferable. Further, the upper surface of the transparent sealing material 3 is formed in a lens shape.

FIG. 1D shows an LED chip 1 to which a phosphor sheet 2 is attached, which is installed on a mounting substrate 5 not provided with a reflector and sealed by a transparent sealing material 3 molded into a lens shape. Is.

In FIG. 1 (e), the phosphor sheet 2 is attached not only to the upper surface of the LED chip 1 but also to the side surface in the configuration shown in FIG. 1 (d).

In FIG. 1 (f), in the configuration shown in FIG. 1 (c), a flip chip type LED chip 1 is used as the LED chip, and the phosphor sheet 2 is not only the upper surface and the side surface which are the light emitting surfaces of the LED chip 1. , It is attached so as to extend to the upper surface of the mounting substrate 5. In this configuration, the phosphor sheet 2 may be attached only to the upper surface and the side surface, which are the light emitting surfaces of the LED chip 1.

In FIG. 1 (g), in the configuration shown in FIG. 1 (d), the configurations of the LED chip 1 and the phosphor sheet 2 are the same as those shown in FIG. 1 (f).

In FIG. 1 (h), the LED chip 1 is installed so as to fit exactly on the portion of the mounting substrate 5 provided with the reflector 4 that does not have the reflector 4, and has the same width as the distance between the reflectors 4 on the upper part of the LED chip 1. The phosphor sheet 2 of No. 2 is attached via an adhesive 8 and further sealed with a transparent sealing material 3.

In FIG. 1 (i), in the configuration shown in FIG. 1 (h), the phosphor sheet 2 with the base material 9 is used as the phosphor sheet 2, and the base material 9 is not peeled off from the phosphor sheet 2. The phosphor sheet 2 is attached via the adhesive 8.

The LED package according to the embodiment of the present invention is not limited to these configurations. For example, the structure may be appropriately combined with the structures of the parts illustrated in FIGS. 1 (a) to 1 (i). Further, a configuration in which the structure of each part exemplified in FIGS. 1 (a) to 1 (i) is replaced with a known part other than these, or illustrated in FIGS. 1 (a) to 1 (i). The configuration may be a combination of the configuration and known parts.

The transparent sealing material 3 may be any material as long as it is excellent in molding processability, transparency, heat resistance, adhesiveness and the like. For example, known materials such as epoxy resin, silicone resin (including cured organopolysiloxane (crosslinked product) such as silicone rubber and silicone gel), urea resin, fluororesin, and polycarbonate resin can be used.

As the adhesive 8, the material used as the transparent sealing material described above can be used.

The material constituting the reflector 4 is not particularly limited, and examples thereof include a material used for the transparent sealing material 3 to which fine particles are added. Examples of the fine particles include titania, silica, alumina, silicone, zirconia, ceria, aluminum nitride, silicon carbide, silicon nitride, barium titanate and the like. Among these fine particles, silica fine particles, alumina fine particles, and titania fine particles are preferably used from the viewpoint of easy availability.

<Method of attaching a fluorescent material sheet, method of manufacturing an LED package using a fluorescent material sheet>
Next, a method of attaching the fluorescent material sheet according to the embodiment of the present invention to the LED chip and a method of manufacturing an LED package using the fluorescent material sheet according to the embodiment of the present invention will be described.

As will be described later, a typical method for manufacturing an LED package using a fluorescent material sheet according to an embodiment of the present invention is as follows: (1) The fluorescent material sheet is cut into individual pieces and then attached to individual LED chips. Method of attaching (for example, see FIG. 2), (2) Dying of the wafer after attaching the phosphor sheet to a large number of LED chips formed on the wafer (hereinafter, “wafer-level LED chips”) at once. And a method of cutting the phosphor sheet all at once (see, for example, FIG. 3), but the present invention is not limited to these. Hereinafter, these steps will be described with reference to FIGS. 2 and 3 as appropriate.

(Process of attaching the fluorescent material sheet to the LED chip)
The phosphor sheet according to the embodiment of the present invention is attached to the LED chip by pressurizing while heating at a desired temperature. This is pasting by heat crimping.

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 heating temperature to 60 ° C. or higher, it is easy to design a resin to increase the difference between the storage elastic modulus G'of the phosphor sheet at room temperature and the elastic modulus G'of the phosphor sheet at the attachment temperature. It becomes. Further, by setting the heating temperature to 250 ° C. or lower, the thermal expansion or contraction of the phosphor sheet can be reduced, so that the position accuracy of sticking can be improved.

In particular, when the phosphor sheet is pre-perforated to align with a predetermined portion on the LED chip, the positioning accuracy of the sticking is important. From the viewpoint of improving the positioning accuracy of pasting, the heating temperature is more preferably 160 ° C. or lower.

As a device for heat-pressing the fluorescent material sheet, any existing device can be used as long as it can be pressure-bonded at a desired temperature. As shown in FIGS. 2 (c) to 2 (d), when the individualized phosphor sheet is heat-bonded, for example, a heat-bonding tool such as a mounter or a flip-chip bonder can be used.

Further, as shown in FIGS. 3 (a) to 3 (b), when the phosphor sheets are collectively attached to the wafer level LED chips, heating having a vacuum laminator or a heated portion of about 100 to 200 mm square is provided. A crimping tool is available.

In either case, the fluorescent material sheet with a base material is pressure-bonded to the LED chip at a desired temperature to heat-fuse the fluorescent material sheet, and then the substrate is allowed to cool to room temperature to peel off the base material from the fluorescent material sheet. Since the phosphor sheet according to the embodiment of the present invention has the storage elastic modulus G'at 25 ° C and 100 ° C as described above, the fluorescent sheet after being allowed to cool to room temperature after heat fusion can be used. It can be easily peeled off from the base material while firmly adhering to the LED chip.

(Step of cutting the fluorescent material sheet)
There are two ways to cut the phosphor sheet: one is to cut it into individual pieces before attaching it to the LED chip, and the other is to attach the phosphor sheet to the wafer level LED chip and then dice the wafer and simultaneously cut the phosphor sheet. There is a way to disconnect.

As shown in FIG. 2, when the phosphor sheet is cut before being attached to the LED chip, the uniformly formed fluorescent sheet is processed into a predetermined shape by processing with a laser or cutting with a cutting tool. ,To divide. Since high energy is applied to the phosphor sheet in the laser processing, the resin in the phosphor sheet may be burnt or the phosphor may be deteriorated depending on the processing conditions. Therefore, as a method for cutting the phosphor sheet, cutting with a cutting tool is desirable.

As a cutting method with a blade, for example, there are a method of pushing a simple blade to cut and a method of cutting with a rotary blade, and any of them can be preferably used. As a device for cutting with a rotary blade, a device called a dicer, which is used for cutting (dicing) a semiconductor substrate into individual chips, can be preferably used. If a dicer is used, the width of the dividing line of the fluorescent material sheet can be precisely controlled by setting the thickness and conditions of the rotary blade, so that higher processing accuracy can be obtained than when cutting the fluorescent material sheet by simply pushing the blade. ..

When cutting the phosphor sheet laminated with the base material, the base material may be individualized, or the fluorescent material sheet may be individualized and the base material may not be cut. Alternatively, the phosphor sheet may be individualized and a notch line that does not penetrate the base material may be formed (so-called half-cut state).

When the fluorescent material sheet is separated together with the base material, the fluorescent material sheet of each piece can be attached to the LED chip by the above-mentioned method. At that time, the base material may be peeled off from the phosphor sheet before it is attached to the LED chip, or after it is attached to the LED chip. Further, the base material may be left as it is without being peeled from the phosphor sheet.

While the fluorescent material sheet is individualized, if the base material is not cut or is in a so-called half-cut state, the fluorescent material sheet of each piece is peeled off from the base material, and then individual LED chips are used by the above method. Can be pasted on.

As shown in FIG. 3, when a phosphor sheet is attached to a wafer-level LED chip and then the phosphor sheet is cut at the same time as dicing the wafer, it is formed into a predetermined shape by processing with a laser or cutting with a cutting tool. It can be divided into processed and individualized LED chips with a fluorescent material sheet. Of these cutting methods, cutting with a cutting tool is preferable.

(Specific example of manufacturing method of LED package using fluorescent material sheet)
FIG. 2 is an example of a series of steps in the case where the phosphor sheet is separated together with the base material and attached to the LED chip. The step of FIG. 2 includes a step of cutting the fluorescent material sheet into individual pieces and a step of attaching the fluorescent material sheet cut into the individual pieces to the LED chip.

FIG. 2A shows a phosphor sheet 2 laminated with the base material 9 fixed to the temporary fixing sheet 11. In the step shown in FIG. 2, since both the phosphor sheet 2 and the base material 9 are separated into individual pieces, they are fixed to the temporary fixing sheet 11 for easy handling. Next, as shown in FIG. 2B, the phosphor sheet 2 and the base material 9 are cut into individual pieces.

Subsequently, as shown in FIG. 2C, the individualized phosphor sheet 2 and the base material 9 are aligned on the LED chip 1 mounted on the mounting substrate 5. Then, as shown in FIG. 2D, the phosphor sheet 2 is crimped to the LED chip 1 at a desired temperature using the heat crimping tool 12. At this time, it is preferable that the crimping step is performed under vacuum or reduced pressure so that air is not caught between the phosphor sheet 2 and the LED chip 1. After crimping, allow to cool to room temperature.

Next, as shown in FIG. 2E, the base material 9 is peeled off from the phosphor sheet 2. Here, when the base material 9 is glass or the like, as shown in FIG. 2 (f), the base material 9 may be left as it is without being peeled off.

FIG. 3 is an example of a series of steps in the case where the phosphor sheet is collectively attached to the wafer level LED chip, and then the wafer dicing and the phosphor sheet are collectively cut. In the process of FIG. 3, a step of collectively attaching a phosphor sheet to a plurality of LED chips formed on a wafer, dicing of the wafer, and individualization of the LED chip to which the phosphor sheet is attached are performed. And is included in the process of performing all at once.

As shown in FIG. 3A, the phosphor sheet 2 laminated with the base material 9 is not preliminarily cut. The side of the phosphor sheet 2 is aligned with the wafer 13 having a plurality of LED chips (not shown) formed on the surface thereof.

Next, as shown in FIG. 3B, the phosphor sheet 2 is heat-bonded to a plurality of LED chips at a desired temperature by the heat-bonding tool 12. At this time, it is preferable that the heat crimping step is performed under vacuum or reduced pressure so that air is not caught between the phosphor sheet 2 and the LED chip. After heat crimping, allow to cool to room temperature.

Next, as shown in FIG. 3C, after the base material 9 is peeled from the fluorescent material sheet 2, the wafer 13 is diced and at the same time, the fluorescent material sheet 2 is cut into individual pieces. Then, as shown in FIG. 3D, an individualized LED chip 25 with a phosphor sheet is obtained.

Further, instead of the steps of FIGS. 3 (c) to 3 (d), as shown in FIG. 3 (e), the base material 9 was not peeled from the phosphor sheet 2, and as shown in FIG. 3 (f). The base material 9 may also be cut together with the phosphor sheet to be individualized. In this way, an individualized LED chip 26 with a base material and a phosphor sheet is obtained. In this case, when the base material 9 is glass or the like, it may be used as it is without peeling from the phosphor sheet 2. When the base material 9 is a plastic film, the base material 9 may be peeled off from the phosphor sheet 2 after the LED chip 26 is mounted on the substrate.

In any of the steps of FIGS. 2 and 3, when the phosphor sheet is attached to the LED chip having the electrode on the upper surface, it is necessary to remove the phosphor sheet in the portion corresponding to the electrode. Therefore, before attaching the phosphor sheet to the LED chip, it is preferable to pre-drill a hole in the portion of the phosphor sheet corresponding to the electrode. The phosphor sheet according to the embodiment of the present invention can be drilled with high precision.

That is, in the method for manufacturing an LED package according to the embodiment of the present invention, it is preferable to attach the phosphor sheet to a portion of the LED chip that avoids the electrodes on the light emitting surface.

The method of drilling is not particularly limited, but for example, a known method such as laser machining or die punching can be preferably used. Laser processing may cause burning of the resin in the phosphor sheet and deterioration of the phosphor depending on the processing conditions. Therefore, punching with a die is more desirable. When the punching process is performed, the punching process is impossible after the phosphor sheet is attached to the LED chip. Therefore, it is essential to perform the punching process before the phosphor sheet is attached to the LED chip.

In the punching process using a die, holes of any shape and size can be drilled by designing the die according to the shape and size of the electrodes provided on the LED chip. In an LED chip having a size of about 1 mm square, the size of the electrode on the upper surface is preferably 500 μm square or less so as not to reduce the area of the light emitting surface. Therefore, it is preferable that the pores formed on the phosphor sheet have a size of 500 μm square or less according to the size thereof. Further, when wire bonding or the like is performed between the electrode on the upper surface of the LED chip and the mounting substrate on which the LED chip is mounted, the upper surface electrode needs to have a certain size, for example, a size of at least about 50 μm square. Become. Therefore, it is preferable that the pores formed on the phosphor sheet have a size of about 50 μm square according to the size thereof.

If the size of the holes provided in the phosphor sheet is larger than the size of the electrodes, the light emitting surface may be exposed and light leakage may occur, resulting in deterioration of the color characteristics of the LED package. On the other hand, if the size of the electrode is too small, the wire may come into contact with the phosphor sheet during wire bonding, causing bonding failure. Therefore, in the hole drilling process with the phosphor sheet, it is preferable to process a small hole having a size of 50 μm square or more and 500 μm square or less with high accuracy within ± 10%.

When a phosphor sheet that has been cut or perforated as necessary is aligned and pasted on a predetermined part of the LED chip, a pasting device having an optical alignment mechanism is available. You will need it. At this time, it is work-wise difficult to align the phosphor sheet and the LED chip in close proximity to each other. Therefore, practically, it is often practiced to perform alignment with the phosphor sheet and the LED chip in light contact with each other.

At this time, if the fluorescent material sheet has adhesiveness, it is very difficult to move the fluorescent material sheet after it is brought into contact with the LED chip. On the other hand, the fluorescent sheet according to the embodiment of the present invention has no adhesiveness at room temperature, so that it is easy to align the fluorescent sheet and the LED chip in a light contact state.

The phosphor sheet according to the embodiment of the present invention can be further heat-treated by an oven or the like, if necessary, after being attached to the LED chip. By performing the heat treatment, the adhesion between the phosphor sheet and the LED chip can be further strengthened.

Further, the LED chips to which the phosphor sheet is attached can be bonded by heat crimping when they are collectively bonded to the mounting substrate, or can be soldered to the mounting substrate by solder reflow.

As another embodiment of the method for manufacturing an LED package using a phosphor sheet according to the embodiment of the present invention, a mass production method for manufacturing an LED package will be described. First, a method for manufacturing an LED chip with a phosphor sheet will be described. As a method of attaching the fluorescent material sheet to the LED chip, for example, as shown in FIG. 4, a method of attaching the individualized fluorescent material sheet laminate 14 to each individual LED chip 1 can be mentioned. Be done. Further, as shown in FIG. 5, there is a method in which the phosphor sheet 2 is attached to a plurality of LED chips 1 at once, the phosphor sheets 2 are coated, and then the package substrate 15 is cut to individualize the LED chips 1.

Next, two methods will be illustrated as still another embodiment of the method for manufacturing an LED package using the phosphor sheet according to the embodiment of the present invention.

The first manufacturing example is shown in FIG. This is a preferable example when the base material provided in the phosphor sheet has fluidity.

As shown in FIG. 6A, the LED chip 1 is temporarily fixed on the pedestal 18 via the double-sided adhesive tape 17. As shown in FIG. 6B, the fluorescent material sheet laminate 14 is laminated so that the fluorescent material sheet 2 is in contact with the LED chip 1.

As shown in FIG. 6 (c), the laminate of FIG. 6 (b) is placed in the lower chamber 20 of the vacuum diaphragm laminator 22, and then the upper chamber 19 and the lower chamber 20 are depressurized while heating. After heating under reduced pressure until the base material 9 flows, the diaphragm 21 is expanded by sucking air into the upper chamber 19 through the intake port 23. Then, the phosphor sheet 2 is pressed through the base material 9 and attached so as to follow the light emitting surface of the LED chip 1.

As shown in FIG. 6D, after returning the upper and lower chambers to atmospheric pressure, the laminate is taken out from the vacuum diaphragm laminator 22, and after allowing to cool, the base material 9 is peeled off from the phosphor sheet 2. Subsequently, the cutting portion 24 between the LED chips is cut with a dicing cutter or the like to produce an individualized LED chip 25 with a phosphor sheet.

As shown in FIG. 6E, the LED chip 25 with a phosphor sheet is bonded to the package electrode 16 on the mounting substrate 15 via the gold bump 7. By the above steps, the LED package 10 as shown in FIG. 6 (f) is manufactured.

A second production example is shown in FIG. This is another preferred example when the substrate provided on the fluorophore sheet has fluidity.

As shown in FIG. 7A, the LED chip 1 is bonded to the package electrode 16 on the mounting substrate 15 via the gold bump 7.

As shown in FIG. 7B, the fluorescent material sheet laminate 14 is laminated so that the fluorescent material sheet 2 is in contact with the LED chip 1.

As shown in FIG. 7 (c), after the laminate of FIG. 7 (b) is placed in the lower chamber 20 of the vacuum diaphragm laminator 22, the phosphor sheet 2 is attached to the LED chip by the same method as in the production example of FIG. Attach it to the light emitting surface of 1.

As shown in FIG. 7D, after returning the upper and lower chambers to atmospheric pressure, the laminate is taken out from the vacuum diaphragm laminator 22, and after allowing to cool, the base material 9 is peeled off from the phosphor sheet 2. Subsequently, the cut portion 24 between the LED packages is cut and separated into individual pieces. Through the above steps, the LED package 10 as shown in FIG. 7 (e) is manufactured.

<Light emitting device, backlight unit, display>
The light emitting device according to the embodiment of the present invention includes the above-mentioned phosphor sheet. For example, this light emitting device includes an LED package in which the above-mentioned phosphor sheet or a cured product thereof is provided on a light emitting surface of an LED chip.

The backlight unit according to the embodiment of the present invention is an application example of this light emitting device. For example, this backlight unit includes an LED package having the above-mentioned phosphor sheet or a cured product thereof. The backlight unit configured in this way can be used for applications such as displays, lighting, interiors, signs, and signboards, and is particularly preferably used for displays and lighting applications.

The display according to the embodiment of the present invention (for example, a liquid crystal display) is an application example of this backlight unit. For example, the display comprises an LED package having the above-mentioned fluorescent sheet or a cured product thereof.

Hereinafter, the present invention will be specifically described with reference to Examples. However, the present invention is not limited thereto.

<Base material>
BX9: Release-treated polyethylene terephthalate (polyethylene terephthalate film) "Therapeutic" BX9 (manufactured by Toray Film Processing Co., Ltd., average film thickness 50 μm)
<Inorganic phosphor>
-Fluorescent body 1 (YAG1):
"YAG81003" manufactured by Nemoto Lumimaterial Co., Ltd. (YAG phosphor)
-Fluorescent substance 2 (β1):
"GR-SW532D" manufactured by Denka Co., Ltd. (β-type Sialon phosphor)
Peak wavelength: 538 nm Average particle size (D50): 16 μm
-Fluorescent body 3 (KSF1):
KSF Fluorescent Sample A manufactured by Nemoto Lumimaterial Co., Ltd.
Average particle size (D50): 50 μm.

<Organic phosphor>
An example of synthesizing an organic phosphor is shown below. ^{1 1} H-NMR was measured in a deuterated chloroform solution using superconducting FTNMR EX-270 (manufactured by JEOL Ltd.). HPLC was measured with a 0.1 g / L chloroform solution using a high performance liquid chromatograph LC-10 (manufactured by Shimadzu Corporation). As a developing solvent for the column, a mixed solution of a 0.1% aqueous phosphoric acid solution and acetonitrile was used. For the absorption spectrum and the fluorescence spectrum, respectively, a U-3200 type spectrophotometer and an F-2500 type fluorescence spectrophotometer (both manufactured by Hitachi, Ltd.) were used in a 4 × 10 ^-6 mol / L dichloromethane solution. The measurement was performed.

(Synthesis Example 1)
The method for synthesizing the organic phosphor (T21) of Synthesis Example 1 will be described below. In the method for synthesizing the organic phosphor (T21), a mixed solution of 12.2 g of 4-t-butylbenzaldehyde, 11.3 g of 4-methoxyacetophenone, 32 ml of a 3M potassium hydroxide aqueous solution and 20 ml of ethanol is mixed under a nitrogen stream at room temperature for 12 hours. Stirred. The precipitated solid was collected by filtration and washed twice with 50 ml of cold ethanol. After vacuum drying, 17 g of 3- (4-t-butylphenyl) -1- (4-methoxyphenyl) propenone was obtained.

Next, a mixed solution of 17 g of 3- (4-t-butylphenyl) -1- (4-methoxyphenyl) propenone, 21.2 g of diethylamine, 17.7 g of nitromethane and 580 ml of methanol was heated under reflux for 14 hours under a nitrogen stream. did. The resulting solution was cooled to room temperature and then evaporated. After purification by silica gel column chromatography and vacuum drying, 16 g of 3- (4-t-butylphenyl) -1- (4-methoxyphenyl) -4-nitrobutane-1-one was obtained.

Next, a mixed solution of 230 ml of methanol and 46 ml of concentrated sulfuric acid was stirred at 0 ° C. under a nitrogen stream. A mixed solution of 1.42 g of pre-prepared 3- (4-t-butylphenyl) -1- (4-methoxyphenyl) -4-nitrobutane-1-one, 40 ml of methanol and 80 ml of tetrahydrofuran was added to potassium hydroxide under a nitrogen stream. 1.12 g of the powder was added, and the mixture was stirred at room temperature for 1 hour and slowly added dropwise, and the mixture was further stirred at room temperature for 1 hour. Then, after cooling to 0 ° C., 50 ml of water was added, neutralized with a 4M aqueous sodium hydroxide solution, and extracted with 50 ml of dichloromethane. The organic layer was washed twice with 30 ml of water, dried over sodium sulfate, and evaporated to obtain a viscous body.

Next, the obtained viscous material, a mixed solution of 1.54 g of ammonium acetate and 20 ml of acetic acid, was heated under reflux at 100 ° C. for 1 hour under a nitrogen stream. Then, after cooling to room temperature, ice water was added, the mixture was neutralized with a 4M aqueous sodium hydroxide solution, and extracted with 50 ml of dichloromethane. The organic layer was washed twice with 30 ml of water, dried over sodium sulfate, and then evaporated. After washing with 20 ml of ethanol and vacuum drying, 555 mg of 4- (4-t-butylphenyl) -2- (4-methoxyphenyl) pyrrole was obtained.

Next, 2-benzoyl-3,5-bis (4-t-butylphenyl) pyrrole 357 mg, 4- (4-t-butylphenyl) -2- (4-methoxyphenyl) pyrrole 250 mg, phosphorus oxychloride 138 mg. A mixed solution of 10 ml of 1,2-dichloroethane was heated and refluxed under a nitrogen stream for 9 hours. Then, after cooling to room temperature, 847 mg of diisopropylethylamine and 931 mg of boron trifluoride diethyl ether complex were added, and the mixture was stirred for 3 hours. 20 ml of water was injected and extracted with 30 ml of dichloromethane. The organic layer was washed twice with 20 ml of water, dried over magnesium sulfate, and then evaporated. After purification by silica gel column chromatography and vacuum drying, the organic phosphor (T21) shown below was synthesized.

^{1 1} H-NMR (CDCl ₃ (d = ppm)): 1.18 (s, 18H), 1.35 (s, 9H), 3.85 (s, 3H), 6.37-6.99 (m) , 17H), 7.45 (d, 2H), 7.87 (d, 4H).

(Synthesis Example 2)
The method for synthesizing the organic phosphor (T22) of Synthesis Example 2 will be described below. In the method for synthesizing the organic phosphor (T22), a mixed solution of 4- (4-t-butylphenyl) -2- (4-methoxyphenyl) pyrrole 300 mg, 2-methoxybenzoyl chloride 201 mg and toluene 10 ml is prepared under a nitrogen stream. It was heated at 120 ° C. for 6 hours. Then, after cooling to room temperature, it was evaporated. After washing with 20 ml of ethanol and vacuum drying, 260 mg of 2- (2-methoxybenzoyl) -3- (4-t-butylphenyl) -5- (4-methoxyphenyl) pyrrole was obtained.

Next, 2- (2-methoxybenzoyl) -3- (4-t-butylphenyl) -5- (4-methoxyphenyl) pyrrole 260 mg, 4- (4-t-butylphenyl) -2- (4-) A mixed solution of 180 mg of methoxyphenyl) pyrol, 206 mg of methanesulfonic anhydride and 10 ml of degassed toluene was heated at 125 ° C. for 7 hours under a nitrogen stream. Then, after cooling to room temperature, 20 ml of water was injected and extracted with 30 ml of dichloromethane. The organic layer was washed twice with 20 ml of water, evaporated and vacuum dried.

Next, a mixed solution of the obtained pyrromethene and 10 ml of toluene was added with 305 mg of diisopropylethylamine and 670 mg of boron trifluoride diethyl ether complex under a nitrogen stream, and the mixture was stirred at room temperature for 3 hours. Then, 20 ml of water was injected and extracted with 30 ml of dichloromethane. The organic layer was washed twice with 20 ml of water, dried over magnesium sulfate, and then evaporated. Purification was performed by silica gel column chromatography to synthesize the organic phosphor (T22) shown below.

^{1 1} H-NMR (CDCl ₃ (d = ppm)): 1.19 (s, 18H), 3.42 (s, 3H), 3.85 (s, 6H), 5.72 (d, 1H), 6.20 (t, 1H), 6.42-6.97 (m, 16H), 7.89 (d, 4H).

(Synthesis Example 3)
The method for synthesizing the organic phosphor (T23) of Synthesis Example 3 will be described below. In the method for synthesizing the organic phosphor (T23), in 30 ml of 1,2-dichloroethane, 5.0 g of 2- (2-methoxybenzoyl) -3,5-bis (4-t-butylphenyl) pyrrole, 2,4 3.3 g of -bis (4-t-butylphenyl) pyrrole and 1.5 g of phosphorus oxychloride were added, and the mixture was reacted under heating and recirculation for 12 hours. Then, after cooling to room temperature, 5.2 g of diisopropylethylamine and 5.6 g of boron trifluoride diethyl ether complex were added, and the mixture was stirred for 6 hours. After adding 50 ml of water and adding dichloromethane, the organic layer is extracted, concentrated, purified by column chromatography using silica gel, and further sublimated and purified to obtain the organic phosphor (T23) shown below. Synthesized.

^{1 1} H-NMR (CDCl ₃ (d = ppm)): 1.07 (s, 9H), 2.13 (s, 6H), 2.39 (s, 6H), 6.47 (t, 4H), 6.63 (s, 8H), 6.75 (d, 2H), 7.23 (d, 4H), 7.80 (d, 4H).

(Synthesis Example 4)
The method for synthesizing the organic phosphor (T24) of Synthesis Example 4 will be described below. In the method for synthesizing the organic phosphor (T24), 3,5-dibromobenzaldehyde (3.0 g), 4-t-butylphenylboronic acid (5.3 g), tetrakis (triphenylphosphine) palladium (0) (0). 4 g) and potassium carbonate (2.0 g) were placed in a flask and replaced with nitrogen. To this, degassed toluene (30 mL) and degassed water (10 mL) were added, and the mixture was refluxed for 4 hours. The reaction solution was cooled to room temperature, and the organic layer was separated and then washed with saturated brine. The organic layer was dried over magnesium sulfate, filtered, and then the solvent was distilled off. The obtained reaction product was purified by silica gel chromatography to obtain 3,5-bis (4-t-butylphenyl) benzaldehyde (3.5 g) as a white solid.

Next, 3,5-bis (4-t-butylphenyl) benzaldehyde (1.5 g) and 2,4-dimethylpyrrole (0.7 g) were added to the reaction solution, and dehydrated dichloromethane (200 mL) and trifluoroacetic acid (200 mL) were added. 1 drop) was added, and the mixture was stirred for 4 hours under a nitrogen atmosphere. Then, a dehydrated dichloromethane solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (0.85 g) was added, and the mixture was further stirred for 1 hour. After completion of the reaction, boron trifluorinated diethyl ether complex (7.0 mL) and diisopropylethylamine (7.0 mL) were added and stirred for 4 hours, then water (100 mL) was further added and stirred to separate the organic layer. did. The organic layer was dried over magnesium sulfate, filtered, and then the solvent was distilled off. The obtained reaction product was purified by silica gel chromatography to synthesize the organic phosphor (T24) shown below.

^{1 1} H-NMR (CDCl ₃ (d = ppm)): 7.95 (s, 1H), 7.63-7.48 (m, 10H), 6.00 (s, 2H), 2.58 (s) , 6H), 1.50 (s, 6H), 1.37 (s, 18H).

(Synthesis Example 5)
The method for synthesizing the organic phosphor (T25) of Synthesis Example 5 will be described below. In the method for synthesizing the organic phosphor (T25), the same as in Synthesis Example 4 except that ethyl 2,4-dimethylpyrrole-3-carboxylate was used as the pyrrole raw material instead of 2,4-dimethylpyrrole. An organic phosphor (T25) was synthesized.

(Synthesis Example 6)
The method for synthesizing the organic phosphor (T26) of Synthesis Example 6 will be described below. In the method for synthesizing the organic phosphor (T26), the same as in Synthesis Example 5 except that 4- (methoxycarbonyl) phenylboronic acid was used instead of 4-t-butylphenylboronic acid as the raw material for boronic acid. An organic phosphor (T26) was synthesized.

<Silicone resin>
The following silicone resins were used.

-Silicone resin 1 (Si1):
(A) component: 28.5 parts by weight, (B) component: 5.7 parts by weight (C) component: 66.0 parts by weight, (D) component: 0.03 parts by weight, reaction inhibitor: 0.025 parts by weight of component (A) _{(MeViSiO 2/2) 0.35 (Ph 2} SiO 2/2) 0.3 (PhSiO 3/2) 0.32 (SiO 4/2) 0.03
Component (B) _{(Me 3 SiO 1/2) 0.3 (} PhViSiO 2/2) 0.4 (PhSiO 3/2) 0.3
(C) Ingredient "HPM-502" (phenylmethylsiloxane copolymer) manufactured by Gerest Co., Ltd.
(D) Component Platinum complex (1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution) Platinum content 5% by weight
Reaction inhibitor 1-ethynylhexanol * However, Me: methyl group, Vi: vinyl group, Ph: phenyl group.

-Silicone resin 2 (Si2):
(A) component: 28.5 parts by weight, (B) component: 5.7 parts by weight (C) component: 66.0 parts by weight, (D) component: 0.03 parts by weight, reaction inhibitor: 0.025 parts by weight of component (A) _{(Me 3 SiO 1/2) 0.01 (} MeViSiO 2/2) 0.34 (Ph 2 SiO 2/2) 0.3 (PhSiO 3/2) 0.32 (SiO 4/2) 0.03
Component (B) _{(Me 3 SiO 1/2) 0.3 (} PhViSiO 2/2) 0.4 (PhSiO 3/2) 0.3
Component (C) (HMe ₂ SiO) ₂ SiPh ₂
(D) Component Platinum complex (1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution) Platinum content 5% by weight
Reaction inhibitor 1-ethynylhexanol
* However, Me: methyl group, Vi: vinyl group, Ph: phenyl group.

-Silicone resin 3 (Si3):
(A) component: 28.5 parts by weight, (B) component: 5.7 parts by weight (C) component: 66.0 parts by weight, (D) component: 0.03 parts by weight, reaction inhibitor: 0.025 parts by weight of component (A) _{(Me 3 SiO 1/2) 0.01 (} MeViSiO 2/2) 0.3 (Ph 2 SiO 2/2) 0.33 (PhSiO 3/2) 0.33 (SiO 4/2) 0.03
Component (B) _{(Me 3 SiO 1/2) 0.3 (} PhViSiO 2/2) 0.4 (PhSiO 3/2) 0.3
Component (C) (HMe ₂ SiO) ₂ SiPh ₂
(D) Component Platinum complex (1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution) Platinum content 5% by weight
Reaction inhibitor 1-ethynylhexanol
* However, Me: methyl group, Vi: vinyl group, Ph: phenyl group.

-Silicone resin 4 (Si4):
(A) component: 28.5 parts by weight, (B) component: 5.7 parts by weight (C) component: 66.0 parts by weight, (D) component: 0.03 parts by weight, reaction inhibitor: 0.025 parts by weight of component (A) _{(Me 3 SiO 1/2) 0.01 (} MeViSiO 2/2) 0.2 (Ph 2 SiO 2/2) 0.38 (PhSiO 3/2) 0.38 (SiO 4/2) 0.03
Component (B) _{(Me 3 SiO 1/2) 0.3 (} PhViSiO 2/2) 0.4 (PhSiO 3/2) 0.3
Component (C) (HMe ₂ SiO) ₂ SiPh ₂
(D) Component Platinum complex (1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution) Platinum content 5% by weight
Reaction inhibitor 1-ethynylhexanol
* However, Me: methyl group, Vi: vinyl group, Ph: phenyl group.

-Silicone resin 5 (Si5):
(A) component: 28.5 parts by weight, (B) component: 5.7 parts by weight (C) component: 66.0 parts by weight, (D) component: 0.03 parts by weight, reaction inhibitor: 0.025 parts by weight of component (A) _{(Me 3 SiO 1/2) 0.01 (} MeViSiO 2/2) 0.34 (Ph 2 SiO 2/2) 0.3 (PhSiO 3/2) 0.32 (SiO 4/2) 0.03
Component (B) _{(Me 3 SiO 1/2) 0.3 (} PhViSiO 2/2) 0.5 (PhSiO 3/2) 0.2
Component (C) (HMe ₂ SiO) ₂ SiPh ₂
(D) Component Platinum complex (1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution) Platinum content 5% by weight
Reaction inhibitor 1-ethynylhexanol
* However, Me: methyl group, Vi: vinyl group, Ph: phenyl group.

-Silicone resin 6 (Si6):
(A) component: 31.4 parts by weight, (B) component: 2.8 parts by weight (C) component: 66.0 parts by weight, (D) component: 0.03 parts by weight, reaction inhibitor: 0.025 parts by weight of component (A) _{(Me 3 SiO 1/2) 0.01 (} MeViSiO 2/2) 0.34 (Ph 2 SiO 2/2) 0.3 (PhSiO 3/2) 0.32 (SiO 4/2) 0.03
Component (B) _{(Me 3 SiO 1/2) 0.3 (} PhViSiO 2/2) 0.4 (PhSiO 3/2) 0.3
Component (C) (HMe ₂ SiO) ₂ SiPh ₂
(D) Component Platinum complex (1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution) Platinum content 5% by weight
Reaction inhibitor 1-ethynylhexanol
* However, Me: methyl group, Vi: vinyl group, Ph: phenyl group.

-Silicone resin 7 (Si7):
(A) component: 17.4 parts by weight, (B) component: 16.8 parts by weight (C) component: 66.0 parts by weight, (D) component: 0.03 parts by weight, reaction inhibitor: 0.025 parts by weight of component (A) _{(Me 3 SiO 1/2) 0.01 (} MeViSiO 2/2) 0.34 (Ph 2 SiO 2/2) 0.3 (PhSiO 3/2) 0.32 (SiO 4/2) 0.03
Component (B) _{(Me 3 SiO 1/2) 0.3 (} PhViSiO 2/2) 0.4 (PhSiO 3/2) 0.3
Component (C) (HMe ₂ SiO) ₂ SiPh ₂
(D) Component Platinum complex (1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution) Platinum content 5% by weight
Reaction inhibitor 1-ethynylhexanol
* However, Me: methyl group, Vi: vinyl group, Ph: phenyl group.

-Silicone resin 8 (Si8): OE6630 (Tole Dow Corning Silicone).

-Silicone resin 9 (Si9):
16.7 parts by weight of resin main component, 16.7 parts by weight of hardness adjuster, 66.7 parts by weight of cross-linking agent, 0.025 parts by weight of reaction inhibitor, 0.03 parts by weight of platinum catalyst Ingredients for blending 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 ((a) corresponding to component)
Hardness modifier _{ViMe 2 SiO (MePhSiO) 17.5 SiMe} 2 Vi ((B) corresponding to the component)
Crosslinking agent _{(HMe 2 SiO) 2 SiPh 2} ((C) corresponding to the component)
* 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) Platinum-containing Amount 5% by weight (corresponding to component (D)).

<Silicone fine particles>
A stirrer, a thermometer, a circulation tube, and a dropping funnel were attached to a 2 L four-necked round bottom flask. In the flask, 2 L of 2.5% aqueous ammonia containing 1 ppm of the polyether-modified siloxane "BYK333" as a surfactant was placed, and the temperature was raised in an oil bath while stirring at 300 rpm. When the internal temperature reached 50 ° C., 200 g of a mixture of methyltrimethoxysilane (MTM) and phenyltrimethoxysilane (PhTM) (MTM / PhTM = 23/77 mol%) was added dropwise from the dropping funnel over 30 minutes. .. After further stirring for 60 minutes at the same temperature, about 5 g of acetic acid (special grade reagent) was added. After stirring the mixture, filtration was performed to obtain particles on the filter. The particles were washed twice with 600 mL of water and once with 200 mL of methanol and filtered respectively. The cake on the filter was taken out, crushed, and freeze-dried for 10 hours to obtain 60 g of white powder. The obtained white powder was monodisperse spherical fine particles when observed by SEM. As a result of measuring the refractive index of these fine particles by the immersion method, it was 1.54. As a result of observing these fine particles with a cross-sectional TEM using a transmission electron microscope (TEM), it was confirmed that the inside of the particles was fine particles having a single structure.

<Dynamic modulus measurement>
The obtained phosphor sheet was cut into a circle having a diameter of 20 mm, the base material was peeled off, and then the storage elastic modulus was measured using the following apparatus.

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

<Evaluation of cutting workability>
The obtained fluorescent sheet was cut into 1 mm × 0.3 mm squares using a cutting device “GCUT” (manufactured by UHT) to prepare 100 pieces of fluorescent sheet. Individual phosphor sheets were observed with an optical microscope, and the number of samples with cracks or chips on the periphery was counted. The smaller the number of samples whose peripheral edges are cracked or chipped, the better the cutting processability. If the evaluation is B or higher, it is practically excellent.
S: 0 pieces Very good cutting workability A: 1 piece or more and 3 pieces or less Good cutting workability B: 4 pieces or more and 10 pieces or less There is no practical problem in cutting workability C: 11 pieces or more and 30 pieces or less Cutting work Poor D: 31 or more Cutting workability is very poor.

<Manufacturing method of LED package>
The obtained fluorescent sheet was cut into 1 mm × 0.3 mm squares using a cutting device “GCUT” (manufactured by UHT) to prepare 100 pieces of fluorescent sheet. Using a flip-chip bonding device (manufactured by Toray Engineering), individual fluorescent material sheets were vacuum-adsorbed with a collet and peeled off from the substrate. The peeled individual phosphor sheet was attached to the surface of the LED chip of the LED package on which the flip-chip type LED chip was mounted under the following attachment conditions. The obtained package was connected to a DC power supply and turned on, and it was confirmed whether or not the light was turned on.

(Paste condition)
Heating conditions: 140 ° C
Pressurization condition: 80N
Pressurization time: 20 seconds.

<Adhesiveness evaluation>
Using the obtained LED package, a twill set was placed at the interface between the LED chip and the phosphor sheet, and then the phosphor sheet was lifted with the tweezers to confirm the adhesiveness between the LED chip and the phosphor sheet. A sample with good adhesiveness does not peel off the phosphor sheet even when lifted with tweezers. For samples with poor adhesiveness, the phosphor sheet will peel off from the LED chip. Observation with an optical microscope was performed, and the number of samples with peeling was counted. The smaller the number of peeled samples, the better the adhesiveness. If the evaluation is B or higher, it is practically excellent.
S: 0 pieces Very good adhesiveness A: 1 piece or more and 5 pieces or less Good adhesiveness B: 6 pieces or more and 10 pieces or less Adhesiveness is practically no problem C: 11 pieces or more and 30 pieces or less Poor adhesiveness D : 31 or more Adhesiveness is very poor.

<Total luminous flux measurement>
The LED chip was turned on by applying 1 W of power to the produced LED package, and the total luminous flux (lm) was measured using a total luminous flux measurement system (HM-3000, manufactured by Otsuka Electronics Co., Ltd.). The relative brightness was calculated when the total luminous flux in Comparative Example 1 was 100.

(Example 1) (Effect of silicone composition)
Using a polyethylene container having a volume of 100 ml, 18.0 g of silicone resin 1 (Si1), 42.0 g of phosphor 1 (YAG1) as an inorganic phosphor, and 2.5 g of butyl carbitol were added and mixed. Then, using a planetary stirring / defoaming device, the mixture was stirred / defoamed at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times with 3 rolls to prepare a fluorescent composition 1.

Using a slit die coater, the phosphor composition 1 is applied onto the release-treated surface of the base material "Therapeutic" BX9, heated at 120 ° C. for 40 minutes, dried, and fluorescent with a thickness of 80 μm and 100 mm square. I got a body sheet. The dynamic elastic modulus was measured and the cut workability was evaluated by the method described above. In addition, an LED package was produced by the method described above, and adhesiveness was evaluated and total luminous flux was measured. The results are shown in Table 1. The result was that the cutting processability was good, the adhesiveness was also improved, and the relative brightness was also improved.

(Example 2) (Change of silicone resin)
A phosphor sheet was produced by the same operation as in Example 1 except that the silicone resin was changed to Si2, and then an LED package was produced, and each measurement and evaluation was performed. The results are shown in Table 1. As shown in Table 1, from the evaluation results of Example 2, it was found that the fluorescent sheet according to the embodiment of the present invention has good cutting processability and adhesiveness. It was also found that the relative brightness was also improved.

(Comparative Example 1)
A phosphor sheet was produced by the same operation as in Example 1 except that the silicone resin was changed to Si8, and then an LED package was produced, and each measurement and evaluation was performed. The results are shown in Table 1. As shown in Table 1, in Comparative Example 1, there was no practical problem in cutting workability, but the adhesiveness was not improved.

(Example 3) (Change of silicone resin, addition of silicone fine particles)
Using a polyethylene container with a volume of 100 ml, 17.0 g of silicone resin 2 (Si2), 42.0 g of phosphor 1 (YAG1) as an inorganic phosphor, 0.6 g of silicone fine particles, and 2.5 g of butyl carbitol. Added and mixed. Then, using a planetary stirring / defoaming device, the mixture was stirred / defoamed at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times with 3 rolls to prepare a fluorescent composition 3.

Using a slit die coater, the phosphor composition 3 is applied onto the release-treated surface of the base material "Therapeutic" BX9, heated at 120 ° C. for 40 minutes, dried, and fluorescent to a thickness of 80 μm and 100 mm square. I got a body sheet. The dynamic elastic modulus was measured and the cut workability was evaluated by the method described above. In addition, an LED package was produced by the method described above, and adhesiveness was evaluated and total luminous flux was measured. The results are shown in Table 1. Good results were obtained in both cutting processability and adhesiveness, and relative brightness was also improved.

(Examples 4 to 8) (Change of silicone composition)
As shown in Table 1, a phosphor sheet was produced by the same operation as in Example 3 except that the silicone resin was changed to Si3 to Si7, respectively, and then an LED package was produced, and each measurement and evaluation was performed. went. The results are shown in Table 1. As shown in Table 1, from the evaluation results of Examples 4 to 8, it was found that the fluorescent sheet according to the embodiment of the present invention has good cutting processability and improved adhesiveness. It was also found that the relative brightness was also improved.

(Comparative Example 2)
As shown in Table 1, a phosphor sheet was prepared by the same operation as in Example 3 except that the silicone resin was changed to Si9, and then an LED package was prepared, and each measurement and evaluation was performed. The results are shown in Table 1. In Comparative Example 2, the cutting processability was not a problem in practical use, but the adhesiveness was not improved. Also, the brightness did not improve.

(Example 9) (Resin content changed to 10.0% by weight)
Using a polyethylene container with a volume of 100 ml, 5.96 g of silicone resin 2 (Si2), 53.6 g of phosphor 1 (YAG1) as an inorganic phosphor, 0.6 g of silicone fine particles, and 2.5 g of butyl carbitol. It was added and mixed. Then, using a planetary stirring / defoaming device, the mixture was stirred / defoamed at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times with 3 rolls to prepare a fluorescent composition 11.

Using a slit die coater, the phosphor composition 11 is applied onto the release-treated surface of the base material "Therapeutic" BX9, heated at 120 ° C. for 40 minutes, dried, and fluorescent with a thickness of 80 μm and 100 mm square. I got a body sheet. The dynamic elastic modulus was measured and the cut workability was evaluated by the method described above. In addition, an LED package was produced by the method described above, and adhesiveness was evaluated and total luminous flux was measured. The results are shown in Table 2. Good results were obtained in both cutting processability and adhesiveness, and relative brightness was also improved.

(Example 10) (Resin content changed to 70.0% by weight)
Using a polyethylene container with a volume of 100 ml, 42.4 g of silicone resin 2 (Si2), 17.5 g of phosphor 1 (YAG1) as an inorganic phosphor, 0.6 g of silicone fine particles, and 2.5 g of butyl carbitol. It was added and mixed. Then, using a planetary stirring / defoaming device, the mixture was stirred / defoamed at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times with 3 rolls to prepare a fluorescent composition 12.

Using a slit die coater, the phosphor composition 12 is applied onto the release-treated surface of the base material "Therapeutic" BX9, heated at 120 ° C. for 40 minutes, dried, and fluorescent with a thickness of 80 μm and 100 mm square. I got a body sheet. The dynamic elastic modulus was measured and the cut workability was evaluated by the method described above. In addition, an LED package was produced by the method described above, and adhesiveness was evaluated and total luminous flux was measured. The results are shown in Table 2. Good results were obtained in both cutting processability and adhesiveness, and relative brightness was also improved.

(Example 11) (Resin content changed to 85.0% by weight)
Using a polyethylene container with a volume of 100 ml, 52.5 g of silicone resin 2 (Si2), 8.6 g of phosphor 1 (YAG1) as an inorganic phosphor, 0.6 g of silicone fine particles, and 2.5 g of butyl carbitol. It was added and mixed. Then, using a planetary stirring / defoaming device, the mixture was stirred / defoamed at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times with 3 rolls to prepare a fluorescent composition 13.

Using a slit die coater, the phosphor composition 13 is applied onto the release-treated surface of the base material "Therapeutic" BX9, heated at 120 ° C. for 40 minutes, dried, and fluorescent with a thickness of 80 μm and 100 mm square. I got a body sheet. The dynamic elastic modulus was measured and the cut workability was evaluated by the method described above. In addition, an LED package was produced by the method described above, and adhesiveness was evaluated and total luminous flux was measured. The results are shown in Table 2. Good results were obtained in both cutting processability and adhesiveness, and relative brightness was also improved.

(Example 12) (Silicone fine particle content is changed to 0.5% by weight)
Using a polyethylene container with a volume of 100 ml, 17.0 g of silicone resin 2 (Si2), 42.0 g of phosphor 1 (YAG1) as an inorganic phosphor, 0.3 g of silicone fine particles, and 2.5 g of butyl carbitol. It was added and mixed. Then, using a planetary stirring / defoaming device, the mixture was stirred / defoamed at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times with 3 rolls to prepare a fluorescent composition 14.

Using a slit die coater, the phosphor composition 14 is applied onto the release-treated surface of the base material "Therapeutic" BX9, heated at 120 ° C. for 40 minutes, dried, and fluorescent with a thickness of 80 μm and 100 mm square. I got a body sheet. The dynamic elastic modulus was measured and the cut workability was evaluated by the method described above. In addition, an LED package was produced by the method described above, and adhesiveness was evaluated and total luminous flux was measured. The results are shown in Table 2. Good results were obtained in both cutting processability and adhesiveness, and relative brightness was also improved.

(Example 13) (Silicone fine particle content is changed to 10.0% by weight)
Using a polyethylene container having a volume of 100 ml, 11.0 g of silicone resin 2 (Si2), 42.0 g of phosphor 1 (YAG1) as an inorganic phosphor, 6 g of silicone fine particles, and 2.5 g of butyl carbitol were added. And mixed. Then, using a planetary stirring / defoaming device, the mixture was stirred / defoamed at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times with 3 rolls to prepare a fluorescent composition 15.

Using a slit die coater, the phosphor composition 15 is applied onto the release-treated surface of the base material "Therapeutic" BX9, heated at 120 ° C. for 40 minutes, dried, and fluorescent with a thickness of 80 μm and 100 mm square. I got a body sheet. The dynamic elastic modulus was measured and the cut workability was evaluated by the method described above. In addition, an LED package was produced by the method described above, and adhesiveness was evaluated and total luminous flux was measured. The results are shown in Table 2. Good results were obtained in both cutting processability and adhesiveness, and relative brightness was also improved.

(Example 14) (Silicone fine particle content is changed to 20.0% by weight)
Using a polyethylene container with a volume of 100 ml, add 6 g of silicone resin 2 (Si2), 42.0 g of phosphor 1 (YAG1) as an inorganic phosphor, 12 g of silicone fine particles, and 2.5 g of butyl carbitol and mix them. did. Then, using a planetary stirring / defoaming device, the mixture was stirred / defoamed at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times with 3 rolls to prepare a fluorescent composition 16.

Using a slit die coater, the phosphor composition 16 is applied onto the release-treated surface of the base material "Therapeutic" BX9, heated at 120 ° C. for 40 minutes, dried, and fluorescent to a thickness of 80 μm and 100 mm square. I got a body sheet. The dynamic elastic modulus was measured and the cut workability was evaluated by the method described above. In addition, an LED package was produced by the method described above, and adhesiveness was evaluated and total luminous flux was measured. The results are shown in Table 2. Good results were obtained in both cutting processability and adhesiveness, and relative brightness was also improved.

(Example 15) (The phosphor content was changed to 38.0% by weight)
Using a polyethylene container with a volume of 100 ml, 36.4 g of silicone resin 2 (Si2), 22.7 g of phosphor 1 (YAG1) as an inorganic phosphor, 0.6 g of silicone fine particles, and 2.5 g of butyl carbitol. It was added and mixed. Then, using a planetary stirring / defoaming device, the mixture was stirred / defoamed at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times with 3 rolls to prepare a fluorescent composition 17.

Using a slit die coater, the phosphor composition 17 is applied onto the release-treated surface of the base material "Therapeutic" BX9, heated at 120 ° C. for 40 minutes, dried, and fluorescent with a thickness of 80 μm and 100 mm square. I got a body sheet. The dynamic elastic modulus was measured and the cut workability was evaluated by the method described above. In addition, an LED package was produced by the method described above, and adhesiveness was evaluated and total luminous flux was measured. The results are shown in Table 3. Good results were obtained in both cutting processability and adhesiveness, and relative brightness was also improved.

(Example 16) (The phosphor content was changed to 40.0% by weight)
Using a polyethylene container with a volume of 100 ml, 35.2 g of silicone resin 2 (Si2), 23.8 g of phosphor 1 (YAG1) as an inorganic phosphor, 0.6 g of silicone fine particles, and 2.5 g of butyl carbitol. It was added and mixed. Then, using a planetary stirring / defoaming device, the mixture was stirred / defoamed at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times with 3 rolls to prepare a fluorescent composition 18.

Using a slit die coater, the phosphor composition 18 is applied onto the release-treated surface of the base material "Therapeutic" BX9, heated at 120 ° C. for 40 minutes, dried, and fluorescent with a thickness of 80 μm and 100 mm square. I got a body sheet. The dynamic elastic modulus was measured and the cut workability was evaluated by the method described above. In addition, an LED package was produced by the method described above, and adhesiveness was evaluated and total luminous flux was measured. The results are shown in Table 3. Good results were obtained in both cutting processability and adhesiveness, and relative brightness was also improved.

(Example 17) (The phosphor content was changed to 63.0% by weight)
Using a polyethylene container with a volume of 100 ml, 21.5 g of silicone resin 2 (Si2), 37.6 g of phosphor 1 (YAG1) as an inorganic phosphor, 0.6 g of silicone fine particles, and 2.5 g of butyl carbitol. It was added and mixed. Then, using a planetary stirring / defoaming device, the mixture was stirred / defoamed at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times with 3 rolls to prepare a fluorescent composition 19.

Using a slit die coater, the phosphor composition 19 is applied onto the release-treated surface of the base material "Therapeutic" BX9, heated at 120 ° C. for 40 minutes, dried, and fluorescent with a thickness of 80 μm and 100 mm square. I got a body sheet. The dynamic elastic modulus was measured and the cut workability was evaluated by the method described above. In addition, an LED package was produced by the method described above, and adhesiveness was evaluated and total luminous flux was measured. The results are shown in Table 3. Good results were obtained in both cutting processability and adhesiveness, and relative brightness was also improved.

(Example 18) (The phosphor content is changed to 80.0% by weight)
Using a polyethylene container with a volume of 100 ml, 11.3 g of silicone resin 2 (Si2), 47.7 g of phosphor 1 (YAG1) as an inorganic phosphor, 0.6 g of silicone fine particles, and 2.5 g of butyl carbitol. It was added and mixed. Then, using a planetary stirring / defoaming device, the mixture was stirred / defoamed at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times with 3 rolls to prepare a fluorescent composition 20.

Using a slit die coater, the phosphor composition 20 is applied onto the release-treated surface of the base material "Therapeutic" BX9, heated at 120 ° C. for 40 minutes, dried, and fluorescent with a thickness of 80 μm and 100 mm square. I got a body sheet. The dynamic elastic modulus was measured and the cut workability was evaluated by the method described above. In addition, an LED package was produced by the method described above, and adhesiveness was evaluated and total luminous flux was measured. The results are shown in Table 3. Good results were obtained in both cutting processability and adhesiveness, and relative brightness was also improved.

(Comparative Example 3)
A phosphor sheet was prepared by the same operation as in Example 15 except that the silicone resin was changed to Si9, and then an LED package was prepared, and each measurement and evaluation was performed. The results are shown in Table 3. As shown in Table 3, the cutting workability was not a problem in practical use, but the adhesiveness was not improved.

(Comparative Example 4)
A phosphor sheet was prepared by the same operation as in Example 16 except that the silicone resin was changed to Si9, and then an LED package was prepared, and each measurement and evaluation was performed. The results are shown in Table 3. As shown in Table 3, the cutting workability was not a problem in practical use, but the adhesiveness was not improved.

(Comparative Example 5)
A phosphor sheet was produced by the same operation as in Example 17 except that the silicone resin was changed to Si9, and then an LED package was produced, and each measurement and evaluation was performed. The results are shown in Table 3. As shown in Table 3, the cutting workability was not a problem in practical use, but the adhesiveness was not improved.

(Comparative Example 6)
A phosphor sheet was prepared by the same operation as in Example 18 except that the silicone resin was changed to Si9, and then an LED package was prepared, and each measurement and evaluation was performed. The results are shown in Table 3. As shown in Table 3, the cutting processability was lowered and the adhesiveness was not improved.

(Example 19) (Change of phosphor-1)
Using a polyethylene container with a volume of 100 ml, 17.0 g of silicone resin 2 (Si2), 16.8 g of phosphor 2 (β1) as an inorganic phosphor, 25.2 g of phosphor 3 (KSF1), and silicone fine particles. 0.6 g and 2.5 g of butyl carbitol were added and mixed. Then, using a planetary stirring / defoaming device, the mixture was stirred / defoamed at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times with 3 rolls to prepare a fluorescent composition 25.

Using a slit die coater, the phosphor composition 25 is applied onto the release-treated surface of the base material "Therapeutic" BX9, heated at 120 ° C. for 30 minutes, dried, and fluorescent with a thickness of 80 μm and 100 mm square. I got a body sheet. The dynamic elastic modulus was measured and the cut workability was evaluated by the method described above. In addition, an LED package was produced by the method described above, and adhesiveness was evaluated and total luminous flux was measured. The results are shown in Table 4. Very good results were obtained in both cutting processability and adhesiveness, and the relative brightness was also greatly improved.

(Comparative Example 7)
A phosphor sheet was produced by the same operation as in Example 19 except that the silicone resin was changed to Si9, and then an LED package was produced, and each measurement and evaluation was performed. The results are shown in Table 4. As shown in Table 4, the cutting workability was not a problem in practical use, but the adhesiveness was not improved.

(Example 20) (Change of phosphor-2)
Using a polyethylene container with a volume of 100 ml, 60.0 g of silicone resin 2 (Si2), 1.24 × 10 ^-3 g of phosphor 4 (type 21) as an organic phosphor, and phosphor 5 (type 24). 1.24 × 10 ^-3 g, 1.0 g of silicone fine particles, and 2.5 g of butyl carbitol were added and mixed. Then, using a planetary stirring / defoaming device, stirring / defoaming was performed at 1000 rpm for 5 minutes to prepare a fluorescent composition 27.

Using a slit die coater, the phosphor composition 27 is applied onto the release-treated surface of the base material "Therapeutic" BX9, heated at 120 ° C. for 30 minutes, dried, and fluorescent with a thickness of 80 μm and 100 mm square. I got a body sheet. The dynamic elastic modulus was measured and the cut workability was evaluated by the method described above. In addition, an LED package was produced by the method described above, and adhesiveness was evaluated and total luminous flux was measured. The results are shown in Table 5. Very good results were obtained in both cutting processability and adhesiveness, and the relative brightness was also improved.

(Examples 21 to 24) (Change of phosphor-3)
In Examples 21 to 24, fluorescent composition (28 to 32) was prepared by the same operation as in Example 20 except that the organic phosphor was appropriately changed as shown in Table 5, and each of them was used in Examples. A phosphor sheet was prepared by the same operation as in No. 20. After that, LED packages were prepared using each of them and evaluated. The results are shown in Table 5. From the evaluation results of Examples 21 to 24, it was found that very good results were obtained in both cutting processability and adhesiveness, and the relative brightness was improved.

(Comparative Example 8)
The phosphor composition 33 was prepared by the same operation as in Example 20 except that the silicone resin was changed to Si9 and the phosphors were changed to phosphor 4 (type 27) and phosphor 5 (type 28). A sheet was prepared. After that, an LED package was manufactured, and each measurement and evaluation was performed. The results are shown in Table 5. As shown in Table 5, the cutting workability was not a problem in practical use, but the adhesiveness was not improved.

1 LED chip 2 Phosphor sheet 3 Transparent encapsulant 4 Reflector 5 Mounting substrate 6 Electrode 7 Gold bump 8 Transparent adhesive 9 Base material 10 LED package 11 Temporary fixing sheet 12 Heat crimping tool 13 Wafer with LED chip formed on the surface 14 Phosphor sheet laminate 15 Package substrate 16 Package electrode 17 Double-sided adhesive tape 18 Pedestal 19 Upper chamber 20 Lower chamber 21 Diaphragm 22 Vacuum diaphragm laminator 23 Intake / exhaust port 24 Cut part 25 LED chip with phosphor sheet 26 Fluorescent material with base material LED chip with seat

Claims (18)

A phosphor sheet containing a phosphor and a silicone resin, which has a storage elastic modulus G'at 0.01 MPa or more and 100 ° C. when measured at an angular frequency of 1 Hz and an angular velocity of 6.2832 rad / sec. 'Do Ri, and less than 0.01MPa is, the storage modulus G when heated to 140 ° C.' storage modulus G when heated to become more than 0.05 MPa, the silicone resin is at least the following ( crosslinked product der Ru phosphor sheet crosslinkable silicone composition comprising a) ~ (D) component.
(A) Average unit formula:

(In the average unit formula (1), R ¹ is a monovalent hydrocarbon group having 1 to 14 carbon atoms, at least one is an aryl group, and at least one is an alkenyl having 2 to 6 carbon atoms. The group. R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. A, b, c, d, and e are 0 ≦ a ≦ 0.1 and 0.2 ≦ b ≦ 0.9. , 0.1 ≦ c ≦ 0.6, 0 ≦ d ≦ 0.2, 0 ≦ e ≦ 0.1, and a + b + c + d + e = 1.
Organopolysiloxane having a branched structure represented by
(B) Average unit formula:

(In the average unit formula (2), R ³ is a monovalent hydrocarbon group having 1 to 14 carbon atoms, at least one of which is an aryl group, and at least one of which is an alkenyl having 2 to 6 carbon atoms. The groups f, g and h are numbers that satisfy 0.1 <f ≦ 0.4, 0.2 ≦ g ≦ 0.5, 0.2 ≦ h ≦ 0.5, and f + g + h = 1. )
Organopolysiloxane having a branched structure represented by
(C) Organopolysiloxane having at least two Si—H bonds in one molecule and 12 to 70 mol% of organic groups bonded to silicon atoms are aryl groups.
(D) Catalyst for hydrosilylation reaction (B) the content of the component, the component (A) 100 weight 10 parts by weight or more relative to portion, or less 95 parts by weight, the phosphor sheet according to claim 1, wherein. (C) Component is average unit formula:

(In the average unit formula (3), R ⁴ is an aryl group, an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group. However, 12 to 70 mol% of ^{R 4 is an aryl group.)}
The fluorescent material sheet according to claim 1 or 2 , which is an organopolysiloxane represented by. The fluorescent material sheet according to any one of claims 1 to 3 , wherein the content of the fluorescent material is 40% by weight or more and 90% by weight or less. The fluorophore is selected from the group consisting of β-type sialone fluorophore and general formula A ₂ MF ₆ : Mn (where A is Li, Na, K, Rb and Cs, and contains at least Na and / or K). is one or more alkali metals, M is Si, Ti, Zr, Hf, is at least one tetravalent element selected from the group consisting of Ge and Sn. Mn activated double fluoride complex phosphor represented by) The fluorescent material sheet according to any one of claims 1 to 4 , which comprises a body. The fluorescent material sheet according to any one of claims 1 to 3 , wherein the fluorescent material is a pyrromethene compound. The fluorescent material sheet according to claim 6 , wherein the fluorescent material is a compound represented by the general formula (4).

(R ⁵ , R ⁶ , Ar ^{1 to} Ar ⁵ and L may be the same or different, hydrogen, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, mercapto group, Alkoxy group, alkylthio group, arylether group, arylthioether group, aryl group, heteroaryl group, heterocyclic group, halogen, haloalkane, haloalkene, haloalkyne, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group. , Amino group, nitro group, silyl group, siroxanyl group, fused ring formed between adjacent substituent and aliphatic ring. M represents m-valent metal, boron, berylium, magnesium, It is at least one selected from chromium, iron, nickel, copper, zinc and platinum.) The phosphor sheet according to claim 7 , wherein M in the general formula (4) is boron, L is fluorine or a fluorine-containing aryl group, and m-1 is 2. The fluorescent material sheet according to claim 7 or 8 ^{, wherein Ar 5} is a group represented by the general formula (5) in the general formula (4).

(R is hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, thiol group, alkoxy group, alkylthio group, arylether group, arylthioether group, aryl group, hetero It is selected from the group consisting of an aryl group, a halogen, a cyano group, an aldehyde group, a carbonyl group, a carboxyl group, an oxycarbonyl group, a carbamoyl group, an amino group, a nitro group, a silyl group, a siloxanyl group, a boryl group and a phosphinoxide group. Is an integer from 1 to 3. When k is 2 or more, r may be the same or different.) An LED chip comprising the phosphor sheet according to any one of claims 1 to 9 or a cured product thereof. An LED package comprising the fluorescent material sheet according to any one of claims 1 to 9 or a cured product thereof. A method for manufacturing an LED package, which comprises a step of cutting the fluorescent substance sheet according to any one of claims 1 to 9 into individual pieces, and a step of attaching the fluorescent substance sheet cut into the individual pieces to an LED chip. The method for manufacturing an LED package according to claim 12 , wherein the phosphor sheet is attached to a portion of the LED chip that avoids electrodes on the light emitting surface. The step of collectively attaching the phosphor sheet according to any one of claims 1 to 9 to a plurality of LED chips formed on the wafer, the dicing of the wafer, and the phosphor sheet being attached. A method for manufacturing an LED package, which comprises a step of collectively performing individualization of LED chips. The method for manufacturing an LED package according to any one of claims 12 to 14 , wherein the heating temperature when the phosphor sheet is attached to the LED chip is 60 ° C. or higher and 250 ° C. or lower. A light emitting device including the LED package according to claim 11. A backlight unit including the LED package according to claim 11. A display comprising the LED package according to claim 11.

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