TW201840722A - Phosphor sheet, led chip using same, led package using same, method for producing led package, and light emitting device, backlight unit and display, each of which comprises said led package - Google Patents

Abstract

The present invention is able to provide a phosphor sheet which has excellent workability such as cutting workability, while exhibiting good adhesion to an LED chip. The present invention is a phosphor sheet which contains a phosphor and a silicone resin, and which has a storage elastic modulus at 25 DEG C of 0.01 MPa or more, a storage elastic modulus at 100 DEG C of less than 0.01 MPa and a storage elastic modulus G' at 140 DEG C of 0.05 MPa or more.

Description

Phosphor sheet, LED chip and LED package using the same, manufacturing method of LED package, light emitting device including LED package, backlight unit, and display

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

Light Emitting Diode (LED) is based on the significant improvement of its luminous efficiency, and has the characteristics of low power consumption, long life, design, etc., not only for backlights for Liquid Crystal Display (LCD), Or in the on-vehicle field, such as the headlights of cars, and for general lighting, they are eager to expand the market. The environmental load of LEDs is also low, so it is expected that a huge market will be formed in the general lighting field in the future.

The emission spectrum of an LED depends on the semiconductor material forming the LED wafer, so its emission color is limited. Therefore, in order to use LEDs to obtain white light for LCD backlighting or general illumination, it is necessary to arrange an inorganic phosphor suitable for each wafer on the LED chip to convert the emission wavelength. Specifically, the following methods have been proposed: a method in which a yellow phosphor is provided on an LED chip emitting blue light; a method in which a red phosphor and a green phosphor are provided on an LED chip emitting blue light, and the like.

As one of the specific methods for arranging a phosphor on an LED chip, a method of attaching a sheet containing a phosphor (hereinafter referred to as a "phosphor sheet") to an LED chip has been proposed (for example, refer to Patent Documents) 1 to Patent Document 4). This method is easier to distribute the phosphors arranged on the LED chip than the method of dispersing the phosphor composition having the phosphor dispersed in the resin on the LED chip and curing it, which is currently in practical use. The amount is set to a certain amount. As a result, it is excellent in that the color or brightness of the obtained white LED can be made uniform. [Prior Art Literature] [Patent Literature]

[Patent Literature 1] Japanese Patent Laid-Open No. 2009-235368 [Patent Literature 2] Japanese Patent Laid-Open No. 2010-123802 [Patent Literature 3] Japanese Patent No. 2011-102004 [Patent Literature 4] Japanese Patent No. 5287935 Bulletin

[Problems to be Solved by the Invention] When a method of attaching a phosphor sheet to an LED chip is used, it is necessary to perform a cutting process when the phosphor sheet is singulated to the size of the LED chip, or In the phosphor sheet, a hole corresponding to an electrode portion or the like on the LED wafer is subjected to a drilling process or the like. Therefore, a phosphor sheet excellent in workability is required.

On the other hand, in order to be attached to an LED chip, the phosphor sheet is required to have adhesiveness. Patent Document 4 discloses that by using a silicone composition containing a specific organic polysiloxane, it is possible to obtain an excellent processability before attaching to an LED chip and an adhesiveness when attaching to an LED chip. Also excellent phosphor sheet. However, after the phosphor sheet was attached to the LED chip, the adhesiveness of the phosphor sheet was insufficient, and sufficient adhesion was not obtained. Therefore, there is a problem that the brightness of the LED chip to which the phosphor sheet is attached is poor due to poor adhesion.

An object of the present invention is to provide a phosphor sheet that achieves both the processability such as cutting and the adhesion to an LED wafer in order to solve the problems. [Means for solving problems]

That is, the present invention is a phosphor sheet comprising a phosphor and a silicone resin. The phosphor sheet has a storage elastic modulus G ′ at 25 ° C. of 0.01 MPa or more and a storage elastic modulus at 100 ° C. The number G 'is less than 0.01 MPa, and the storage elastic modulus G' at 140 ° C is 0.05 MPa or more. [Effect of the invention]

According to the present invention, it is possible to provide a phosphor sheet which is excellent in workability such as cutting and has good adhesiveness to an LED wafer.

Hereinafter, preferred embodiments of the phosphor sheet, the LED chip and the LED package using the same, the method for manufacturing the LED package, and the light emitting device, the backlight unit, and the display including the LED package will be described in detail. However, the present invention is not limited to the following embodiments, and can be implemented with various changes in accordance with the purpose or application.

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

The phosphor elastic sheet according to the embodiment of the present invention has a storage elastic modulus G ′ of at least 0.01 MPa at 25 ° C., thereby being sufficiently elastic at room temperature (25 ° C.). Therefore, it is possible to cut the phosphor sheet without deformation around the cutting portion with respect to rapid shear stress such as cutting processing using a blade body, and it is possible to obtain workability with high dimensional accuracy.

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 of the sample.

The phosphor elastic sheet according to the embodiment of the present invention has a storage elastic modulus G ′ of less than 0.01 MPa at 100 ° C., whereby the sheet has sufficient viscosity at 100 ° C. and 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 will rapidly flow and deform according to the shape of the light emitting surface of the LED chip. High adhesion between the phosphor sheet and the LED chip is obtained. Thereby, the light exportability 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 during heat-adhesion on the LED chip, it cannot be maintained at the time of attachment Since the shape previously processed by cutting or opening, the lower limit of the storage elastic modulus G ′ is preferably 0.005 MPa or more.

The storage elastic modulus G 'of the phosphor sheet according to the embodiment of the present invention at 140 ° C. is 0.05 MPa or more, so that the LED chip can be stably operated finally. When a phosphor sheet having this physical property is heated at 140 ° C. or higher, complete hardening of the sheet is completed quickly and the entire resin is integrated, so the adhesion between the phosphor sheet and the LED chip is improved. As a result, the brightness of the LED package is also improved. In addition, since the interface portion between the LED chip and the fluorescent sheet is hardly affected by the heat when the LED is turned on, peeling of the LED chip and the fluorescent sheet is suppressed. Therefore, the reliability of the LED package is improved.

The storage elastic modulus G ′ described here refers to a storage elastic modulus G ′ when a dynamic viscoelasticity measurement (temperature dependence) of a phosphor sheet is performed using a rheometer. The so-called dynamic viscoelasticity refers to the following method: When a shearing strain is applied to a material at a certain sinusoidal frequency, the shear stress that occurs when the material reaches a steady state is decomposed into components consistent with the phase of the strain (elasticity Components) and components (viscous components) that differ from the strain phase by 90 ° to analyze the dynamic mechanical properties of the material.

For dynamic viscoelasticity measurement (temperature dependence), dynamic viscoelasticity measurement can be performed using a general viscosity / viscoelasticity measuring device. In the present invention, the values are measured when measured under the following conditions.

Measuring device: Viscosity and viscoelasticity measuring device HAAKE MARSIII (manufactured by Thermo Fisher SCIENTIFIC) Measuring conditions: OSC temperature-dependent measuring geometry: Parallel disc type (20 mm) Measuring time: 1980 second angular frequency: 1 Hz angular velocity: 6.2832 rad / sec temperature range: 25 ℃ ～ 200 ℃ (with low temperature control function) heating rate: 0.08333 ℃ / sec sample shape: round (18 mm diameter) 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 thickness of the sample is less than 50 μm, a plurality of sheets can be superposed and heat-pressed on a 100 ° C. hot plate to form an integrated film (sheet) to produce a sample of a desired thickness.

The storage elastic modulus G 'is obtained by dividing the stress component whose phase is consistent with the shear strain by the shear strain. The storage elastic modulus G ′ is an elasticity of a material against dynamic strain at each temperature, and is related to the hardness of the phosphor sheet. Therefore, the storage elastic modulus G 'at each measurement temperature affects the following characteristics related to the phosphor sheet. For example, the storage elastic modulus G 'affects the processability of the phosphor sheet at 25 ° C, the flowability and adhesion of the phosphor sheet at 100 ° C, and the hardening and curing properties of the phosphor sheet at 140 ° C. Then sex.

The thickness of the phosphor sheet according to the embodiment of the present invention is not particularly limited, but it 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, even more preferably 100 μm or less, and still more 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 it is 200 μm or less, the heat resistance is particularly excellent.

The phosphor sheet according to the embodiment of the present invention may be a laminated body including other layers, if necessary. Examples of the other layers include a base material and a barrier layer.

(Silicon Resin) The phosphor sheet according to the embodiment of the present invention mainly includes a silicone resin in terms of transparency and heat resistance.

As the silicone resin used in the present invention, a curable silicone resin is preferred. The hardening type silicone resin may be composed of any one-liquid type or two-liquid type (three-liquid type). Examples of the hardening type silicone resin include a dealcoholization type, a deoxime type, a deacetic acid type, and a dehydroxyamine type, which are types that undergo a condensation reaction by moisture or catalyst in the air. In addition, there is an addition reaction type which is a type in which a hydrosilylation reaction occurs by a catalyst. Any of these types of hardened silicone resins can be used. In particular, the addition reaction type silicone resin is more preferable in terms of no by-products accompanying the hardening reaction, small hardening shrinkage, and easy to accelerate hardening by heating.

As an example, an addition reaction type silicone resin is formed by a hydrosilylation reaction of 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, and Bornyltrimethoxysilane, octenyltrimethoxysilane, etc. Examples of the "compound having a hydrogen atom bonded to a silicon atom" include methylhydropolysiloxane, dimethylpolysiloxane-CO-methylhydropolysiloxane, and ethylhydropolysiloxane. Oxane, methyl hydrogen polysiloxane-CO-methylphenyl polysiloxane, etc. Examples of the addition reaction type silicone resin include those formed by a hydrosilylation reaction of such a material. In addition, as the silicone resin, for example, a known person described in Japanese Patent Application Laid-Open No. 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, in the silicone resin, the crosslinked product of the present composition is preferably 20% by weight or more, more preferably 50% by weight or more, and even more preferably 80% by weight or more.

(A) Average unit formula:

[Chemical 1]

(In the average unit formula (1), R ¹ is a monovalent hydrocarbon group having 1 to 14 carbons, at least one is an aryl group, and at least one is an alkenyl group having 2 to 6 carbons; R ² is a hydrogen atom or a carbon number 1 ~ 6 alkyl groups; a, b, c, d, and e satisfy 0 ≦ a ≦ 0.1, 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) The organopolysiloxane having a branch structure represented by the number).

(B) Average unit formula:

[Chemical 2]

(In the average unit formula (2), R ³ 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 group having 2 to 6 carbon atoms; f, g, and h satisfy 0.1 < f ≦ 0.4, 0.2 ≦ g ≦ 0.5, 0.2 ≦ h ≦ 0.5, and f + g + h = 1), and the organopolysiloxane having a branched structure is represented.

(C) An organic polysiloxane having at least two Si-H bonds in one molecule, and 12 to 70 mol% of an organic group bonded to a silicon atom being an aryl group.

(D) Catalyst for hydrosilylation.

The organopolysiloxane of the component (A) has an aryl group, thereby improving compatibility with the components (B) to (D). In addition, the organopolysiloxane of the component (A) has an alkenyl group having 2 to 6 carbon atoms, whereby a cross-linking reaction of the components (A) to (C) can occur. In addition, the organopolysiloxane of the component (A) has a branched structure, whereby the hardenability is improved, and good adhesion to the LED chip can be obtained.

The so-called branched structure means a structure in which a basic constituent unit has a T unit (RSiO _3/2 ) or a Q unit (SiO _4/2 ) in an 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 referred to as a T unit, and an organic substituent represented by R is not attached to a silicon atom. A tetrafunctional unit is called a Q unit.

Since the branched structure is incorporated in the organopolysiloxane of the component (A), the crosslinking reaction speed is increased, and good hardenability can be obtained in the phosphor sheet.

The existence of the branched structure in the organopolysiloxane can be confirmed by performing a method such as methyl orthoformate decomposition on the organopolysiloxane, and then performing nuclear magnetic resonance (NMR) analysis or coagulation. Gel permeation chromatography (GPC) -multi-angle light scattering (MALS) analysis.

Especially in GPC-MALS analysis, the molecular weight distribution and rotation radius of the organopolysiloxane can be obtained. Therefore, the existence of a branched structure can be confirmed by identifying a structure with a small rotation radius in the organopolysiloxane of the same molecular weight component.

In the average unit formula (1), each value of a, b, c, d, and e is sufficient for the obtained crosslinked product to obtain sufficient hardness at room temperature and softening at high temperature to implement the scope of the present invention.

The organopolysiloxane of the component (B) has an aryl group, thereby being compatible with the component (A). Thereby, the mechanical strength and transparency of the cured film of the phosphor sheet containing the silicone resin can be maintained. In addition, the organopolysiloxane having the component (B) has an alkenyl group having 2 to 6 carbon atoms, whereby a crosslinking reaction of the components (A) to (C) can occur. In addition, since the organopolysiloxane having the component (B) has a branch structure, the hardenability is improved, and good adhesion to the LED chip can be obtained.

Moreover, it is preferable that the viscosity at 25 degreeC of the organopolysiloxane of a component (B) is 20 Pa * s or less from a viewpoint of the favorable handleability in preparation of a sample etc.

The content of the component (B) is preferably in a range of 10 parts by weight to 95 parts by weight based on 100 parts by weight of the component (A). This is a range for sufficiently softening the obtained crosslinked product at a high temperature.

The organopolysiloxane of the component (C) has at least two Si-H bonds in one molecule, whereby a cross-linking reaction of the components (A) to (C) can occur. In addition, in the organic polysiloxane of the component (C), 12 mol% to 70 mol% of the organic group bonded to the silicon atom is an aryl group, whereby the obtained crosslinked product is sufficiently softened at a high temperature. And maintain the transparency and mechanical strength of the crosslinked product.

Especially in the present invention, the organopolysiloxane of the component (C) is preferably an average unit formula:

[Chemical 3]

(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; wherein 12 to 70 mol% of R ⁴ is an aryl group) Organic polysiloxane.

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 for R ⁴ include methyl, ethyl, propyl, butyl, pentyl, and heptyl. Examples of the cycloalkyl group for R ⁴ include cyclopentyl and cycloheptyl. The content of the phenyl group in R ⁴ is preferably in the range of 30 mol% 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 ensured.

The content of the component (C) is preferably a 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 (A) component and the alkenyl group in the (B) component. An amount in the range of 0.5 to 2. This is for obtaining sufficient hardness of the obtained crosslinked product at room temperature.

The catalyst for the hydrosilylation reaction of the component (D) is a catalyst for promoting the hydrosilylation reaction of the alkenyl group in the component (A) and the component (B) with the hydrogen atom bonded to the silicon atom in the component (C). Media. Examples of the (D) component include a platinum-based catalyst, a rhodium-based catalyst, and a palladium-based catalyst. Among these, a platinum-based catalyst is preferred because it can significantly accelerate the curing of the composition.

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

Examples of the alkenylsiloxane include 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3,5,7-tetramethyl-1,3 , 5,7-tetravinylcyclotetrasiloxane, a part of these alkenylsiloxanes is substituted with ethyl, phenyl and the like, alkenylsiloxanes, and the vinyl groups of these alkenylsiloxanes Alkenyl siloxane substituted with allyl, hexenyl and the like. In particular, in terms of good stability of the platinum-alkenylsiloxane complex, 1,3-divinyl-1,1,3,3-tetramethyldisilazane is preferred.

In addition, it is preferable to add 1,3-divinyl-1,1,3,3 to the complex in terms of improving the stability of the platinum-alkenylsiloxane compound. -Tetramethyldisilazane, 1,3-diallyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1,3-dimethyl- 1,3-diphenyldisilazane, 1,3-divinyl-1,1,3,3-tetraphenyldisilazane, 1,3,5,7-tetramethyl-1, Alkyl siloxane such as 3,5,7-tetravinylcyclotetrasiloxane and organic siloxane oligomers such as dimethyl siloxane oligomer. It is particularly preferable to add an alkenylsiloxane to the complex.

If the content of the component (D) is an amount sufficient to promote the hydrosilylation reaction between the alkenyl group in the component (A) and the component (B) and the hydrogen atom bonded to the silicon atom in the component (C), then There is no particular limitation. The content of the component (D) is preferably an amount in the range of 0.01 ppm to 500 ppm in terms of mass units of the metal atoms in the component (D) relative to the present composition. Further, the content of the (D) component is preferably an amount in which the metal atom falls within a range of 0.01 to 100 ppm, and more preferably an amount in which the metal atom falls within a range of 0.01 ppm to 50 ppm. This is a range in which the present composition is sufficiently crosslinked without causing problems such as coloration.

This composition may also contain the following ingredients as other optional ingredients: ethynylhexanol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 2 -Alkynyl alcohols such as phenyl-3-butyne-2-ol; enynes such as 3-methyl-3-pentene-1-yne, 3,5-dimethyl-3-hexene-1-yne Compound; 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7 -Tetrahexenyl cyclotetrasiloxane, benzotriazole and other reaction inhibitors. The content of the reaction inhibitor is not limited, but it is preferably in the range of 1 ppm to 5,000 ppm based on the weight of the composition. The storage elastic modulus of the obtained silicone resin can also be adjusted by adjusting the content of the reaction inhibitor.

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, and more preferably 30% by weight or more of the entire phosphor 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.

As described in detail later, the phosphor sheet according to the embodiment of the present invention is particularly preferably used for surface coating of LEDs. In this case, a light-emitting device exhibiting excellent performance can be obtained when the content ratio of the silicone resin in the phosphor sheet is in the range described above.

(Fluorescent body) A fluorescent body absorbs light emitted from an LED chip and converts the wavelength of the light to emit light having a different wavelength from the light of the LED chip. Thereby, a part of the light emitted from the LED chip and a part of the light emitted from the phosphor are mixed to obtain a white multi-color LED. Specifically, a white LED system can be obtained by optically combining a blue LED chip with a phosphor that absorbs light emitted from the LED chip and emits light of a yellow emission color. Glow.

As described above, there are various phosphors such as a phosphor that emits green light, a phosphor that emits blue light, a phosphor that emits yellow light, and a phosphor that emits red light. Specific phosphors used in the present invention include known phosphors such as inorganic phosphors, organic phosphors, and quantum dots. As the phosphor, any one of a fluorescent pigment and a fluorescent dye can be used.

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

As the organic phosphor, it is preferable that the emission spectrum has a peak in a region of a wavelength of 500 nm to 700 nm. Such a phosphor is excited by excitation light having a wavelength in a range of 400 nm to 500 nm and emits light in a range of 500 nm to 700 nm. Examples of the phosphors as described above include phosphors that emit green light, phosphors that emit yellow light, and phosphors that emit red light. Examples of the organic phosphor used in the present invention include a pyrrole methylene compound, a coumarin pigment, a phthalocyanine pigment, a stilbene pigment, a cyanine pigment, a polybenzene pigment, Rhodamine pigments, pyridine pigments, pyrrole methylene pigments, porphyrin pigments, oxazine pigments, pyrazine pigments, allyl sulfonamide melamine formaldehyde co-condensation dyes, or fluorene fluorescence体 等。 Body and so on. From the viewpoint of color reproducibility, it is preferable to use a pyrrole methylene compound, and it is particularly preferable to use an organic compound represented by the general formula (4) described later.

The so-called quantum dots are semiconductor nano particles that emit fluorescence by being excited by excitation light. The quantum dots used in the present invention are preferably core-shell type semiconductor nano particles from the viewpoint of improving durability. As the core, a group II-VI semiconductor nanoparticle, a group III-V semiconductor nanoparticle, and a multicomponent semiconductor nanoparticle can be used. Specific examples include, but are not limited to, CdSe, CdTe, CdS, ZnS, ZnSe, ZnTe, InP, InAs, and InGaP. Among these, CdSe, CdTe, InP, and InGaP are preferable from the viewpoint of emitting visible light with high efficiency. As a shell, CdS, ZnS, ZnO, GaAs, and these composites can be used, but it is not limited to these. The emission wavelength of a quantum dot can usually be adjusted by the particle composition and size.

A ligand having a Lewis basic ligand may be coordinated to the surface of the quantum dot. Examples of the Lewis basic coordination group include an amine group, a carboxyl group, a mercapto group, a phosphine group, and a phosphine oxide group. Specifically, hexylamine, decylamine, cetylamine, octadecylamine, oleylamine, myristylamine, laurylamine, oleic acid, mercaptopropionic acid, trioctylphosphine, and Trioctylphosphine oxide, etc. Among them, cetylamine, trioctylphosphine, and trioctylphosphine oxide are preferred, and trioctylphosphine oxide is particularly preferred.

The quantum dots coordinated with these ligands can be produced by a known synthesis method. For example, CB Murray, DJ Norris, MG Bawendi, Journal of the American Chemical Society, 1993, 115 (19), pp8706-8715 , Or the method described in The Journal Physical Chemistry, 101, pp 9463-9475, 1997. In addition, a commercially available product can be used for the quantum dot coordinated with a ligand without any restriction. For example, Lumidot (manufactured by Sigma-Aldrich) may be mentioned.

Examples of the phosphor that can be particularly preferably used in the present invention include inorganic phosphors. Hereinafter, the inorganic phosphor used in the present invention will be described.

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

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

Examples of the inorganic phosphors used in the present invention include yttrium aluminum garnet (YAG) based phosphors, ytterbium aluminum garnet (TAG) based phosphors, silicate phosphors, and nitrides. Based phosphors, oxynitride phosphors, nitride phosphors, oxynitride phosphors, Mn-activated composite fluoride complex phosphors, and the like. Preferable examples of the oxynitride phosphor include a β-silicon aluminum oxynitride (Sialon) type phosphor.

Among them, nitride phosphors, oxynitride phosphors, Mn-activated composite fluoride complex phosphors can be preferably used, and β-type silicon aluminum oxynitride phosphors, Mn activation can be more preferably used. Complex fluoride complex phosphor. By using these phosphors, a high-luminance phosphor sheet can be obtained.

In addition, the phosphor sheet according to the embodiment of the present invention preferably includes a β-type silicon aluminum nitride oxide phosphor and a Mn-activated composite fluoride complex phosphor.

(Β-type silicon-aluminum oxynitride phosphor) β-type silicon-aluminum oxynitride is a solid solution of β-type silicon nitride. Dissolved in N position. The unit cell (unit lattice) of the β-type silicon aluminum oxynitride has atoms of 2 formulas. Therefore, as a general formula, Si _6-Z Al _z O _z N _8-z can be used. Here, z is 0 to 4.2. The solid solution range of β-type silicon aluminum nitride oxide is very wide. In addition, the molar ratio of (Si, Al) / (N, O) needs to be maintained at 3/4. The general method for producing β-type silicon aluminum oxynitride is a method in which, in addition to silicon nitride, silicon oxide and aluminum nitride, or aluminum oxide and aluminum nitride are added and heated.

β-type silicon-aluminum oxynitride has a wavelength of 520 nm to 550 nm due to the light-emitting elements (Eu, Sr, Mn, Ce, etc.) incorporated in the crystal structure, which are excited by blue light from ultraviolet rays. Green emitting β-type silicon aluminum nitride oxide phosphor.

The β-type silicon aluminum oxynitride phosphor used in the present invention preferably has a light emission spectrum having a peak in a region of a wavelength of 535 nm to 550 nm. Within this range, when the phosphor sheet according to the embodiment of the present invention is used for an LED package, good light emitting characteristics can be obtained. The average particle diameter of the β-type silicon aluminum nitride oxide phosphor is preferably 1 μm or more, more preferably 10 μm or more, and even more preferably 16 μm or more. The thickness is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 19 μm or less. Within this range, when the phosphor sheet according to the embodiment of the present invention is used for an LED package, good light emitting characteristics can be obtained.

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

The Mn-activated complex fluoride complex phosphor is of the general formula A ₂ MF ₆ : Mn (here, A is selected from the group consisting of Li, Na, K, Rb, and Cs and contains at least Na and / or One or more alkali metals of K, and M is one or more tetravalent elements selected from the group consisting of Si, Ti, Zr, Hf, Ge, and Sn). In the above general formula, K ₂ SiF ₆ : Mn is a KSF phosphor. As the Mn-activated composite fluoride complex phosphor used in the present invention, the KSF phosphor is preferred.

The average particle diameter of the Mn-activated composite fluoride complex phosphor is preferably 1 μm or more, more preferably 10 μm or more, and even more preferably 20 μm or more. The thickness is preferably 100 μm or less, more preferably 70 μm or less, and even more preferably 40 μm or less. Within this range, when the phosphor sheet according to the embodiment of the present invention is used for an LED package, good light emitting characteristics can be obtained.

In the present invention, the average particle diameter refers to a median diameter (D50). The average particle diameter can be measured by observing a phosphor sheet with a scanning electron microscope (SEM). Based on the two-dimensional image obtained by observing the cross section of the phosphor sheet, calculate the largest distance among the distances between the two intersections of a straight line that intersects two points with the outer edges of the phosphor particles, and It is defined as the individual particle diameters of the phosphor particles. By this method, the particle size of 200 of the observed phosphor particles is calculated, and in the particle size distribution obtained based on this, the particle size of 50% of the cumulative pass from the small particle size side is set to D50 .

When an LED light-emitting device equipped with a phosphor sheet is targeted, a mechanical polishing method, a microtome method, a cross-section polisher (CP) method, and a focused ion beam (Focused Ion Beam) can be used. , FIB) grinding in any method so that the cross section of the phosphor sheet can be observed, and then the obtained cross section is observed by SEM to obtain a two-dimensional image, and the average is calculated based on the two-dimensional image. Particle size.

In the present invention, the content of the inorganic phosphor in the phosphor sheet is preferably 35% by weight or more of the entire phosphor sheet, more preferably 40% by weight or more, and still more preferably 60% by weight or more. By setting the phosphor content in the phosphor sheet to such a range, the brightness of the phosphor sheet can be increased. In addition, the upper limit of the phosphor content is not particularly limited, but from the viewpoint of easily making a fluorescent sheet having excellent workability, the content of the fluorescent substance in the fluorescent sheet is preferably fluorescent The whole body sheet is 90% by weight or less, more preferably 85% by weight or less, still more preferably 80% by weight or less, and still more preferably 70% by weight or less.

As the phosphor which can be used particularly preferably in the present invention, an organic compound represented by the general formula (4) can also be cited as the organic phosphor. Hereinafter, the organic compound represented by the general formula (4) used in the present invention will be described.

(Organic compound represented by general formula (4))

[Chemical 4]

In the general formula (4) showing the organic compound in this embodiment, R ⁵ , R ⁶ , Ar ¹ to Ar ^5, and L may be the same or different, and are selected from hydrogen, alkyl, cycloalkyl, and arane. Alkyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, mercapto, alkoxy, alkylthio, arylether, arylthioether, aryl, heteroaryl, heterocyclyl, halogen, haloalkyl, Formed between haloalkenyl, haloalkynyl, cyano, aldehyde, carbonyl, carboxyl, ester, carbamoyl, amine, nitro, silyl, siloxy, and adjacent substituents Condensation ring and aliphatic ring. M represents an m-valent metal and is at least one selected from the group consisting of boron, beryllium, magnesium, chromium, iron, nickel, copper, zinc, and platinum. Of all the groups, hydrogen may be deuterium. The same applies to the organic compounds or partial structures described below.

In addition, in the following description, for example, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms means that all carbon numbers including the carbon number contained in the substituent substituted in the aryl group are 6 to 40 aryl. The same applies to other substituents having a specified carbon number.

In addition, among the above-mentioned groups, as a substituent when substituted, an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a hydroxyl group, a thiol group, Alkoxy, alkylthio, arylether, arylthioether, aryl, heteroaryl, halogen, cyano, aldehyde, carbonyl, carboxyl, oxycarbonyl, carbamoyl, amine, nitrate Group, silane group, siloxy group, oxyboryl group, and phosphine oxide group, and more preferably, specific substituents which are considered to be preferable in the description of each substituent. These substituents may be further substituted with the substituents.

The term "unsubstituted" in the case of "substituted or unsubstituted" means that a hydrogen atom or a deuterium atom has been substituted. In the organic compound or a partial structure described below, the case where it is referred to as "substituted or unsubstituted" is the same as described above.

In addition, in all the groups, the "alkyl group" means a saturated aliphatic hydrocarbon group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, or third butyl. The alkyl group may or may not have a substituent. In the case of substitution, the additional substituent is not particularly limited, and examples thereof include an alkyl group, an aryl group, a heteroaryl group, and the like. This point is also common to the following description. The number of carbon atoms of the alkyl group is not particularly limited, and it is preferably in the range of 1 or more and 20 or less, and more preferably in the range of 1 or more and 8 in terms of ease of acquisition and cost.

The "cycloalkyl group" means, for example, a saturated alicyclic hydrocarbon group such as cyclopropyl, cyclohexyl, norbornyl, and adamantyl, and it may or may not have a substituent. The number of carbon atoms in the alkyl portion is not particularly limited, but is preferably in the range of 3 or more and 20 or less.

The aralkyl group means, for example, an aromatic hydrocarbon group such as a benzyl group, a phenylethyl group, and the like through an aliphatic hydrocarbon. These aliphatic hydrocarbons and aromatic hydrocarbons may be unsubstituted and may have a substituent.

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

The term "cycloalkenyl" refers to, for example, an unsaturated alicyclic hydrocarbon group containing a double bond, such as a cyclopentenyl group, a cyclopentadienyl group, and a cyclohexenyl group.

The alkynyl group means, for example, an unsaturated aliphatic hydrocarbon group containing a triple bond such as an ethynyl group, and it may or may not have a substituent. The number of carbon atoms 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 means, for example, a functional group having an aliphatic hydrocarbon group bonded via an ether bond, such as a methoxy group, an ethoxy group, and a propoxy group. The aliphatic hydrocarbon group may or may not have a substituent. 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 an oxygen atom of an ether bond of an alkoxy group is substituted with a sulfur atom. 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 means, for example, a functional group having an aromatic hydrocarbon group bonded via an ether bond such as a phenoxy group. The aromatic hydrocarbon group may or may not have a substituent. 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 so-called aryl sulfide group is one in which an oxygen atom of an ether bond of an aryl ether group is substituted with a sulfur atom. The aromatic hydrocarbon group in the arylene sulfide group may or may not have a substituent. The number of carbon atoms of the arylene sulfide group is not particularly limited, but is usually in the range of 6 or more and 40 or less.

The aryl group means, for example, aromatic hydrocarbon groups such as phenyl, naphthyl, biphenyl, fluorenyl, phenanthryl, triphenylenyl, and bitriphenyl. 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.

The so-called heteroaryl group means furyl, thienyl, pyridyl, quinolinyl, pyrazinyl, pyrimidinyl, triazinyl, naphthyridinyl, benzofuranyl, benzothienyl, indolyl, etc. Or a plurality of cyclic aromatic groups having atoms other than carbon in the 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 means, for example, an aliphatic ring having an atom other than carbon in the ring, such as a pyran ring, a piperidine ring, and a cyclic amidine. The heterocyclic group 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.

A carbonyl group, a carboxyl group, and a 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 amine group is a substituted or unsubstituted amine group. The amine group may or may not have a substituent. Examples of the substituent in the case of substitution include an aryl group, a heteroaryl group, a linear alkyl group, and a branched alkyl group. As an aryl group and a 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 even more preferably 6 or more and 30 or less.

The term halogen means fluorine, chlorine, bromine or iodine. The so-called haloalkyl, haloalkenyl, and haloalkynyl represent, for example, trifluoromethyl and the like, such as trifluoromethyl, in which a part or all of the alkyl, alkenyl, and alkynyl are substituted with the halogen, and the rest may be unsubstituted or may be Was replaced. In addition, aldehyde groups, carbonyl groups, ester groups, and carbamate groups also include those substituted with aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and heterocyclic rings. Furthermore, aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons are included. The hydrocarbon and heterocyclic ring may be unsubstituted or substituted.

The term “silyl group” means, for example, 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 silane 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 term "siloxyalkyl group" refers to a silicon compound group having an ether bond interposed therebetween, such as trimethylsiloxyalkyl 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 a small peak half-value width of the emission spectrum, so that both efficient color conversion and high color purity can be achieved.

Among the metal complexes in the organic compound represented by the general formula (4), a complex in which M is boron is particularly preferred in terms of high fluorescence quantum yield. Furthermore, in terms of ease of material acquisition or ease of synthesis, a boron fluoride complex in which L is fluorine or a fluorine-containing aryl group and m-1 is 2 is particularly preferred.

In addition, two adjacent adjacent substituents (for example, R ⁵ and Ar ^{2 in the} general formula (4)) may be bonded to each other to form a conjugated or non-conjugated condensed ring. As a constituent element of such a condensed ring, in addition to carbon, an element selected from nitrogen, oxygen, sulfur, phosphorus, and silicon may be included. The condensed ring may be further condensed with another ring.

The organic compound represented by the general formula (4) as described above can adjust various characteristics and physical properties such as luminous efficiency, color purity, thermal stability, light stability, and dispersibility by introducing a suitable substituent to a suitable position. .

For example, the substituent Ar ⁵ greatly affects the durability of the organic compound represented by the general formula (4), that is, the aging intensity of the organic compound decreases with time. Specifically, when Ar ⁵ is hydrogen, the hydrogen is highly reactive, and therefore, the hydrogen easily reacts with moisture or oxygen in the air. This causes decomposition of Ar ⁵ . In addition, when Ar ⁵ is a substituent having a large degree of freedom in movement of an alkyl-like molecular chain, the reactivity does decrease, but organic compounds in the sheet condense with each other over time. As a result, concentration extinction is caused. The reduction of the luminous intensity. Therefore, Ar ^{5 is} preferably a group which is rigid and has a small degree of freedom of movement and is difficult to cause aggregation. Specifically, it is preferably a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. Either base.

From the viewpoint of providing higher fluorescence quantum yield and making it difficult to thermally decompose, and from the viewpoint of light stability, Ar ^{5 is} preferably a substituted or unsubstituted aryl group. As an aryl group, a phenyl group, a biphenyl group, a bitriphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, and an anthryl group are preferable from a viewpoint which does not impair a light emission wavelength.

Furthermore, in order to improve the light stability of the organic compound, it is necessary to moderately suppress the bending of the carbon-carbon bond of Ar ⁵ and the pyrrole methylene skeleton. The reason for this is that if the bending is too large, the reactivity to the excitation light becomes high, and the light stability decreases. From this viewpoint, as Ar ⁵ , a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted tritriphenyl group, a substituted or unsubstituted The substituted naphthyl group is more preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted bitriphenyl group. Particularly preferred is substituted or unsubstituted phenyl.

In addition, Ar ^{5 is} preferably a substituent having a moderately large volume. By having a large volume to some extent, Ar ⁵ can prevent the aggregation of molecules. As a result, the luminous efficiency or durability of the organic compound is further improved.

Better Examples of such bulky substituent group include the following structural formula (5) is represented by Ar ^5.

[Chemical 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 selected from the group consisting of hydrogen, alkyl, cycloalkyl, heterocyclyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, thiol, alkoxy, and alkane. Thio, aryl ether, aryl thio ether, aryl, heteroaryl, halogen, cyano, aldehyde, carbonyl, carboxyl, oxycarbonyl, carbamate, amino, nitro, silane, Siloxane, oxyboryl, and phosphine oxide groups. k is an integer from 1 to 3. When k is 2 or more, r may be the same or different.

Among 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, and a heteroaryl group. These substituents may be further substituted.

From the viewpoint of providing a higher fluorescence quantum yield, r is preferably a substituted or unsubstituted aryl group. Among the aryl groups, phenyl and naphthyl are particularly preferred. When r is an aryl group, k of the general formula (5) is preferably 1 or 2, and k is more preferably 2 from the viewpoint of further preventing molecular aggregation. Furthermore, when k is 2 or more, at least one of r is preferably substituted with an alkyl group. As an alkyl group in this case, a methyl group, an ethyl group, and a tertiary butyl group are mentioned as a particularly preferable example from a viewpoint of thermal stability.

In addition, from the viewpoint of controlling the fluorescence wavelength or the absorption wavelength or improving the compatibility with the solvent, r is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a halogen. , More preferably methyl, ethyl, third butyl, and methoxy. From the viewpoint of dispersibility, third butyl and methoxy are particularly preferred. In terms of preventing matting caused by the aggregation of molecules, it is more effective that r is a third butyl group or a methoxy group.

Compared to a case where all of Ar ¹ to Ar ⁴ are hydrogen, at least one of Ar ¹ to Ar ⁴ is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, a substituted or unsubstituted group The case of heteroaryl shows more good thermal stability and light stability.

In the case where 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 bitriphenyl group, a naphthyl group, and more preferably a benzene group. Radical, biphenyl. Especially preferred is phenyl.

In the case where 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 quinolyl group, or a thienyl group, and more preferably a pyridyl group or a quinyl group Porphyrinyl. Especially preferred is pyridyl.

In addition, in the general formula (4) representing the organic compound, Ar ¹ to Ar ⁴ may be the same or different, respectively, and a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group is preferred. Aryl. The reason is that it exhibits better thermal stability and light stability. In the phosphor composition and the like of this embodiment, when the organic compound converts the light emitted from the light emitter into light with a longer wavelength than the inorganic phosphor combined with the organic compound, the general formula ( All of Ar ¹ to Ar ⁴ shown in 5) may be the same or different, and are more preferably a substituted or unsubstituted aryl group, and particularly preferably a phenyl group. In this case, for example, if the light emitted from the luminous body is blue light, the inorganic phosphor converts the blue light into green light, and the organic compound converts the blue light into a color conversion more than the inorganic phosphor. It is long-wavelength light, which is converted into red light.

Furthermore, 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). This makes it possible to achieve both high color purity and durability.

[Chemical 6]

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.

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

From the viewpoints of heat resistance and color purity, Ar ¹ and Ar ⁴ , and Ar ² and Ar ^{3 are} preferably aryl groups each having the same structure. Furthermore, from the viewpoint of dispersibility, it is more preferable that 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. . Among them, as an example of at least one of Ar ¹ to Ar ⁴ , a third butyl group, a methoxy group, or a third butoxy group is particularly preferable.

In the general formula (6), n is preferably an integer of 1 to 3, and in terms of ease of obtaining and synthesizing raw materials, 1 or 2 is more preferable.

On the other hand, in the general formula (4) representing the organic compound, since the dispersibility in the film is improved and high-efficiency light emission can be obtained, it is particularly preferable that Ar ¹ ≠ Ar ² or Ar ³ ≠ Ar ⁴ . Here, "≠" indicates a group having a different structure. For example, Ar ¹ ≠ Ar ² represents a group in which Ar ¹ and Ar ² have different structures. Ar ³ ≠ Ar ⁴ represents a group in which Ar ³ and Ar ⁴ have different structures. The term Ar ¹ ≠ Ar ² or Ar ³ ≠ Ar ^{4 means} , in other words, "Ar ¹ = Ar ² and Ar ³ = Ar ⁴ ". That is, it means that (1) Ar ¹ = Ar ² = Ar ³ = Ar ⁴ and (2) Ar ¹ = Ar ² and Ar ³ = Ar ⁴ and Ar ¹ in any combination of Ar ¹ to Ar ⁴ . ≠ Ar ³

The aryl group represented by the general formula (6) affects various characteristics and physical properties such as the luminous efficiency, color purity, heat resistance, and light resistance of the organic compound represented by the general formula (4). Although it also has an aryl group which enhances a plurality of properties, it does not exist at all in all properties which exhibit sufficient performance. It is particularly difficult to balance high luminous efficiency with high color purity. Therefore, if a plurality of aryl groups can be introduced into the organic compound represented by the general formula (4), an organic compound that is balanced in terms of light emission characteristics, color purity, and the like can be expected.

The organic compound of Ar ¹ = Ar ² = Ar ³ = Ar ⁴ may have only one kind of aryl group. In addition, in an organic compound in which Ar ¹ = Ar ² and Ar ³ = Ar ⁴ and Ar ¹ ≠ Ar ³ , an aryl group having specific physical properties is biased toward one of the pyrrole rings. In this case, in terms of the relationship between the luminous efficiency and the color purity, as described later, it is difficult to extract the physical properties of each aryl group to the maximum.

In contrast, the organic compound according to the embodiment of the present invention can arrange substituents having certain physical properties in the right and left pyrrole rings in a well-balanced manner. Therefore, compared with the case where the substituents are concentrated in one of the pyrrole rings, the organic compound can be maximized. Give play to its physical properties.

This effect is particularly excellent in that the luminous efficiency and color purity are improved in a well-balanced manner. From the point that the conjugated system expands to obtain light emission with high color purity, it is preferred that each of the pyrrole rings on both sides has one or more aryl groups which affect color purity. However, if an organic compound in which Ar ¹ = Ar ² and Ar ³ = Ar ⁴ and Ar ¹ ≠ Ar ³ has introduced an aryl group that has an effect on color purity in one pyrrole ring, if the organic compound has another pyrrole ring If an aryl group having an effect on luminous efficiency is introduced in the middle, the aryl group having an effect on color purity will be concentrated in the pyrrole ring on one side, so the conjugated system is not sufficiently expanded and the color purity is not sufficiently improved. In addition, if an aryl group having another structure that also affects color purity is introduced into another pyrrole ring, luminous efficiency cannot be improved.

In contrast, in the organic compound according to the embodiment of the present invention, one or more aryl groups having an effect on color purity may be introduced into the pyrrole ring on both sides, and aryl groups having an effect on luminous efficiency may be introduced into other positions. . Therefore, the organic compound according to the embodiment of the present invention is preferable because it can maximize the two properties of color purity and luminous efficiency. Further, at the position of Ar ² and Ar ³ in the case where the aryl group is introduced affects the color purity will conjugated maximally expanded, and therefore preferred.

When at least one of Ar ¹ to Ar ⁴ is a substituted or unsubstituted alkyl group, the alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Alkyl group having 1 to 6 carbons such as second butyl, third butyl, pentyl, and hexyl. Furthermore, as this alkyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a second butyl group, and a third butyl group are preferred from the viewpoint of excellent thermal stability. In addition, from the viewpoint of preventing concentration extinction and improving light emission quantum yield, the alkyl group is more preferably a tertiary bulky third butyl group. On the other hand, from the viewpoint of ease of synthesis and ease of obtaining raw materials, as the alkyl group, a methyl group can also be preferably used.

On the other hand, in the general formula (4) representing the organic compound, in the case where Ar ¹ to Ar ⁴ may be the same or different, and are substituted or unsubstituted alkyl groups, A resin or a solvent is preferred because it has good solubility. In this case, the alkyl group is preferably a methyl group in terms of ease of synthesis and ease of obtaining raw materials. For example, in the phosphor composition and the like of this embodiment, when the organic compound converts the light emitted from the light emitter into light of shorter wavelength than the inorganic phosphor combined with the organic compound, All of Ar ¹ to Ar ⁴ represented by formula (4) may be the same or different, and are substituted or unsubstituted alkyl groups, and preferably methyl. Specifically, if the light emitted from the light emitter is blue light, the inorganic phosphor converts the blue light into red light, and the organic compound converts the blue light into a color shorter than the color of the inorganic phosphor. Wavelength of light, that is, converted into 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 of hydrogen, alkyl, carbonyl, oxycarbonyl, and aryl, and from the viewpoint of thermal stability, hydrogen or alkyl is preferred. In particular, at least one of R ⁵ and R ⁶ is more preferably hydrogen from the viewpoint that it is easy to obtain a narrow half-value width in the emission spectrum.

In addition, L is preferably an alkyl group, an aryl group, a heteroaryl group, a fluorine group, a fluorine-containing alkyl group, a fluorine-containing heteroaryl group, or a fluorine-containing aryl group. In particular, the case where L is fluorine or a fluorine-containing aryl group is more stable because it is stable to the excitation light and a higher fluorescence quantum yield can be obtained. Furthermore, in terms of ease of synthesis, L is more preferably fluorine.

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

In another aspect 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. It is particularly preferable that (1) at least one of R ¹ , R ² , and 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 At least one of ˜Ar ⁴ is an electron withdrawing group and Ar ⁵ is an electron withdrawing group. By introducing an electron-withdrawing group into the pyrrole methylene skeleton of an organic compound like this, the electron density of the pyrrole methylene skeleton can be greatly reduced. Thereby, 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.

The so-called electron-withdrawing group, also known as an electron-accepting group, refers to an atomic group that attracts electrons from a substituted atomic group through an inductive effect or a resonance effect in organic electron theory. Examples of the electron withdrawing group include a group that takes a positive value as the substituent constant (σp (para)) of the Hammett's equation. The substituent constant (σp (para-position)) of the Hammett's equation can be quoted from the Revised 5th Edition of the Fundamentals of Chemistry (Page II-380). In addition, although the phenyl group also has an example of taking a positive value as described above, in the present invention, the phenyl group is not included in the electron withdrawing group.

Examples of the electron-withdrawing group 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 ethyl), -CONH ² (σp: +0.38), -COR ¹² (σp: +0.49 when R ¹² is methyl), -CF 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 each independently represents a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, and a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms 1, substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms, and substituted or unsubstituted cycloalkyl groups having 1 to 30 carbon atoms. Specific examples of the respective groups include the same examples as described above.

Examples of preferred electron withdrawing groups include fluorine, fluoroaryl, fluoroheteroaryl, fluoroalkyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted ester, and Substituted or unsubstituted amido, substituted or unsubstituted sulfofluorenyl, or cyano. The reason is that these groups are difficult to chemically decompose.

More preferred electron withdrawing groups include fluorinated alkyl groups, substituted or unsubstituted fluorenyl groups, substituted or unsubstituted ester groups, or cyano groups. The reason is that these groups bring the effects of preventing concentration extinction and increasing the luminescence quantum yield. Particularly preferred electron withdrawing groups are substituted or unsubstituted ester groups.

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 color purity, and as a result, the durability of the organic compound can be improved.

In the general formula (5) representing Ar ⁵ of the organic compound, r is more preferably an electron withdrawing group. The reason is that the stability of the organic compound represented by the general formula (4) with respect to oxygen can be further improved without impairing the luminous efficiency and color purity, and as a result, the durability of the organic compound can be greatly improved.

As a preferable example of the organic compound represented by the general formula (4), the following cases may be mentioned: Ar ¹ to Ar ⁴ may be the same or different, and are substituted or unsubstituted alkyl groups, and further Ar ⁵ Is a group represented by general formula (5). In this case, Ar ^{5 is} particularly preferably a group represented by general formula (5) containing r as a substituted or unsubstituted phenyl group.

In addition, as another preferable example of the organic compound represented by the general formula (4), the following cases may be mentioned: Ar ¹ to Ar ⁴ may be the same or different, and are selected from the general formula (6) Or, 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) containing r as a third butyl group and a methoxy group, and particularly preferably a group represented by the general formula (5) containing r as a methoxy group. Represented groups.

An example of the organic compound represented by the general formula (4) is shown below, but the organic compound of this embodiment is not limited to these examples.

[Chemical 7]

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[Chemical 31]

The organic compound represented by the general formula (4) can be produced, for example, by a method described in Japanese Patent Application Publication No. Hei 8-509471 or Japanese Patent Application Publication No. 2000-208262. That is, the target pyrromethene-based metal complex can be obtained by reacting a pyrromethene compound with a metal salt in the presence of a base.

For the synthesis of pyrrole methylene-boron fluoride complex, please refer to "Journal of Organic Chemistry (J. Org. Chem.)" (Vol. 64, No. 21, pp. 7813-7819 (1999)) , "Applied Chemistry International Edition (Angew. Chem., Int. Ed. Engl.)" (Vol. 36, pp. 1333-1335 (1997)), etc. to produce the formula (4) Organic compounds.

The phosphor composition according to the embodiment of the present invention may suitably contain other compounds in addition to the organic compound represented by the general formula (4), if necessary. For example, in order to further improve the energy transfer efficiency of self-excitation light to the organic compound represented by the general formula (4), an auxiliary dopant such as rubrene may be contained. In addition, when a light emitting color other than the light emitting color of the organic compound represented by the general formula (4) is to be added, a desired organic light emitting material may be added, such as a coumarin-based dye, a fluorene-based dye, and phthalocyanine. Pigments, stilbene pigments, cyanine pigments, polybenzene pigments, rhodamine pigments, pyridine pigments, pyrromethylene pigments, porphyrin pigments, oxazine pigments, pyrazine pigments And other compounds. In addition to these organic light-emitting materials, known light-emitting materials such as inorganic phosphors, fluorescent pigments, fluorescent dyes, and quantum dots may be added in combination.

An example of an organic light-emitting material other than the organic compound represented by the general formula (4) is shown below, but the present invention is not particularly limited to these examples.

[Chemical 32]

Although the content of the organic compound represented by the general formula (4) in the phosphor composition according to the embodiment of the present invention also depends on the molar absorption coefficient of the organic compound, the fluorescence quantum yield, the absorption intensity at the excitation wavelength, and the production thickness or transmittance of the film, but generally with respect to the entire weight of the phosphor composition and ^10-5% by weight to 10% by weight, more preferably ^10-4% by weight to 5% by weight, particularly preferably 10 ^{- 3} weight percent to 2 weight percent.

(Solvent) The phosphor 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 resin in which the flow state can be adjusted. Examples of the solvent include toluene, methyl ethyl ketone, methyl isobutyl ketone, hexane, acetone, terpineol, and 2,2,4-trimethyl-1,3-pentanediol. Isobutyrate (Texanol), methyl cellosolve, butylcarbitol, butylcarbitol acetate, propylene glycol monomethyl ether acetate, etc.

(Other components) The phosphor sheet of the embodiment of the present invention may contain a dispersant or leveling agent for stabilizing the coating film, a silane coupling agent as a modifier of the surface of the phosphor sheet, and other adjuvants. Wait.

The phosphor sheet according to the embodiment of the present invention may contain fine particles. Examples of the fine particles include silicone fine particles or titanium dioxide, silicon dioxide, aluminum oxide, silicone, zirconia, cerium oxide, aluminum nitride, silicon carbide, silicon nitride, barium titanate, and the like. In addition, in order to reduce the storage elastic modulus G ′ at 100 ° C., the phosphor sheet according to the embodiment of the present invention may contain a silyl alcohol group-containing methylphenyl-based silicone resin as a heating adhesive. From the viewpoint of easy availability, silicone fine particles, silicon dioxide fine particles, and alumina fine particles can be preferably used, and silicone fine particles can be particularly preferably used.

By containing silicone fine particles, the phosphor sheet according to the embodiment of the present invention has good adhesion and processability as well as uniform film thickness. In particular, by using silicone fine particles having an average particle diameter (median diameter: D50) of 0.1 μm or more and 2.0 μm or less, excellent ejection properties and uniform film thickness can be obtained when a slit die coater is used. Excellent fluorescent sheet.

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

The silicone fine particles are preferably particles containing a silicone resin and / or a silicone rubber. Particularly preferred are silicone microparticles obtained by the following method: organic trialkoxysilane or organic dialkoxysilane, organic triacetoxysilane, organic diacetoxysilane, and organic trioxime silicone And other organic silanes, such as organic dioxime silane, are hydrolyzed and then condensed. Among these, when the organic silane and / or a partial hydrolysate thereof is hydrolyzed and condensed to produce spherical organic polysilsesquioxane fine particles, it is preferably used as disclosed in Japanese Patent Laid-Open No. 2003-342370. The reported silicone fine particles obtained by a method of adding a polymer dispersant to a reaction solution.

In addition, when producing silicone microparticles, it is also possible to use silicone microparticles produced by hydrolyzing and condensing an organic silane and / or a part of the hydrolysate thereof, and having a high function as a protective colloid in a solvent In a state where a molecular dispersant and a salt are present in an acidic aqueous solution, an organic silane and / or a hydrolyzate thereof is added to obtain a hydrolysate, and then a base is added to cause a condensation reaction to proceed.

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

(Substrate) The substrate is an example of a support of the phosphor sheet of the present invention. The substrate is not particularly limited, and for example, known metals, films, glass, ceramics, and paper can be used. Specific examples include: aluminum (also aluminum alloy), zinc, copper, iron and other metal plates or foils; cellulose acetate, polyethylene terephthalate (PET), polyethylene, polyethylene Esters, polyamidoamine, polyamidoimide, polyphenylene sulfide, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, aramid, silicone, polyolefin, thermoplastic fluororesin Film of plastics, such as ethylene-tetrafluoroethylene (ETFE); copolymers containing alpha-polyolefin resin, polycaprolactone resin, acrylic resin, silicone resin, and copolymer resins of these resins with ethylene Plastic film; paper laminated with the plastic, or paper coated with the plastic, paper laminated or vapor-deposited with the metal, plastic film laminated or vapor-deposited with the metal, and the like. In addition, when the base material is a metal plate, the surface of the metal plate may be subjected to a plating treatment such as chromium or nickel, or a ceramic treatment.

Among these, glass or a plastic film can be preferably used in terms of ease of production of the phosphor sheet or ease of singulation of the phosphor sheet. In particular, in terms of adhesiveness when a phosphor sheet is attached to an LED chip, the base material is preferably a soft film. In addition, a high-strength film is preferred so that there is no concern such as breakage when the film-shaped substrate is processed. In terms of these characteristics or economical requirements, a plastic film is preferred. 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 handling. In addition, when the phosphor sheet is dried or when a high temperature of 200 ° C. or higher is required when the phosphor sheet is attached to the LED chip, a polyimide film is preferred in terms of heat resistance. Regarding the ease of peeling of the phosphor sheet from the substrate, the surface of the substrate may be subjected to a release treatment in advance.

The thickness of the substrate is not particularly limited, and the lower limit is preferably 25 μm or more, and more preferably 38 μm or more. The upper limit is preferably 5,000 μm or less, and more preferably 3,000 μm or less.

(Other layers) The phosphor sheet according to the embodiment of the present invention may include a barrier layer. The barrier layer can be suitably used in the case where the gas barrier properties of the phosphor sheet are improved.

Examples of the barrier layer having a barrier function against oxygen include silicon oxide, aluminum oxide, tin oxide, indium oxide, yttrium oxide, magnesium oxide, or a mixture of these, or metals in which other elements are added. Oxide films; films containing various resins such as nylon, polyvinylidene chloride, copolymers of ethylene and vinyl alcohol, etc.

Examples of the barrier layer having a barrier function against moisture include polyethylene, polypropylene, nylon, polyvinylidene chloride, copolymers of vinylidene chloride and vinyl chloride, and copolymerization of vinylidene chloride and acrylonitrile. Of various resins such as resins and fluorine resins.

In addition, the phosphor sheet according to the embodiment of the present invention may further have an anti-reflection function, an anti-glare function, an anti-reflection and anti-glare function, a light diffusion function, and a hard coating function (resistant Friction function), anti-static function, anti-fouling function, electromagnetic wave shielding function, infrared cut-off function, ultraviolet cut-off function, polarizing function, auxiliary function of color correction function.

<Method for Producing Phosphor Sheet> Hereinafter, an example of a method for producing a phosphor sheet according to an embodiment of the present invention will be described. Note that the production method described below is an example, and the production method of the phosphor sheet is not limited to this.

First, a composition in which a phosphor is dispersed in a silicone resin (hereinafter referred to as a “fluorescent composition”) is prepared as a coating liquid for forming a phosphor sheet. A predetermined amount of the above-mentioned additives such as silicone resin, phosphor, and optional silicone fine particles, a solvent, and the like are mixed. After mixing the ingredients so as to have a predetermined composition, the mixture is homogeneously mixed and dispersed by using a homogenizer, a rotary revolution mixer, a three-roller, a ball mill, a planetary ball mill, and a bead mill. This gives a phosphor composition.

After mixing or dispersing, or during the process of mixing and dispersing, it is also preferable to perform defoaming under vacuum or reduced pressure. In addition, a specific component may be mixed in advance, and the resulting phosphor composition may be subjected to treatment such as aging. The solvent may be removed from the mixed and dispersed mixture by an evaporator and adjusted to a desired solid content concentration.

The phosphor composition produced by the above method is applied to a substrate and dried to produce a phosphor sheet. Coating can be performed by reverse roll coater, blade coater, slot die coater, direct gravure coater, offset gravure coater (offset gravure coater), kiss coater, natural roll coater, air knife coater, roll blade coater, dual flow coater Two-stream coater, rod coater, wire bar coater, applicator, dip coater, curtain coating It is performed by a curtain coater, a spin coater, a knife coater, and the like. In order to obtain the uniformity of the film thickness of the phosphor sheet, it is preferable to perform coating using 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 performed at 40 ° C to 250 ° C for 1 minute to 5 hours, and preferably 60 ° C to 200 ° C for 2 minutes to 4 hours. In addition, stepwise drying such as step cure may be performed.

After making the phosphor sheet, the substrate can be changed as needed. In this case, examples of a simple method include a method of transferring a substrate using a hot plate, or a method of transferring a substrate using a vacuum laminator or a dry film laminator.

<Application Example of Phosphor Sheet> By attaching a phosphor sheet or a cured product thereof according to an embodiment of the present invention to a light emitting surface of an LED chip, a band having a phosphor sheet on a surface area layer of the LED wafer can be formed. LED chip with phosphor sheet. The LED chip to which the phosphor sheet of the embodiment of the present invention can be applied is not particularly limited, and examples thereof include LED chips of a general structure such as a lateral type, a vertical type, and a flip chip type. As such LED wafers, vertical-type and flip-chip-type LED wafers having a large light emitting area are particularly preferred. The light-emitting surface of the LED wafer refers to a surface on which light from the LED wafer is led out.

Here, there are a case where the light emitting surface of the LED wafer is a single plane and a case where it is not a single plane. As a case of a single plane, an LED wafer which mainly has only an upper light emitting surface is mentioned. Specifically, an example is a vertical type LED wafer, or an LED wafer that covers the side surface of the LED wafer with a reflective layer and only emits light from the upper surface. On the other hand, examples of cases other than a single plane include an LED wafer having an upper light emitting surface and a side light emitting surface, an LED wafer having a curved light emitting surface, and the like.

Among these LED chips, an LED chip having a light emitting surface other than a single plane can be brightened by light emission from the side portions, and is therefore preferred. In particular, a flip-chip type LED chip having an upper light-emitting surface and a side light-emitting surface is preferred in terms of increasing the light-emitting area and making the manufacturing process of the LED chip easy. In addition, the surface of the light emitting surface may be textured based on an optical design to improve the light emitting 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 through an adhesive such as a transparent resin. 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, it is more preferable that the phosphor sheet according to the embodiment of the present invention is directly attached to the LED chip. This makes it possible to obtain white light with low color unevenness, high efficiency, and uniformity.

An LED package can be manufactured by mounting the LED chip with a phosphor sheet obtained by these methods on a wiring substrate provided with metal wiring, etc., and packaging. After that, the LED package is assembled into a module, and can be suitably used in various kinds of lighting, or various light-emitting devices typified by a liquid crystal backlight and a headlight.

A suitable example of the LED package according to the embodiment of the present invention is shown in FIGS. 1A and 1B. FIG. 1A (a) shows a case where the LED chip 1 to which the phosphor sheet 2 is attached is mounted on a mounting substrate 5 including a reflector 4 and the upper surface of the LED chip 1 is partially sealed with a transparent sealing material 3. .

FIG. 1A (b) shows that the LED chip 1 to which the phosphor sheet 2 is attached is installed on a mounting substrate 5 including a reflector 4, and the upper surface portion and the side portion of the LED wafer 1 are sealed by a transparent sealing material 3. Become.

FIG. 1A (c) is obtained by attaching a phosphor sheet 2 not only to the upper surface of the LED chip 1 but also to the side in the configuration shown in FIG. 1A (b). In this embodiment, it is also preferable to convert the emission wavelength from the side surface of the LED chip by the phosphor sheet 2. Furthermore, the upper surface of the transparent sealing material 3 is formed in a lens shape.

FIG. 1A (d) shows a case where the LED chip 1 with the phosphor sheet 2 attached thereto is mounted on a mounting substrate 5 having no reflector, and is sealed with a transparent sealing material 3 molded into a lens shape.

FIG. 1A (e) is obtained by attaching a phosphor sheet 2 not only to the upper surface of the LED chip 1 but also to the side in the configuration shown in FIG. 1A (d).

FIG. 1A (f) is a configuration shown in FIG. 1A (c), in which a flip chip type LED chip 1 is used as the LED chip, and the phosphor sheet 2 is not only used as the light emitting surface of the LED chip 1 The upper surface and side surfaces of the mounting substrate 5 are attached 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 surfaces of the light emitting surface of the LED chip 1.

(G) of FIG. 1B shows the configuration shown in (d) of FIG. 1A, in which the configurations of the LED chip 1 and the phosphor sheet 2 are the same as those shown in (f) of FIG. 1A.

(H) of FIG. 1B shows that the LED chip 1 is provided so as to completely fit the portion of the mounting substrate 5 having the reflector 4 without the reflector 4. The interval between the reflectors 4 is a phosphor sheet 2 having the same width, and is further sealed with a transparent sealing material 3.

(I) of FIG. 1B is the structure shown in (h) of FIG. 1B. As the phosphor sheet 2, a phosphor sheet 2 with a substrate 9 is used and is not peeled off from the phosphor sheet 2. A state in which the phosphor sheet 2 is attached via the adhesive 8 in the state of the base material 9.

The LED package according to the embodiment of the present invention is not limited to these configurations. For example, it is good also as a structure which combined the structure of each component illustrated in (a) of FIG. 1A-(i) of FIG. 1B suitably. In addition, a configuration in which the structure of each component illustrated in (a) to (i) of FIG. 1A is replaced with other known components, or (a) to (a) to FIG. 1A The configuration exemplified in (i) of 1B is a combination of known components.

The transparent sealing material 3 may be any material as long as it is a material having excellent moldability, transparency, heat resistance, and adhesiveness. For example, known materials such as epoxy resin, silicone resin (including silicone polysiloxane cured products (crosslinked products) such as silicone rubber and silicone gel), urea resin, fluororesin, and polycarbonate resin can be used.

As the adhesive 8, a material that can be used as the transparent sealing material can be used.

The material constituting the reflector 4 is not particularly limited, and examples thereof include those in which particles are added to the material used in the transparent sealing material 3. Examples of the fine particles include titanium dioxide, silicon dioxide, aluminum oxide, silicone, zirconia, cerium dioxide, aluminum nitride, silicon carbide, silicon nitride, and barium titanate. Among these fine particles, silicon dioxide fine particles, alumina fine particles, and titanium dioxide fine particles can be preferably used from the viewpoint of easy availability.

<A method for attaching a phosphor sheet, and a method for manufacturing an LED package using the phosphor sheet> Next, a method for attaching a phosphor sheet to an LED chip according to an embodiment of the present invention, and a method using a phosphor according to an embodiment of the present invention A method for manufacturing the LED package of the light body sheet will be described.

The representative manufacturing method of the LED package using the phosphor sheet according to the embodiment of the present invention is as described below. (1) The phosphor sheet is cut into a single piece and then attached to individual LED chips. (For example, refer to (a) to (f) of FIG. 2), (2) a plurality of LED chips formed by uniformly attaching a phosphor sheet to a wafer (hereinafter referred to as “wafer-level LED chips”) Then, the method of cutting the wafer and cutting the phosphor sheet in a unified manner (for example, referring to (a) to (f) of FIG. 3) are not limited to these methods. Hereinafter, these steps will be described with reference to (a) to (f) of FIG. 2 and (a) to (f) of FIG. 3 as appropriate.

(Procedure for Adhering Phosphor Sheet to LED Chip) The phosphor sheet according to the embodiment of the present invention is attached to the LED chip by heating and pressing at a desired temperature. This is an application by thermal compression bonding.

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. Resin for increasing the difference in storage elastic modulus G 'of the phosphor sheet at room temperature and the elastic modulus G' of the phosphor sheet at the attachment temperature by setting the heating temperature to 60 ° C or higher Design becomes easy. In addition, by setting the heating temperature to 250 ° C. or lower, the thermal expansion or thermal contraction of the phosphor sheet can be reduced, and thus the accuracy of the position of the attachment can be improved.

In particular, in the case where a hole is processed in advance on the phosphor sheet and alignment is performed with a predetermined portion on the LED chip, the position accuracy of the attachment is important. From the viewpoint of improving the accuracy of the placement position, the heating temperature is more preferably 160 ° C or lower.

As a device for thermally crimping a phosphor sheet, any existing device can be used as long as it can be crimped at a desired temperature. In the case where the singulated phosphor sheet is heat-pressed as shown in (c) to (d) of FIG. 2, for example, a mounter or a flip chip bonding machine (flip) can be used. chip bonder).

In addition, in a case where the phosphor sheet is uniformly attached to the wafer-level LED wafer as shown in (a) to (b) of FIG. 3, a vacuum laminator or a square having a size of about 100 mm to 200 mm can be used. Heating crimping tool for the heating part.

In either case, the phosphor sheet with the substrate is pressure-bonded to the LED chip at a desired temperature to thermally fuse the phosphor sheet, and then left to cool to room temperature, and the substrate Peeled from the phosphor sheet. The storage elastic modulus G ′ of the phosphor sheet according to the embodiment of the present invention at 25 ° C. and 100 ° C. has a relationship as described above, and therefore, the phosphor sheet can be solid after being left to cool to room temperature after heat welding. The ground is tightly adhered to the LED chip, and at the same time, it is easily peeled from the substrate.

(Step for cutting the phosphor sheet) Among the methods for cutting the phosphor sheet, there are the following methods: a method of cutting into a single piece in advance before attaching to the LED chip; and a wafer-level LED chip A method of cutting a phosphor sheet simultaneously with dicing of a wafer after attaching the phosphor sheet.

As shown in (a) to (f) of FIG. 2, in the case where the phosphor sheet is cut before being attached to the LED chip, a uniformly formed one is formed by laser processing or cutting by a cutter. The phosphor sheet is processed into a predetermined shape and divided. Since processing with lasers imparts high energy to the phosphor sheet, depending on the processing conditions, the resin in the phosphor sheet may be burnt or the phosphor may be deteriorated. Therefore, as a method for cutting the phosphor sheet, it is desirable to use cutting by a cutter.

As a cutting method using a cutter, for example, there are a simple method of cutting by pressing the cutter into, and a method of cutting with a rotary blade, and any method can be suitably used. As a device for cutting with a rotary blade, a device for cutting (dicing) a semiconductor substrate into individual wafers, which is called a dicer, can be suitably used. If a microtome is used, the width of the dividing line of the phosphor sheet can be precisely controlled by the thickness or condition setting of the rotary knife. Therefore, the phosphor sheet can be cut compared with a simple pressing of a knife. In the case, high machining accuracy can be obtained.

When cutting the phosphor sheet in a laminated state with the substrate, the phosphor sheet may be singulated together with the substrate, or the phosphor sheet may be singulated without cutting the substrate. Alternatively, the phosphor sheet may be singulated, and a cut line that is not penetrated may be engraved on the substrate (a so-called half cut state).

When the phosphor sheet is singulated together with the base material, the phosphor sheet of each single sheet can be attached to the LED chip by the method described above. At this time, the substrate may be peeled from the phosphor sheet before being attached to the LED chip or after being attached to the LED chip. In addition, the substrate may be left in a state where it is not peeled from the phosphor sheet.

In the case where the phosphor sheet is singulated without cutting the substrate or in a so-called half-cut state, the phosphor sheet of each single sheet can be affixed by the method after being peeled from the substrate. On individual LED chips.

As shown in (a) to (f) of FIG. 3, after attaching a phosphor sheet to a wafer-level LED wafer, the phosphor sheet can be cut simultaneously with the dicing of the wafer. It is processed into a predetermined shape by laser processing or cutting with a cutter, and divided into singulated LED chips with phosphor sheets. Among these cutting methods, cutting by a cutter is preferred.

(Specific example of manufacturing method of LED package using phosphor sheet) (a) to (f) of FIG. 2 are a case where the phosphor sheet is singulated together with the base material and attached to the LED chip. An example of a series of steps. The steps (a) to (f) of FIG. 2 include a step of cutting the phosphor sheet into a single piece, and a step of attaching the cut phosphor sheet to the LED chip. .

(A) of FIG. 2 is a case where the phosphor sheet 2 in a state of being laminated with the base material 9 is fixed to the temporary fixing sheet 11. In the steps shown in (a) to (f) of FIG. 2, since the phosphor sheet 2 and the substrate 9 are singulated, they are fixed to the temporary fixing sheet 11 in an easy-to-handle manner. Next, as shown in FIG. 2 (b), the phosphor sheet 2 and the substrate 9 are cut to be singulated.

Then, as shown in FIG. 2 (c), the singulated phosphor sheet 2 is aligned with the base material 9 on the LED wafer 1 mounted on the mounting substrate 5. Then, as shown in FIG. 2 (d), the phosphor chip 2 is crimped to the LED chip 1 at a desired temperature by using the heat crimping tool 12. At this time, it is preferable to perform the crimping step under vacuum or reduced pressure so that air is not mixed between the phosphor sheet 2 and the LED chip 1. After crimping, it was left to cool to room temperature.

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

(A)-(f) of FIG. 3 is a series of steps in the case where a wafer-level LED wafer is uniformly attached with a phosphor sheet, and then the wafer is cut and the phosphor sheet is uniformly cut. An example. The steps (a) to (f) of FIG. 3 include the steps of uniformly attaching a phosphor sheet to a plurality of LED wafers formed on a wafer, and uniformly dicing and attaching the wafer. Step of singulating an LED chip with a phosphor sheet.

As shown in FIG. 3 (a), the phosphor sheet 2 in a state of being laminated with the base material 9 is not subjected to cutting processing in advance. The side of the phosphor sheet 2 is aligned with a wafer 13 on which a plurality of LED chips (not shown) are formed on the surface.

Next, as shown in FIG. 3 (b), the phosphor sheet 2 is uniformly heated and crimped to a plurality of LED wafers at a desired temperature by using a heat crimping tool 12. At this time, it is preferable to perform the heat-compression bonding step under vacuum or reduced pressure so that air is not mixed between the phosphor sheet 2 and the LED chip. After heating and compression bonding, it is left to cool to room temperature.

Next, as shown in FIG. 3 (c), after the substrate 9 is peeled from the phosphor sheet 2, the wafer 13 is sliced, and the phosphor sheet 2 is cut to be singulated. Then, as shown in FIG. 3D, a singulated LED chip 25 with a phosphor sheet is obtained.

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

In any of the steps (a) to (f) of FIG. 2 and (a) to (f) of FIG. 3, when a phosphor sheet is attached to an LED wafer having an electrode on the upper surface, The phosphor sheet needs to be removed from the part corresponding to the electrode. Therefore, before attaching the phosphor sheet to the LED chip, it is preferable to pre-perforate a portion of the phosphor sheet corresponding to the electrode. The phosphor sheet according to the embodiment of the present invention can perform high-precision drilling processing.

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

The method of the hole processing is not particularly limited, and for example, a known method such as laser processing and die punching can be suitably used. Laser processing may cause burning of the resin in the phosphor sheet or deterioration of the phosphor depending on the processing conditions. Therefore, it is more desirable to use a die for punching. When punching is performed, punching cannot be performed after the phosphor sheet is attached to the LED chip. Therefore, punching must be performed before the phosphor sheet is attached to the LED chip.

In the punching process using a mold, a mold is designed according to the shape or size of an electrode included in the LED wafer, so that a hole of any shape or size can be opened. In the LED chip having a size of about 1 mm square, in order not to reduce the area of the light emitting surface, the size of the electrode on the upper surface is preferably 500 μm square or less. Therefore, the hole provided to the phosphor sheet is preferably a size of 500 μm square or less in accordance with the size of the electrode. In addition, when wire bonding or the like is performed between an electrode on the upper surface of the LED chip and a 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. Therefore, it is preferable that the hole provided to the phosphor sheet is approximately 50 μm square in accordance with the size of the electrode.

If the size of the hole applied to the phosphor sheet is much larger than the size of the electrode, the light-emitting surface is exposed and light leakage occurs, which may cause a decrease in color characteristics of the LED package. In addition, if it is much smaller than the size of the electrode, the lead may contact the phosphor sheet during wire bonding, which may cause poor bonding. Therefore, in the hole processing in the phosphor sheet, it is preferable to process small holes with a size of 50 μm or more and 500 μm or less with high accuracy within ± 10%.

When the phosphor sheet that has been subjected to the cutting process and the hole-opening process as required is aligned with a predetermined portion of the LED wafer for attachment, an attachment device having an optical alignment (alignment) mechanism is required. In this case, it is difficult to align the phosphor sheet and the LED chip in terms of work. Therefore, in practical terms, alignment is often performed in a state where the phosphor sheet and the LED wafer are lightly contacted.

At this time, if the phosphor sheet has adhesiveness, it is very difficult to move the phosphor sheet after contacting the LED chip. On the other hand, the phosphor sheet according to the embodiment of the present invention does not have adhesiveness at room temperature, so it is easy to perform alignment in a state where the phosphor sheet and the LED chip are lightly contacted.

After the phosphor sheet according to the embodiment of the present invention is attached to the LED chip, it may be further subjected to a heat treatment using an oven or the like as necessary. By performing the heat treatment, the bonding between the phosphor sheet and the LED chip can be made stronger.

In addition, when the LED chip to which the phosphor sheet is attached is uniformly bonded to the mounting substrate, the bonding may be performed by heat compression bonding or soldering to the mounting substrate by reflow soldering.

As another embodiment of a method for manufacturing an LED package using a phosphor sheet according to an embodiment of the present invention, a method for mass-producing a LED package will be described. First, a method for manufacturing an LED wafer with a phosphor sheet will be described. As a method of attaching the phosphor sheet to the LED chip, for example, as shown in (1) and (2) of FIG. 4, the individualized phosphor sheet laminates 14 are attached one by one to Method on each LED wafer 1. In addition, as shown in (1) and (2) of FIG. 5, a plurality of LED chips 1 are collectively attached with phosphor sheets 2 and covered, and then the package substrate 15 is cut to separate the LED chips 1 individually. Method.

Next, as another embodiment of the manufacturing method of the LED package using a phosphor sheet according to the embodiment of the present invention, two methods are exemplified.

(A)-(f) of FIG. 6 shows a 1st manufacturing example. This is a preferable example in the case where the base material included in the phosphor sheet has fluidity.

As shown in FIG. 6 (a), the LED chip 1 is temporarily fixed to the base 18 via the double-sided adhesive tape 17. As shown in FIG. 6 (b), the phosphor sheet laminate 14 is laminated so that the phosphor sheet 2 contacts the LED wafer 1.

As shown in FIG. 6 (c), the laminate in FIG. 6 (b) is placed in the lower chamber 20 of the vacuum diaphragm laminator 22, and the upper chamber 19 and the lower chamber are heated while being heated. The chamber 20 is decompressed. Decompression heating is performed until the base material 9 flows, and then the diaphragm 21 is expanded by sucking the atmosphere into the upper chamber 19 through the suction port 23. Then, the phosphor sheet 2 is pressed through the base material 9, and the phosphor sheet 2 is attached so as to follow the light emitting surface of the LED wafer 1.

As shown in FIG. 6 (d), after the upper and lower chambers are returned to atmospheric pressure, the laminate is taken out from the vacuum diaphragm laminator 22 and left to cool, and the substrate 9 is peeled from the phosphor sheet 2. Then, a cutting site 24 between the LED wafers is cut by a dicing cutter or the like to produce a singulated LED wafer 25 with a phosphor sheet.

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

(A)-(e) of FIG. 7 shows a 2nd manufacturing example. This is another preferred example when the base material included in the phosphor sheet has fluidity.

As shown in FIG. 7 (a), the LED wafer 1 is bonded to the package electrode 16 on the mounting substrate 15 via the gold bump 7.

As shown in FIG. 7 (b), the phosphor sheet laminate 14 is laminated so that the phosphor sheet 2 contacts the LED wafer 1.

As shown in FIG. 7 (c), the laminate in FIG. 7 (b) is placed in the lower chamber 20 of the vacuum diaphragm laminator 22, and then the same as in FIGS. 6 (a) to (f) In the same manner as in the production example, the phosphor sheet 2 is attached to the light-emitting surface of the LED chip 1.

As shown in FIG. 7 (d), after the upper and lower chambers are returned to atmospheric pressure, the laminate is taken out from the vacuum diaphragm laminator 22 and left to cool, and the substrate 9 is peeled from the phosphor sheet 2. Then, the cutting | disconnection part 24 between LED packages is cut | disconnected, and it is singulated. 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 phosphor sheet. For example, the light emitting device includes an LED package, and the LED package includes the phosphor sheet or a cured product thereof 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 the light emitting device. For example, the backlight unit includes an LED package having the phosphor sheet or a cured product thereof. The backlight unit configured in this way can be used for displays, lighting, interiors, signs, signs, and the like, and is particularly suitable for display or lighting applications.

A display (such as a liquid crystal display) according to an embodiment of the present invention is an application example of the backlight unit. For example, the display includes an LED package having the phosphor sheet or a cured product thereof. [Example]

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

<Substrate> BX9: Released polyethylene terephthalate (polyethylene terephthalate film) "Cerapeel" BX9 (Toray film processing (shares ), Average film thickness is 50 μm) <Inorganic phosphor> ＞ Phosphor 1 (YAG1): "YAG81003" (YAG phosphor) manufactured by Nemoto Lumi-Materials (Stock Corporation) ･ Phosphor 2 (β1): "GR-SW532D" (β-type silicon aluminum oxynitride phosphor) manufactured by Denka Co., Ltd. Peak wavelength: 538 nm Average particle diameter (D50): 16 μm ･ Phosphor 3 (KSF1): KSF phosphor sample A, manufactured by Nemoto Lumi-Materials, average particle diameter (D50): 50 μm.

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

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

Then, under nitrogen gas flow, 17 g of 3- (4-third-butylphenyl) -1- (4-methoxyphenyl) propenone, 21.2 g of diethylamine, 17.7 g of nitromethane and A mixed solution of 580 ml of methanol was heated under reflux for 14 hours. The resulting solution was cooled to room temperature and evaporated. After purification by silica gel column chromatography and vacuum drying, 3- (4-third butylphenyl) -1- (4-methoxyphenyl) -4-nitrobutane-1 was obtained -Ketone 16 g.

Then, a mixed solution of 230 ml of methanol and 46 ml of concentrated sulfuric acid was stirred at 0 ° C under a nitrogen gas stream. Slowly add 1.42 g of 3- (4-tert-butylphenyl) -1- (4-methoxyphenyl) -4-nitrobutane-1-one prepared in advance under nitrogen flow, A mixed solution of 40 ml of methanol and 80 ml of tetrahydrofuran was added to 1.12 g of potassium hydroxide powder and stirred at room temperature for 1 hour, and further stirred at room temperature for 1 hour. Subsequently, after cooling to 0 ° C, 50 ml of water was added, neutralized with a 4 M sodium hydroxide aqueous 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 to obtain a thick substance.

Then, the obtained viscous substance, a mixed solution of 1.54 g of ammonium acetate and 20 ml of acetic acid were heated and refluxed for 1 hour under a nitrogen gas flow at 100 ° C. Subsequently, after cooling to room temperature, ice water was added, neutralization was performed with a 4 M sodium hydroxide aqueous solution, and extraction was performed 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-third-butylphenyl) -2- (4-methoxyphenyl) pyrrole was obtained.

Then, p- 2-benzylidene-3,5-bis (4-third-butylphenyl) pyrrole 357 mg, 4- (4-third-butylphenyl) -2- (4 -A mixed solution of 250 mg of methoxyphenyl) pyrrole, 138 mg of phosphorus oxychloride, and 10 ml of 1,2-dichloroethane was heated under reflux for 9 hours. Subsequently, after cooling to room temperature, 847 mg of diisopropylethylamine and 931 mg of boron trifluoride diethyl ether complex were added and stirred for 3 hours. Inject 20 ml of water and extract 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 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).

[Chemical 33]

(Synthesis Example 2) Hereinafter, a synthesis method of the organic phosphor (T22) in Synthesis Example 2 will be described. In a method for synthesizing organic phosphor (T22), 4- (4-tert-butylphenyl) -2- (4-methoxyphenyl) pyrrole 300 mg under nitrogen gas flow at 120 ° C A mixed solution of 201 mg of 2-methoxybenzidine chloride and 10 ml of toluene was heated for 6 hours. Subsequently, after cooling to room temperature, evaporation was performed. After washing with 20 ml of ethanol and vacuum drying, 2- (2-methoxybenzyl) -3- (4-thirdbutylphenyl) -5- (4-methoxybenzene Yl) pyrrole 260 mg.

Then, under nitrogen gas flow, 2- (2-methoxybenzyl) -3- (4-third butylphenyl) -5- (4-methoxyphenyl) pyrrole 260 mg, A mixed solution of 4- (4-tert-butylphenyl) -2- (4-methoxyphenyl) pyrrole 180 mg, methanesulfonic anhydride 206 mg, and degassed toluene 10 ml was performed at 125 ° C. Heat for 7 hours. Subsequently, after cooling to room temperature, 20 ml of water was poured, and extraction was performed with 30 ml of dichloromethane. The organic layer was washed twice with 20 ml of water, and evaporated and dried under vacuum.

Then, under a nitrogen gas stream, 305 mg of diisopropylethylamine and 670 mg of boron trifluoride diethyl ether complex were added to a mixed solution of the obtained pyrrole methylene body and 10 ml of toluene. Stir for 3 hours. Subsequently, 20 ml of water was injected, and extraction was performed with 30 ml of dichloromethane. The organic layer was washed twice with 20 ml of water, dried over magnesium sulfate, and then evaporated. The organic phosphor (T22) shown below was synthesized by purification by silica gel column chromatography.

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).

[Chem 34]

(Synthesis Example 3) Hereinafter, a synthesis method of the organic phosphor (T23) of Synthesis Example 3 will be described. In the synthesis method of organic phosphor (T23), put 2- (2-methoxybenzyl) -3,5-bis (4-th 5.0 g of tributylphenyl) pyrrole, 3.3 g of 2,4-bis (4-third butylphenyl) pyrrole, and 1.5 g of phosphorus oxychloride were reacted under heating and refluxing for 12 hours. Subsequently, after cooling to room temperature, 5.2 g of diisopropylethylamine and 5.6 g of boron trifluoride diethyl ether complex were added, and stirred for 6 hours. After adding 50 ml of water, the dichloromethane was extracted, and the organic layer was extracted and concentrated. After purification by column chromatography using silica gel, sublimation purification was performed to synthesize the organic phosphor (T23) shown below. .

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).

[Chemical 35]

(Synthesis Example 4) Hereinafter, a synthesis method of the organic phosphor (T24) in Synthesis Example 4 will be described. In the method for synthesizing organic phosphor (T24), 3,5-dibromobenzaldehyde (3.0 g), 4-third 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. Degassed toluene (30 mL) and degassed water (10 mL) were added thereto, and refluxed for 4 hours. The reaction solution was cooled to room temperature, and the organic layer was separated and washed with saturated brine. After the organic layer was dried with magnesium sulfate and filtered, the solvent was distilled off. The obtained reaction product was purified by silica gel column chromatography to obtain 3,5-bis (4-tert-butylphenyl) benzaldehyde (3.5 g) as a white solid.

Next, 3,5-bis (4-third butylphenyl) benzaldehyde (1.5 g) and 2,4-dimethylpyrrole (0.7 g) were put into the reaction solution, and dehydrated dichloromethane (200 mL) and trifluoroacetic acid (1 drop), and stirred under a nitrogen atmosphere for 4 hours. Subsequently, a solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (0.85 g) in dehydrated dichloromethane was added, and the mixture was further stirred for 1 hour. After the reaction was completed, boron trifluoride diethyl ether complex (7.0 mL) and diisopropylethylamine (7.0 mL) were added and stirred for 4 hours, and then water (100 mL) was added for stirring, and The organic layer was separated. After the organic layer was dried with magnesium sulfate and filtered, the solvent was distilled off. The obtained reaction product was purified by silica gel column chromatography, and an organic phosphor (T24) shown below was synthesized.

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).

[Chemical 36]

(Synthesis Example 5) Hereinafter, a synthesis method of the organic phosphor (T25) of Synthesis Example 5 will be described. The method for synthesizing organic phosphor (T25) was the same as that of Synthesis Example 4 except that instead of 2,4-dimethylpyrrole, ethyl 2,4-dimethylpyrrole-3-carboxylic acid was used as the raw material for pyrrole. Ground synthetic organic phosphor (T25).

[Chemical 37]

(Synthesis Example 6) Hereinafter, a synthesis method of the organic phosphor (T26) of Synthesis Example 6 will be described. In the method for synthesizing an organic phosphor (T26), an organic compound was synthesized in the same manner as in Synthesis Example 5 except that 4- (methoxycarbonyl) phenylboronic acid was used as a raw material for boronic acid instead of 4-thirdbutylphenylboronic acid. Phosphor (T26).

[Chemical 38]

<Silicone resin> The following is used as the silicone resin.

･ 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 part by weight, reaction inhibitor: 0.025 Parts by weight (A) component (MeViSiO _2/2 ) _0.35 (Ph ₂ SiO _2/2 ) _0.3 (PhSiO _3/2 ) _0.32 (HO _4/2 ) _0.03 (B) component (Me ₃ SiO _1/2 ) _0.3 ( PhViSiO _2/2 ) _0.4 (PhSiO _3/2 ) _0.3 (C) Component "HPM-502" (phenylmethylsiloxane copolymer) (D) component platinum complex made by Gelest (1,3-divinyl-1,1,3,3-tetramethyldisilaxane solution) Platinum content is 5% by weight Reaction inhibitor 1-ethynylhexanol ※ Among them, Me: methyl, Vi : Vinyl, Ph: phenyl.

･ 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 part by weight, reaction inhibitor: 0.025 (A) parts by weight (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 (B) component ( Me ₃ SiO _1/2 ) _0.3 (PhViSiO _2/2 ) _0.4 (PhSiO _3/2 ) _0.3 (C) component (HMe ₂ SiO) ₂ SiPh ₂ (D) component platinum complex (1,3-divinyl -1,1,3,3-tetramethyldisilaxane solution) platinum content is 5% by weight reaction inhibitor 1-ethynylhexanol ※ Among them, Me: methyl, Vi: vinyl, Ph: phenyl .

･ 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 part by weight, reaction inhibitor: 0.025 (A) parts by weight (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 (B) component ( Me ₃ SiO _1/2 ) _0.3 (PhViSiO _2/2 ) _0.4 (PhSiO _3/2 ) _0.3 (C) component (HMe ₂ SiO) ₂ SiPh ₂ (D) component platinum complex (1,3-divinyl -1,1,3,3-tetramethyldisilaxane solution) platinum content is 5% by weight reaction inhibitor 1-ethynylhexanol ※ Among them, Me: methyl, Vi: vinyl, Ph: phenyl .

･ 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 part by weight, reaction inhibitor: 0.025 Parts by weight (A) component (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 (B) component ( Me ₃ SiO _1/2 ) _0.3 (PhViSiO _2/2 ) _0.4 (PhSiO _3/2 ) _0.3 (C) component (HMe ₂ SiO) ₂ SiPh ₂ (D) component platinum complex (1,3-divinyl -1,1,3,3-tetramethyldisilaxane solution) platinum content is 5% by weight reaction inhibitor 1-ethynylhexanol ※ Among them, Me: methyl, Vi: vinyl, Ph: phenyl .

･ 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 part by weight, reaction inhibitor: 0.025 (A) parts by weight (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 (B) component ( Me ₃ SiO _1/2 ) _0.3 (PhViSiO _2/2 ) _0.5 (PhSiO _3/2 ) _0.2 (C) component (HMe ₂ SiO) ₂ SiPh ₂ (D) component platinum complex (1,3-divinyl -1,1,3,3-tetramethyldisilaxane solution) platinum content is 5% by weight reaction inhibitor 1-ethynylhexanol ※ Among them, Me: methyl, Vi: vinyl, Ph: phenyl .

･ 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 part by weight, reaction inhibitor: 0.025 (A) parts by weight (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 (B) component ( Me ₃ SiO _1/2 ) _0.3 (PhViSiO _2/2 ) _0.4 (PhSiO _3/2 ) _0.3 (C) component (HMe ₂ SiO) ₂ SiPh ₂ (D) component platinum complex (1,3-divinyl -1,1,3,3-tetramethyldisilaxane solution) platinum content is 5% by weight reaction inhibitor 1-ethynylhexanol ※ Among them, Me: methyl, Vi: vinyl, Ph: phenyl .

･ 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 part by weight, reaction inhibitor: 0.025 (A) parts by weight (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 (B) component ( Me ₃ SiO _1/2 ) _0.3 (PhViSiO _2/2 ) _0.4 (PhSiO _3/2 ) _0.3 (C) component (HMe ₂ SiO) ₂ SiPh ₂ (D) component platinum complex (1,3-divinyl -1,1,3,3-tetramethyldisilaxane solution) platinum content is 5% by weight reaction inhibitor 1-ethynylhexanol ※ Among them, Me: methyl, Vi: vinyl, Ph: phenyl .

･ Silicone resin 8 (Si8): OE6630 (Toray ･ Dow Corning silicone).

･ Silicone resin 9 (Si9): 16.7 parts by weight of the main component of the resin, 16.7 parts by weight of the hardness modifier, 66.7 parts by weight of the crosslinking agent, 0.025 parts by weight of the reaction inhibitor, and 0.03 parts by weight of the platinum catalyst. Ingredient 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 (equivalent to component (A)) hardness modifier ViMe ₂ SiO (MePhSiO ) _17.5 SiMe ₂ Vi (corresponding to (B) component) Crosslinker (HMe ₂ SiO) ₂ SiPh ₂ (corresponding to (C) component) ※ Among them, Me: methyl, Vi: vinyl, Ph: phenyl reaction Inhibitor 1-ethynylhexanol platinum catalyst platinum complex (1,3-divinyl-1,1,3,3-tetramethyldisilaxane solution) Platinum content is 5 wt% (equivalent (D) ingredients).

<Silicone fine particles> A 2 L four-neck round bottom flask was equipped with a stirrer, a thermometer, a reflux tube, and a dropping funnel. Put 2 L of 2.5% ammonia water containing 1 ppm of polyether-modified silicone "BYK" 333 as a surfactant into this flask, and heat up in an oil bath while stirring at 300 rpm . When the internal temperature reached 50 ° C, a mixture of methyltrimethoxysilane (MTM) and phenyltrimethoxysilane (PhTM) was added dropwise from the dropping funnel over 30 minutes (MTH / PhTM = 23 mol% / 77 mol% ) 200 g. After maintaining the temperature for 60 minutes, about 5 g of acetic acid (special grade reagent) was added. The mixture was stirred and then filtered 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 separately. The cake on the filter was taken out and pulverized, and freeze-dried for 10 hours to obtain 60 g of a white powder. Observation of the obtained white powder by SEM revealed monodisperse spherical fine particles. The refractive index of the fine particles was measured by the immersion method, and it was 1.54. The microparticles were observed with a cross-section TEM using a transmission electron microscope (TEM). As a result, they were confirmed to be microparticles having a single structure within the particles.

<Dynamic Elastic Modulus Measurement> The obtained phosphor sheet was cut out in a circular shape having a diameter of 20 mm, and after the substrate was peeled off, the storage elastic modulus was measured using the following apparatus.

Measuring device: Viscosity and viscoelasticity measuring device HAAKE MARSIII (manufactured by Thermo Fisher SCIENTIFIC) Measuring conditions: OSC temperature-dependent measuring geometry: Parallel disc type (20 mm) Measuring time: 1980 second angular frequency: 1 Hz angular velocity: 6.2832 rad / sec temperature range: 25 ℃ ～ 200 ℃ (with low temperature control function) heating rate: 0.08333 ℃ / sec sample shape: round (18 mm diameter).

<Evaluation of cutting processability> The obtained phosphor sheet was cut into 1 mm × 0.3 mm squares using a cutting device “GCUT” (manufactured by UHT Co., Ltd.) to prepare 100 single-piece phosphor sheets. A single phosphor sheet was observed with an optical microscope, and the number of samples having cracks or notches in the peripheral portion was counted. The smaller the number of samples having cracks or notches in the peripheral portion, the better the cutting workability. When it is evaluated as B or more, it is practically excellent. S: 0 cutting processability is very good A: 1 or more, 3 or less cutting processability is good B: 4 or more, 10 cutting processability is practically no problem C: 11 or more, 30 The following cutting workability was poor D: 31 or more cutting workability was very poor.

<Manufacturing method of LED package> The obtained phosphor sheet was cut into 1 mm × 0.3 mm squares using a cutting device “GCUT” (manufactured by UHT Co., Ltd.) to produce 100 single-piece phosphor sheets. Using a flip-chip bonding apparatus (manufactured by Toray Engineering), a single phosphor sheet was vacuum-adsorbed by a collet to peel it from the substrate. The peeled single-piece phosphor sheet was attached to the surface of an LED chip of an LED package in which a flip-chip type LED chip was mounted under the following attaching conditions. The obtained package was connected to a DC power source and turned on, and it was confirmed whether or not it was turned on.

(Attachment conditions) Heating conditions: 140 ° C Pressing conditions: 80 N Pressing time: 20 seconds.

<Adhesion Evaluation> Using the obtained LED package, tweezers were placed in the interface between the LED chip and the phosphor sheet, and then the phosphor sheet was lifted up with tweezers to confirm the adhesiveness between the LED chip and the phosphor sheet. In the sample with good adhesion, the phosphor sheet did not peel even when lifted by tweezers. In the sample with poor adhesion, the phosphor sheet was peeled from the LED chip. Observation was performed with an optical microscope, and the number of samples with peeling was counted. The smaller the number of samples where peeling occurred, the better the adhesion. When it is evaluated as B or more, it is practically excellent. S: 0 adhesiveness is very good A: 1 or more and 5 or less good adhesiveness B: 6 or more and 10 or less adhesiveness is practically no problem C: 11 or more and 30 or less poor adhesion D: 31 The adhesion is very poor.

<Total Luminous Flux Measurement> The LED package was lighted 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 Corporation). The relative brightness when the total luminous flux in Comparative Example 1 was set to 100 was calculated.

(Example 1) (Effect of silicone composition) Using a polyethylene container with a volume of 100 ml, 18.0 g of silicone resin 1 (Si1) and 42.0 g of phosphor 1 (YAG1) as an inorganic phosphor were added. And 2.5 g of butylcarbitol and mixed. After that, using a planetary stirring / defoaming device, stirring and defoaming were performed at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times with a three-roller to prepare a phosphor composition 1.

Using a slit die coater, the phosphor composition 1 was coated on the release-treated surface of "Cerapeel" BX9 as a substrate, and heated and dried at 120 ° C for 40 minutes to obtain 80 μm thick, 100 mm square phosphor sheet. The method described above was used to measure the dynamic elastic modulus and evaluate the cutting processability. In addition, an LED package was produced by the method described above, and adhesiveness evaluation and total luminous flux measurement were performed. The results are shown in Table 1. As a result, good cutting workability and improved adhesion can be obtained, and relative brightness can be 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. Thereafter, 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 can be seen that the phosphor sheet according to the embodiment of the present invention has good cutting workability and adhesiveness. It can also be seen that the relative brightness is 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, although cutting workability was not a practical problem, the adhesiveness was not improved.

(Example 3) (Change of silicone resin, addition of silicone fine particles) A polyethylene container having a volume of 100 ml was used, and 17.0 g of silicone resin 2 (Si2) was added, and phosphor 1 (as an inorganic phosphor) was added. YAG1) 42.0 g, silicone fine particles 0.6 g, and butylcarbitol 2.5 g were mixed. Thereafter, a planetary stirring / defoaming device was used to perform stirring / defoaming at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times using a three-roller to prepare a phosphor composition 3.

Using a slit die coater, the phosphor composition 3 was coated on the release-treated surface of "Cerapeel" BX9 as a substrate, and heated and dried at 120 ° C for 40 minutes to obtain 80 μm thick, 100 mm square phosphor sheet. The method described above was used to measure the dynamic elastic modulus and evaluate the cutting processability. In addition, an LED package was produced by the method described above, and adhesiveness evaluation and total luminous flux measurement were performed. The results are shown in Table 1. Both good cutting processability and good adhesion were obtained, and the relative brightness was also improved.

(Example 4 to Example 8) (Change of silicone composition) A phosphor sheet was produced by the same operation as in Example 3 except that the silicone resin was changed to Si3 to Si7 as shown in Table 1. 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 Examples 4 to 8, it can be seen that if the phosphor sheet is an embodiment of the present invention, the cutting workability is good, and the adhesiveness is also improved. It can also be seen that the relative brightness is also improved.

(Comparative Example 2) A phosphor sheet was produced by the same operation as in Example 3, except that the silicone resin was changed to Si9 as shown in Table 1. Thereafter, an LED package was produced, and each measurement and evaluation was performed. The results are shown in Table 1. In Comparative Example 2, although cutting workability was not a practical problem, the adhesiveness was not improved. In addition, the brightness has not been improved.

(Example 9) (Change the resin content to 10.0% by weight) Using a polyethylene container with a volume of 100 ml, 5.96 g of silicone resin 2 (Si2) was added, and phosphor 1 (YAG1) as an inorganic phosphor was added. 53.6 g, silicone fine particles 0.6 g, and butylcarbitol 2.5 g were mixed. Thereafter, a planetary stirring / defoaming device was used to perform stirring / defoaming at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times with a three-roller to prepare a phosphor composition 11.

Using a slit die coater, the phosphor composition 11 was coated on the release-treated surface of "Cerapeel" BX9 as a substrate, and heated and dried at 120 ° C for 40 minutes to obtain 80 μm thick, 100 mm square phosphor sheet. The method described above was used to measure the dynamic elastic modulus and evaluate the cutting processability. In addition, an LED package was produced by the method described above, and adhesiveness evaluation and total luminous flux measurement were performed. The results are shown in Table 2. Both good cutting processability and good adhesion were obtained, and the relative brightness was also improved.

(Example 10) (Change the resin content to 70.0% by weight) A polyethylene container with a volume of 100 ml was used, and 42.4 g of silicone resin 2 (Si2) was added, and phosphor 1 (YAG1) as an inorganic phosphor was added. 17.5 g, silicone fine particles 0.6 g, and butylcarbitol 2.5 g were mixed. Thereafter, a planetary stirring / defoaming device was used to perform stirring / defoaming at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times with a three-roller to prepare a phosphor composition 12.

Using a slit die coater, the phosphor composition 12 was coated on the release-treated surface of "Cerapeel" BX9 as a substrate, and heated and dried at 120 ° C for 40 minutes to obtain 80 μm thick, 100 mm square phosphor sheet. The method described above was used to measure the dynamic elastic modulus and evaluate the cutting processability. In addition, an LED package was produced by the method described above, and adhesiveness evaluation and total luminous flux measurement were performed. The results are shown in Table 2. Both good cutting processability and good adhesion were obtained, and the relative brightness was also improved.

(Example 11) (Change the resin content to 85.0% by weight) Using a polyethylene container with a volume of 100 ml, 52.5 g of silicone resin 2 (Si2) was added, and phosphor 1 (YAG1) as an inorganic phosphor was added. 8.6 g, silicone fine particles 0.6 g, and butylcarbitol 2.5 g were mixed. Thereafter, using a planetary agitation defoaming device, stirring and defoaming were performed at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times with a three-roller to prepare a phosphor composition 13.

Using a slit die coater, the phosphor composition 13 was coated on the release-treated surface of "Cerapeel" BX9 as a substrate, and heated and dried at 120 ° C for 40 minutes to obtain 80 μm thick, 100 mm square phosphor sheet. The method described above was used to measure the dynamic elastic modulus and evaluate the cutting processability. In addition, an LED package was produced by the method described above, and adhesiveness evaluation and total luminous flux measurement were performed. The results are shown in Table 2. Both good cutting processability and good adhesion were obtained, and the relative brightness was also improved.

(Example 12) (Change the content of silicone fine particles to 0.5% by weight) Using a polyethylene container with a volume of 100 ml, 17.0 g of silicone resin 2 (Si2) was added, and phosphor 1 (as an inorganic phosphor) YAG1) 42.0 g, silicone fine particles 0.3 g, and butylcarbitol 2.5 g were mixed. After that, using a planetary stirring / defoaming device, stirring and defoaming were performed at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times with a three-roller to prepare a phosphor composition 14.

Using a slit die coater, the phosphor composition 14 was coated on the release-treated surface of "Cerapeel" BX9 as a substrate, and heated and dried at 120 ° C for 40 minutes to obtain 80 μm thick, 100 mm square phosphor sheet. The method described above was used to measure the dynamic elastic modulus and evaluate the cutting processability. In addition, an LED package was produced by the method described above, and adhesiveness evaluation and total luminous flux measurement were performed. The results are shown in Table 2. Both good cutting processability and good adhesion were obtained, and the relative brightness was also improved.

(Example 13) (Change the content of silicone fine particles to 10.0% by weight) Using a polyethylene container with a volume of 100 ml, 11.0 g of silicone resin 2 (Si2) was added, and phosphor 1 (as an inorganic phosphor) YAG1) 42.0 g, silicone fine particles 6 g, and butylcarbitol 2.5 g were mixed. Thereafter, using a planetary stirring / defoaming device, stirring and defoaming were performed at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times with a three-roller to prepare a phosphor composition 15.

Using a slit die coater, the phosphor composition 15 was coated on the release-treated surface of "Cerapeel" BX9 as a substrate, and heated and dried at 120 ° C for 40 minutes to obtain 80 μm thick, 100 mm square phosphor sheet. The method described above was used to measure the dynamic elastic modulus and evaluate the cutting processability. In addition, an LED package was produced by the method described above, and adhesiveness evaluation and total luminous flux measurement were performed. The results are shown in Table 2. Both good cutting processability and good adhesion were obtained, and the relative brightness was also improved.

(Example 14) (Change the content of silicone fine particles to 20.0% by weight) Using a polyethylene container with a volume of 100 ml, 6 g of silicone resin 2 (Si2) was added, and phosphor 1 as an inorganic phosphor ( YAG1) 42.0 g, silicone fine particles 12 g, and butylcarbitol 2.5 g were mixed. Thereafter, a planetary stirring / defoaming device was used to perform stirring / defoaming at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times with a three-roller to prepare a phosphor composition 16.

Using a slit die coater, the phosphor composition 16 was coated on the release-treated surface of "Cerapeel" BX9 as a substrate, and heated and dried at 120 ° C for 40 minutes to obtain 80 μm thick, 100 mm square phosphor sheet. The method described above was used to measure the dynamic elastic modulus and evaluate the cutting processability. In addition, an LED package was produced by the method described above, and adhesiveness evaluation and total luminous flux measurement were performed. The results are shown in Table 2. Both good cutting processability and good adhesion were obtained, and the relative brightness was also improved.

(Example 15) (Change the phosphor content to 38.0% by weight) Using a polyethylene container with a volume of 100 ml, 36.4 g of silicone resin 2 (Si2) was added, and phosphor 1 as an inorganic phosphor ( YAG1) 22.7 g, silicone fine particles 0.6 g, and butylcarbitol 2.5 g were mixed. Thereafter, using a planetary stirring / defoaming device, stirring and defoaming were performed at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times with a three-roller to prepare a phosphor composition 17.

Using a slit die coater, the phosphor composition 17 was coated on the release-treated surface of "Cerapeel" BX9 as a substrate, and heated and dried at 120 ° C for 40 minutes to obtain 80 μm thick, 100 mm square phosphor sheet. The method described above was used to measure the dynamic elastic modulus and evaluate the cutting processability. In addition, an LED package was produced by the method described above, and adhesiveness evaluation and total luminous flux measurement were performed. The results are shown in Table 3. Both good cutting processability and good adhesion were obtained, and the relative brightness was also improved.

(Example 16) (Change the phosphor content to 40.0% by weight) Using a polyethylene container with a volume of 100 ml, 35.2 g of silicone resin 2 (Si2) was added, and phosphor 1 as an inorganic phosphor ( YAG1) 23.8 g, silicone fine particles 0.6 g, and butylcarbitol 2.5 g were mixed. Thereafter, using a planetary stirring / defoaming device, stirring and defoaming were performed at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times with a three-roller to prepare a phosphor composition 18.

Using a slit die coater, the phosphor composition 18 was coated on the release-treated surface of "Cerapeel" BX9 as a substrate, and heated and dried at 120 ° C for 40 minutes to obtain 80 μm thick, 100 mm square phosphor sheet. The method described above was used to measure the dynamic elastic modulus and evaluate the cutting processability. In addition, an LED package was produced by the method described above, and adhesiveness evaluation and total luminous flux measurement were performed. The results are shown in Table 3. Both good cutting processability and good adhesion were obtained, and the relative brightness was also improved.

(Example 17) (Change the phosphor content to 63.0% by weight) Using a polyethylene container with a volume of 100 ml, 21.5 g of silicone resin 2 (Si2) was added, and phosphor 1 as an inorganic phosphor ( YAG1) 37.6 g, silicone fine particles 0.6 g, and butylcarbitol 2.5 g were mixed. Thereafter, a planetary stirring / defoaming device was used to perform stirring / defoaming at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times using a three-roller to prepare a phosphor composition 19.

Using a slit die coater, the phosphor composition 19 was coated on the release-treated surface of "Cerapeel" BX9 as a substrate, and heated and dried at 120 ° C for 40 minutes to obtain 80 μm thick, 100 mm square phosphor sheet. The method described above was used to measure the dynamic elastic modulus and evaluate the cutting processability. In addition, an LED package was produced by the method described above, and adhesiveness evaluation and total luminous flux measurement were performed. The results are shown in Table 3. Both good cutting processability and good adhesion were obtained, and the relative brightness was also improved.

(Example 18) (Change the phosphor content to 80.0% by weight) Using a polyethylene container with a volume of 100 ml, 11.3 g of silicone resin 2 (Si2) was added, and phosphor 1 as an inorganic phosphor ( YAG1) 47.7 g, silicone fine particles 0.6 g, and butylcarbitol 2.5 g were mixed. Thereafter, a planetary stirring / defoaming device was used to perform stirring / defoaming at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times with a three-roller to prepare a phosphor composition 20.

Using a slit die coater, the phosphor composition 20 was coated on the release-treated surface of "Cerapeel" BX9 as a substrate, and heated and dried at 120 ° C for 40 minutes to obtain 80 μm thick, 100 mm square phosphor sheet. The method described above was used to measure the dynamic elastic modulus and evaluate the cutting processability. In addition, an LED package was produced by the method described above, and adhesiveness evaluation and total luminous flux measurement were performed. The results are shown in Table 3. Both good cutting processability and good adhesion were obtained, and the relative brightness was also improved.

(Comparative Example 3) A phosphor sheet was produced by the same operation as in Example 15 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, although the cutting workability is practically not a problem, the adhesion is not improved.

(Comparative Example 4) A phosphor sheet was produced by the same operation as in Example 16 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, although the cutting workability is practically not a problem, the adhesion is 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, although the cutting workability is practically not a problem, the adhesion is not improved.

(Comparative Example 6) A phosphor sheet was produced by the same operation as in Example 18 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 low, and the adhesion was not improved.

(Example 19) (Change of phosphor-1) A polyethylene container with a volume of 100 ml was used, and 17.0 g of silicone resin 2 (Si2) was added, and phosphor 2 (β1) 16.8 as an inorganic phosphor was added. g, 25.2 g of phosphor 3 (KSF1), 0.6 g of silicone fine particles, and 2.5 g of butylcarbitol. Thereafter, a planetary stirring / defoaming device was used to perform stirring / defoaming at 1000 rpm for 5 minutes, and then mixed and dispersed 6 times with a three-roller to prepare a phosphor composition 25.

Using a slit die coater, a phosphor composition 25 was coated on the release-treated surface of "Cerapeel" BX9 as a substrate, and heated and dried at 120 ° C for 30 minutes to obtain 80 μm thick, 100 mm square phosphor sheet. The method described above was used to measure the dynamic elastic modulus and evaluate the cutting processability. In addition, an LED package was produced by the method described above, and adhesiveness evaluation and total luminous flux measurement were performed. The results are shown in Table 4. Both cutting processability and adhesion were very good, 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, although cutting workability was not a practical problem, the adhesiveness was not improved.

(Example 20) (Change of phosphor-2) Using a 100 ml polyethylene container, 60.0 g of silicone resin 2 (Si2) was added and phosphor 4 (type 21) as an organic phosphor 1.24 × 10 ^-3 g, phosphor 5 (type 24) 1.24 × 10 ^-3 g, silicone fine particles 1.0 g, and butylcarbitol 2.5 g were mixed. Thereafter, a planetary stirring and defoaming device was used to stir and defoam at 1000 rpm for 5 minutes, thereby producing a phosphor composition 27.

Using a slit die coater, a phosphor composition 27 was coated on the release-treated surface of "Cerapeel" BX9 as a substrate, and heated and dried at 120 ° C for 30 minutes to obtain 80 μm thick, 100 mm square phosphor sheet. The method described above was used to measure the dynamic elastic modulus and evaluate the cutting processability. In addition, an LED package was produced by the method described above, and adhesiveness evaluation and total luminous flux measurement were performed. The results are shown in Table 5. Both cutting processability and adhesion were very good, and the relative brightness was improved.

(Example 21 to Example 24) (Change of Phosphor-3) In Examples 21 to 24, except that the organic phosphor was appropriately changed as shown in Table 5, it was the same as Example 20 The phosphor composition (28 to 32) was produced by the operation described above, and a phosphor sheet was produced by the same operation as in Example 20 using each phosphor composition. Thereafter, an LED package was produced using each phosphor sheet and evaluated. The results are shown in Table 5. From the evaluation results of Examples 21 to 24, it can be seen that the results of very good cutting processability and adhesiveness are obtained, and the relative brightness is improved.

(Comparative Example 8) Except that the silicone resin was changed to Si9 and the phosphor was changed to phosphor 4 (type 27) and phosphor 5 (type 28), it was produced by the same operation as in Example 20. The phosphor composition 33 is used to make a phosphor sheet. Thereafter, an LED package was produced, and each measurement and evaluation was performed. The results are shown in Table 5. As shown in Table 5, although the cutting workability was practically not a problem, the adhesiveness was not improved.

[Chemical 39]

[Chemical 40]

[TABLE 1] [TABLE 1]

[TABLE 2] [TABLE 2]

[TABLE 3] [TABLE 3]

[TABLE 4] [TABLE 4]

[TABLE 5] [TABLE 5]

1‧‧‧LED chip

2‧‧‧ phosphor film

3‧‧‧ transparent sealing material

4‧‧‧ reflector

5‧‧‧Mounting base

6‧‧‧ electrode

7‧‧‧ gold bump

8‧‧‧ Transparent Adhesive / Adhesive

9‧‧‧ substrate

10‧‧‧LED Package

11‧‧‧ temporary fixing piece

12‧‧‧Heat crimping tool

13‧‧‧ Wafers / wafers with LED chips on the surface

14‧‧‧ phosphor sheet laminate

15‧‧‧ package substrate

16‧‧‧ packaged electrodes

17‧‧‧ double-sided adhesive tape

18‧‧‧ pedestal

19‧‧‧ Upper chamber

20‧‧‧lower chamber

21‧‧‧ diaphragm

22‧‧‧Vacuum Diaphragm Laminator

23‧‧‧ Suction / Exhaust

24‧‧‧ Cut off part

25‧‧‧LED chip with phosphor sheet

26‧‧‧LED chip / LED chip with phosphor sheet with substrate

(A)-(f) of FIG. 1A is an example of the LED package using the phosphor sheet which concerns on embodiment of this invention. (G)-(i) of FIG. 1B is an example of the LED package using the phosphor sheet which concerns on embodiment of this invention. (A)-(f) of FIG. 2 is an example of the manufacturing method of the LED package using the fluorescent sheet which concerns on embodiment of this invention. FIGS. 3A to 3F are examples of a method for attaching a phosphor sheet according to an embodiment of the present invention. (1) and (2) of FIG. 4 are examples of a method for attaching a phosphor sheet according to an embodiment of the present invention. (1) and (2) of FIG. 5 are examples of a method for attaching a phosphor sheet according to an embodiment of the present invention. (A)-(f) is an example of the manufacturing method of the LED package using the fluorescent sheet which concerns on embodiment of this invention. FIGS. 7A to 7E are examples of a method for manufacturing an LED package using a phosphor sheet according to an embodiment of the present invention.

Claims (19)

A phosphor sheet comprising a phosphor and a silicone resin, and the storage elastic modulus G 'of the phosphor sheet at 25 ° C is 0.01 MPa or more, and the storage elastic modulus G' at 100 ° C is less than The storage elastic modulus G 'at 0.01 MPa and 140 ° C is 0.05 MPa or more. The phosphor sheet according to item 1 of the scope of patent application, wherein the silicone resin is a crosslinked product of a crosslinkable silicone composition containing at least the following components (A) to (D); (A ) Average unit: (In the average unit formula (1), R ¹ is a monovalent hydrocarbon group having 1 to 14 carbons, at least one is an aryl group, and at least one is an alkenyl group having 2 to 6 carbons; R ² is a hydrogen atom or a carbon number 1 ~ 6 alkyl groups; a, b, c, d, and e satisfy 0 ≦ a ≦ 0.1, 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) The average unit formula of the organopolysiloxane (B) with a branch structure represented by: (In the average unit formula (2), R ³ 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 group having 2 to 6 carbon atoms; f, g, and h satisfy 0.1 < f ≦ 0.4, 0.2 ≦ g ≦ 0.5, 0.2 ≦ h ≦ 0.5, and f + g + h = 1) The organopolysiloxane (C) having a branch structure represented by at least two in one molecule An organic polysiloxane (D) catalyst for the hydrosilylation of Si-H bond and an organic group of 12 mol% to 70 mol% bonded to a silicon atom. The phosphor sheet according to item 2 of the scope of patent application, wherein the content of the (B) component is 10 parts by weight or more and 95 parts by weight or less based on 100 parts by weight of the (A) component. The phosphor sheet according to any one of claims 1 to 3, wherein (C) component is an 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; wherein 12 to 70 mol% in R ⁴ is an aryl group) Organic polysiloxane. The phosphor sheet according to any one of items 1 to 4 of the scope of patent application, wherein the content of the phosphor is 40% by weight or more and 90% by weight or less. The phosphor sheet according to any one of claims 1 to 5, wherein the phosphor includes a β-type silicon aluminum nitride oxide phosphor and a general formula A ₂ MF ₆ : Mn ( Here, A is one or more alkali metals selected from the group consisting of Li, Na, K, Rb, and Cs and including at least Na and / or K, and M is selected from the group consisting of Si, Ti, Zr, Hf, and Ge Mn-activated composite fluoride phosphors represented by one or more tetravalent elements in the group consisting of and Sn). The phosphor sheet according to any one of claims 1 to 4, wherein the phosphor is a pyrrole methylene compound. The phosphor sheet according to item 7 of the scope of patent application, wherein the phosphor 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, and are selected from hydrogen, alkyl, cycloalkyl, aralkyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, mercapto, Alkoxy, alkylthio, arylether, arylthioether, aryl, heteroaryl, heterocyclyl, halogen, haloalkane, haloalkene, haloalkyne, cyano, aldehyde, carbonyl , Carboxyl, ester, carbamoyl, amine, nitro, silyl, siloxy, and condensed rings and aliphatic rings formed between adjacent substituents; M represents an m-valent metal, and It is at least one selected from the group consisting of boron, beryllium, magnesium, chromium, iron, nickel, copper, zinc, and platinum). The phosphor sheet according to item 8 of the scope of patent application, wherein M in the general formula (4) is boron, L is fluorine or a fluorine-containing aryl group, and m-1 is 2. The phosphor sheet according to item 8 or item 9 of the scope of patent application, wherein in the general formula (4), Ar ⁵ is a group represented by the general formula (5); (R is selected from the group consisting of hydrogen, alkyl, cycloalkyl, heterocyclyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, thiol, alkoxy, alkylthio, arylether, arylthioether , Aryl, heteroaryl, halogen, cyano, aldehyde, carbonyl, carboxyl, oxycarbonyl, carbamoyl, amine, nitro, silyl, siloxyalkyl, oxyboryl, phosphine oxide In the group formed, k is an integer of 1 to 3; when k is 2 or more, r may be the same or different). A light-emitting diode wafer includes the phosphor sheet or the cured product thereof according to any one of the first to tenth of the scope of patent application. A light-emitting diode package includes the phosphor sheet or a cured product thereof according to any one of claims 1 to 10 in the scope of patent application. A manufacturing method of a light emitting diode package includes the steps of cutting the phosphor sheet as described in any one of the first to tenth of the scope of patent application into a single sheet, and cutting into a single sheet. A step of attaching the phosphor sheet to a light emitting diode wafer. The method for manufacturing a light-emitting diode package according to item 13 of the scope of patent application, wherein the phosphor sheet is attached to a portion of the light-emitting surface of the light-emitting diode wafer that avoids an electrode. A method for manufacturing a light-emitting diode package, comprising: attaching a plurality of light-emitting diodes formed by uniformly attaching a phosphor sheet according to any one of claims 1 to 10 of a patent application scope to a wafer The steps on the polar wafer and the step of singulating the wafer and singulating the light emitting diode wafer to which the phosphor sheet is attached are unified. The method for manufacturing a light-emitting diode package according to any one of claims 13 to 15, wherein a heating temperature when the phosphor sheet is attached to the light-emitting diode wafer is Above 60 ° C and below 250 ° C. A light-emitting device includes the light-emitting diode package according to item 12 of the scope of patent application. A backlight unit includes the light-emitting diode package according to item 12 of the scope of patent application. A display includes the light-emitting diode package according to item 12 of the scope of patent application.