WO2018155253A1

WO2018155253A1 - 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

Info

Publication number: WO2018155253A1
Application number: PCT/JP2018/004863
Authority: WO
Inventors: 石田豊; 神崎達也; 長瀬亮
Original assignee: 東レ株式会社
Priority date: 2017-02-23
Filing date: 2018-02-13
Publication date: 2018-08-30
Also published as: JPWO2018155253A1; KR102215781B1; TW201840722A; JP6863367B2; CN110312954A; KR20190118153A; CN110312954B; TWI753113B

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°C of 0.01 MPa or more, a storage elastic modulus at 100°C of less than 0.01 MPa and a storage elastic modulus G' at 140°C of 0.05 MPa or more.

Description

Phosphor sheet, LED chip and LED package using the same, LED package manufacturing method, 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 phosphor sheet, a method for manufacturing the LED package, and a light emitting device including the LED package, a backlight unit, and a display.

Light-emitting diodes (LEDs, Light Emitting Diodes) are backed by remarkable improvements in their luminous efficiencies, featuring low power consumption, long life, and design, etc., for backlights of liquid crystal displays (LCD, Liquid Crystal Display), The market is rapidly expanding not only for in-vehicle fields such as car headlights but also for general lighting. LEDs are expected to form a huge market in the general lighting field because of their low environmental impact.

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

As a specific method for installing the phosphor on the LED chip, a method of attaching a phosphor-containing sheet (hereinafter referred to as “phosphor sheet”) on the LED chip has been proposed (for example, Patent Documents 1 to 4). This method has a constant amount of the phosphor disposed on the LED chip, compared to a method in which a phosphor composition in which a phosphor is dispersed in a resin is dispensed on the LED chip and cured. It is easy to make the quantity. As a result, it is excellent in that the color and brightness of the obtained white LED can be made uniform.

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

When using the method of sticking the phosphor sheet on the LED chip, it corresponds to a cutting process when the phosphor sheet is singulated to the size of the LED chip, or an electrode portion on the LED chip in the phosphor sheet. It is necessary to drill holes in the part. Therefore, a phosphor sheet excellent in processability is required.

On the other hand, the phosphor sheet is required to have adhesiveness so as to be stuck on the LED chip. In Patent Document 4, by using a silicone composition containing a specific organopolysiloxane, it is excellent in processability before being attached to the LED chip, and is excellent in adhesiveness when being attached to the LED chip. It is disclosed that a phosphor sheet can be obtained. However, since this phosphor sheet has insufficient curability of the phosphor sheet after being attached to the LED chip, satisfactory adhesiveness has not been obtained. As a result, the LED chip to which the phosphor sheet is attached has a problem that the luminance is lowered due to poor adhesion.

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

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

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

An example of the LED package using the fluorescent substance sheet which concerns on embodiment of this invention. An example of the LED package using the fluorescent substance sheet which concerns on embodiment of this invention. An example of the manufacturing method of the LED package using the fluorescent substance sheet which concerns on embodiment of this invention. An example of the sticking method of the fluorescent substance sheet which concerns on embodiment of this invention. An example of the sticking method of the fluorescent substance sheet which concerns on embodiment of this invention. An example of the sticking method of the fluorescent substance sheet which concerns on embodiment of this invention. An example of the manufacturing method of the LED package using the fluorescent substance sheet which concerns on embodiment of this invention. An example of the manufacturing method of the LED package using the fluorescent substance sheet which concerns on embodiment of this invention.

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

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

The phosphor sheet according to the embodiment of the present invention is sufficiently elastic at room temperature (25 ° C.) because the storage elastic modulus G ′ at 25 ° C. is 0.01 MPa or more. For this reason, the phosphor sheet is cut without deformation around the cut portion against fast shearing stress such as cutting with a blade, and processability with high dimensional accuracy is obtained.

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

The phosphor sheet according to the embodiment of the present invention has a storage elastic modulus G ′ at 100 ° C. of less than 0.01 MPa, so that the sheet is sufficiently viscous at 100 ° C. and has high fluidity. For this reason, the phosphor sheet having this physical property is heated and heated at 100 ° C. or more to the LED chip, so that the phosphor sheet quickly flows and deforms according to the shape of the light emitting surface of the LED chip. High adhesion between the LED chip and the LED chip can be obtained. Thereby, the light extraction property from the LED chip is improved, and the luminance is improved.

The lower limit of the storage elastic modulus G ′ at 100 ° C. is not particularly limited. However, if the flowability of the phosphor sheet is too high at the time of heat pasting on the LED chip, it is processed by cutting or punching before pasting. Since the shape cannot be retained at the time of pasting, it is preferably 0.005 MPa or more.

The phosphor sheet according to the embodiment of the present invention has a storage elastic modulus G ′ at 140 ° C. of 0.05 MPa or more, so that the LED chip can finally be stably operated. If the phosphor sheet having this physical property is heated at 140 ° C. or higher, complete curing of the sheet is completed quickly and the entire resin is integrated, so that the adhesion between the phosphor sheet and the LED chip is improved. Thereby, the brightness of the LED package is also improved. Moreover, since it becomes difficult to receive the influence of the heat at the time of LED lighting in the interface part of a LED chip and a fluorescent substance sheet, peeling of a LED chip and a fluorescent substance sheet is suppressed. Therefore, the reliability of the LED package is increased.

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

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

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

If the thickness of the measurement sample is 50 μm or more, the dynamic viscoelasticity measurement can be stably performed. When the sample thickness is less than 50 μm, several films are stacked and heat-pressed on a 100 ° C. hot plate to produce an integrated film (sheet), and a sample with a desired thickness can be manufactured.

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

The thickness of the phosphor sheet according to the embodiment of the present invention is not particularly limited, but is preferably 10 μm or more and 1000 μm or less. As a minimum, it is more preferable that it is 30 micrometers or more. As an upper limit, it is more preferable that it is 200 micrometers or less, It is still more preferable that it is 100 micrometers or less, It is further more preferable that it is 50 micrometers 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 laminate including other layers as necessary. Examples of other layers include a substrate and a barrier layer.

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

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

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

Examples of the “compound containing an alkenyl group bonded to a silicon atom” include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, propenyltrimethoxysilane, norbornenyltrimethoxysilane, octenyltrimethoxysilane Etc. Examples of the “compound having a hydrogen atom bonded to a silicon atom” include, for example, methyl hydrogen polysiloxane, dimethyl polysiloxane-CO-methyl hydrogen polysiloxane, ethyl hydrogen polysiloxane, methyl hydrogen polysiloxane-CO-methyl. Examples thereof include phenyl polysiloxane. Examples of the addition reaction type silicone rubber include those formed by a hydrosilylation reaction of such a material. In addition, as the silicone resin, other well-known resins as described in, for example, JP 2010-159411 A 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 cross-linked product of the present composition is preferably 20% by weight or more, more preferably 50% by weight or more, and further preferably 80% by weight or more.

(A) Average unit formula:

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

(B) Average unit formula:

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

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

(D) Catalyst for hydrosilylation reaction.

The organopolysiloxane of the component (A) can have improved compatibility with the components (B) to (D) by having an aryl group. Further, the organopolysiloxane of component (A) has an alkenyl group having 2 to 6 carbon atoms, thereby causing a crosslinking reaction of components (A) to (C). Moreover, the organopolysiloxane of the component (A) has a branched structure, whereby the curability is improved and good adhesion to the LED chip can be obtained.

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

(B) By incorporating a branched structure into the organopolysiloxane of component (A), the crosslinking reaction rate is improved and good curability is obtained in the phosphor sheet.

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

In particular, the GPC-MALS analysis can determine the molecular weight distribution and rotational radius of the organopolysiloxane. Therefore, the presence of a branched structure can be confirmed by specifying an organopolysiloxane having the same molecular weight component with a small rotation radius.

In the average unit formula (1), each value of a, b, c, d and e indicates that the obtained cross-linked product has sufficient hardness at room temperature, and softening at high temperature implements the present invention. This is a sufficient range.

(B) Component organopolysiloxane has an aryl group and is compatible with component (A). Thereby, the mechanical strength and transparency of the cured film of the phosphor sheet containing the silicone resin can be maintained. The (B) component organopolysiloxane has an alkenyl group having 2 to 6 carbon atoms to cause a crosslinking reaction of the (A) component to the (C) component. In addition, the organopolysiloxane of component (B) has a branched structure, so that the curability is improved and good adhesion to the LED chip can be obtained.

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

The content of component (B) is preferably in the range of 10 to 95 parts by weight with respect to 100 parts by weight of component (A). This is a range for the obtained cross-linked product to be sufficiently softened at a high temperature.

The organopolysiloxane of component (C) has at least two Si—H bonds in one molecule, thereby causing a crosslinking reaction of components (A) to (C). In addition, the organopolysiloxane of component (C) is such that 12 to 70 mol% of the organic groups bonded to silicon atoms are aryl groups, so that the resulting crosslinked product is sufficiently softened at high temperature, and is crosslinked. Maintain the transparency and mechanical strength of objects.

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

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

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 a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a heptyl group. Examples of the cycloalkyl group for R ⁴ include a cyclopentyl group and a cycloheptyl group. Of R ⁴ , the phenyl group content is preferably in the range of 30 to 70 mol%. This is a range in which the obtained crosslinked product can be sufficiently softened at a high temperature and the transparency and mechanical strength of the crosslinked product can be maintained.

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

The catalyst for hydrosilylation reaction of component (D) promotes hydrosilylation reaction between alkenyl groups in component (A) and component (B) and hydrogen atoms bonded to silicon atoms in component (C). It is a catalyst for. Examples of component (D) include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Of these, platinum-based catalysts are preferred because they can significantly accelerate the curing of the composition.

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

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

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

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

The composition comprises, as other optional components, ethynylhexanol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyne-2- Alkyne alcohols such as all; Enyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; 1,3,5,7-tetramethyl-1,3 , 5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, and a reaction inhibitor such as benzotriazole. The content of the reaction inhibitor is not limited, but is preferably in the range of 1 to 5,000 ppm with respect to the weight of the present composition. By adjusting the content of the reaction inhibitor, it is possible to adjust the storage elastic modulus of the resulting silicone resin.

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. Further, the content of the silicone resin is preferably 90% by weight or less, more preferably 85% by weight or less, and still more preferably 70% by weight or less.

The phosphor sheet according to the embodiment of the present invention is particularly preferably used for surface coating of LEDs, as will be described in detail later. In that case, the light-emitting device which shows the outstanding performance can be obtained because the content rate of the silicone resin in a fluorescent substance sheet is the above ranges.

(Phosphor)
The phosphor absorbs light emitted from the LED chip, converts the wavelength of the light, and emits light having a wavelength different from that of the LED chip. 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 multicolor LED including white. Specifically, a single LED chip is used by optically combining a blue LED chip and a phosphor that emits a yellow emission color by absorbing light emitted from the LED chip. White light emission can be obtained.

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

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

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

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

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

Quantum dots coordinated with these ligands can be produced by a known synthesis method. For example, C.I. B. Murray, D.M. J. et al. Norris, M.M. G. It can be synthesized by a method described in Bawendi, Journal American Chemical Society, 1993, 115 (19), pp 8706-8715, or The Journal Physical Chemistry, 101, pp 9463-9475, 1997. Moreover, the quantum dot which the ligand coordinated can use a commercially available thing without a restriction | limiting at all. For example, Lumidot (manufactured by Sigma Aldrich) can be mentioned.

Fluorescent substances particularly preferably used in the present invention include inorganic fluorescent substances. The inorganic phosphor used in the present invention is described below.

(Inorganic phosphor)
The inorganic phosphor used in the present invention preferably has a peak in the region where the emission spectrum has a wavelength of 500 to 700 nm. Such a phosphor is excited by excitation light in the wavelength range of 400 to 500 nm and emits light in the wavelength range of 500 to 700 nm. Examples of the phosphors 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 inorganic phosphors used in the present invention include YAG phosphors, TAG phosphors, silicate phosphors, nitride phosphors, oxynitride phosphors, nitride phosphors, and oxynitride phosphors. And Mn-activated double fluoride complex phosphor. A preferred example of the oxynitride phosphor is a β sialon phosphor.

Of these, nitride phosphors, oxynitride phosphors, and Mn-activated bifluoride complex phosphors are preferably used, and β-sialon phosphors and Mn-activated bifluoride complex phosphors are more preferably used. 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 sialon phosphor and a Mn-activated bifluoride complex phosphor.

(Β-type sialon phosphor)
β-type sialon is a solid solution of β-type silicon nitride in which Al is substituted at the Si position and O is substituted at the N position. Since there are two amounts of atoms in the unit cell (unit cell) of β-sialon, Si _6-z Al _z O _z N _8-z is used as a general formula. Here, z is 0 to 4.2. The solid solution range of β-sialon is very wide, and the molar ratio of (Si, Al) / (N, O) must be maintained at 3/4. A general method for producing β-sialon 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 sialon is a β-type sialon that emits green light with a wavelength of 520 to 550 nm when excited by ultraviolet to blue light by incorporating a light emitting element such as rare earth (Eu, Sr, Mn, Ce, etc.) into the crystal structure. Becomes a phosphor.

The β-sialon phosphor used in the present invention preferably has an emission spectrum having a peak in the wavelength region of 535 to 550 nm. If it is such a range, when the fluorescent substance sheet which concerns on embodiment of this invention is applied to an LED package, a favorable light emission characteristic will be acquired. Further, the average particle diameter of the β-type sialon phosphor is preferably 1 μm or more, more preferably 10 μm or more, and further preferably 16 μm or more. Moreover, 100 micrometers or less are preferable, 50 micrometers or less are more preferable, and 19 micrometers or less are further more preferable. If it is such a range, when the fluorescent substance sheet which concerns on embodiment of this invention is applied to an LED package, a favorable light emission characteristic will be acquired.

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

The Mn-activated bifluoride complex phosphor has the general formula A ₂ MF ₆ : Mn (where A is selected from the group consisting of Li, Na, K, Rb and Cs, and contains at least Na and / or 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 double fluoride complex phosphor used in the present invention, this KSF phosphor is preferable.

The average particle size of the Mn-activated bifluoride complex phosphor is preferably 1 μm or more, more preferably 10 μm or more, and preferably 20 μm or more. Moreover, 100 micrometers or less are preferable, 70 micrometers or less are more preferable, and 40 micrometers or less are further more preferable. If it is such a range, when the fluorescent substance sheet which concerns on embodiment of this invention is applied to an LED package, a favorable light emission characteristic will be acquired.

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

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

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 preferably 60% by weight or more. Further preferred. The brightness | luminance of a fluorescent substance sheet can be raised by making the fluorescent substance content rate in a fluorescent substance sheet into such a range. In addition, although the upper limit of the phosphor content is not particularly specified, the phosphor content in the phosphor sheet is 90% by weight or less of the entire phosphor sheet from the viewpoint that it is easy to create a phosphor sheet excellent in workability. Preferably, it is 85% by weight or less, more preferably 80% by weight or less, and even more preferably 70% by weight or less.

Examples of the phosphor that is particularly preferably used in the present invention include organic compounds represented by the general formula (4) as the organic phosphor. The organic compound represented by the general formula (4) used in the present invention is described below.

(Organic compound represented by general formula (4))

In the general formula (4) representing the organic compound in the present embodiment, R ⁵ , R ⁶ , Ar ¹ to Ar ⁵ and L may be the same or different, and hydrogen, an alkyl group, a cycloalkyl group, an aralkyl group Alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, mercapto group, alkoxy group, alkylthio group, aryl ether group, aryl thioether group, aryl group, heteroaryl group, heterocyclic group, halogen, haloalkyl group, haloalkenyl group, Haloalkynyl group, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, condensed ring and aliphatic ring formed between adjacent substituents Chosen from. M represents an m-valent metal and is at least one selected from boron, beryllium, magnesium, chromium, iron, nickel, copper, zinc, and platinum. In all of the above groups, hydrogen may be deuterium. The same applies to an organic compound or a partial structure thereof described below.

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

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

In the case of “substituted or unsubstituted”, “unsubstituted” means that a hydrogen atom or a deuterium atom is substituted. The same applies to the case of “substituted or unsubstituted” in an organic compound or a partial structure thereof described below.

In addition, among all the groups described above, the alkyl group is, for example, a saturated aliphatic group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group. A hydrocarbon group is shown. This alkyl group may or may not further have a substituent. There is no restriction | limiting in particular in the additional substituent in the case of being substituted, For example, an alkyl group, an aryl group, heteroaryl group etc. can be mentioned, This point is common also in the following description. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 or more and 20 or less, more preferably 1 or more and 8 or less, from the viewpoint of availability and cost.

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

The aralkyl group is an aromatic hydrocarbon group via an aliphatic hydrocarbon such as a benzyl group or a phenylethyl group. Any of these aliphatic hydrocarbons and aromatic hydrocarbons may be unsubstituted or may have a substituent.

An alkenyl group refers to an unsaturated aliphatic hydrocarbon group containing a double bond such as a vinyl group, an allyl group, or a butadienyl group, which may or may not have a substituent. Although carbon number of an alkenyl group is not specifically limited, Usually, it is the range of 2-20.

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

The alkynyl group indicates, for example, an unsaturated aliphatic hydrocarbon group containing a triple bond such as an ethynyl group, which may or may not have a substituent. Although carbon number of an alkynyl group is not specifically limited, Usually, it is the range of 2-20.

The alkoxy group refers to, for example, a functional group having an aliphatic hydrocarbon group bonded through an ether bond such as a methoxy group, an ethoxy group, or a propoxy group, and the aliphatic hydrocarbon group may have a substituent. It may not have. 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 a group in which an oxygen atom of an ether bond of an alkoxy group is substituted with a sulfur atom. The hydrocarbon group of the alkylthio group may or may not have a substituent. Although carbon number of an alkylthio group is not specifically limited, Usually, it is the range of 1-20.

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

The aryl thioether group is a group 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 aryl ether group may or may not have a substituent. Although carbon number of an aryl ether group is not specifically limited, Usually, it is the range of 6 or more and 40 or less.

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

A heteroaryl group is one or more atoms other than carbon such as furanyl, thiophenyl, pyridyl, quinolinyl, pyrazinyl, pyrimidinyl, triazinyl, naphthyridyl, benzofuranyl, benzothiophenyl, indolyl, etc. The cyclic aromatic group which has in an individual ring is shown, This may be unsubstituted or substituted. The number of carbon atoms of the heteroaryl group is not particularly limited, but is preferably in the range of 2 or more and 30 or less.

The heterocyclic group refers to an aliphatic ring having atoms other than carbon, such as a pyran ring, a piperidine ring, and a cyclic amide, in the ring, which may or may not have a substituent. . Although carbon number of a heterocyclic group is not specifically limited, Usually, it is the range of 2-20.

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

An amino group is a substituted or unsubstituted amino group. The amino 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 the aryl group and heteroaryl group, a phenyl group, a naphthyl group, a pyridyl group, and a quinolinyl group are preferable. These substituents may be further substituted. Although carbon number is not specifically limited, Preferably it is 2 or more and 50 or less, More preferably, it is 6 or more and 40 or less, Especially preferably, it is the range of 6 or more and 30 or less.

Halogen means fluorine, chlorine, bromine or iodine. A haloalkyl group, a haloalkenyl group, or a haloalkynyl group is a group in which a part or all of the aforementioned alkyl group, alkenyl group, or alkynyl group such as a trifluoromethyl group is substituted with the aforementioned halogen, and the rest This part may be unsubstituted or substituted. In addition, the aldehyde group, carbonyl group, ester group, and carbamoyl group include those substituted with aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic rings, and the like. The alicyclic hydrocarbon, aromatic hydrocarbon, and heterocyclic ring may be unsubstituted or substituted.

The silyl group refers to, 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. Although carbon number of a silyl group is not specifically limited, Usually, it is the range of 3-20. The number of silicon is usually 1 or more and 6 or less.

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

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

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

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

The organic compound represented by the general formula (4) as described above has a light emitting efficiency, a color purity, a thermal stability, a light stability, a dispersibility and the like by introducing an appropriate substituent at an appropriate position. Various properties and physical properties can be adjusted.

For example, the substituent Ar ⁵ greatly affects the durability of the organic compound represented by the general formula (4), that is, the decrease in the emission intensity of the organic compound over time. Specifically, when Ar ⁵ is hydrogen, the reactivity of this hydrogen is high, so that this hydrogen easily reacts with moisture and oxygen in the air. This causes degradation of Ar ^5. In addition, when Ar ⁵ is a substituent having a large degree of freedom of movement of the molecular chain such as an alkyl group, for example, the reactivity is certainly lowered, but the organic compounds aggregate with time in the sheet, and the result In particular, the emission intensity is reduced due to concentration quenching. Therefore, Ar ⁵ is preferably a group that is rigid and has a low degree of freedom of movement and is unlikely to cause aggregation. Specifically, it is a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. It is preferable that it is either.

Ar ⁵ is preferably a substituted or unsubstituted aryl group from the viewpoint of giving a higher fluorescence quantum yield, being harder to thermally decompose, and from the viewpoint of light stability. As the aryl group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, and an anthracenyl group are preferable from the viewpoint of not impairing the emission wavelength.

Furthermore, in order to increase the light stability of the organic compound, it is necessary to moderately suppress the twist of the carbon-carbon bond of Ar ⁵ and the pyromethene skeleton. This is because, when the twist is excessively large, the light stability is lowered, for example, the reactivity to the excitation light is increased. From this point of view, Ar ⁵ is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, or a substituted or unsubstituted naphthyl group. Of these, a phenyl group, a substituted or unsubstituted biphenyl group, and a substituted or unsubstituted terphenyl group are more preferable. Particularly preferred is a substituted or unsubstituted phenyl group.

Ar ⁵ is preferably a moderately bulky substituent. Since Ar ⁵ has a certain amount of bulkiness, aggregation of molecules can be prevented. As a result, the luminous efficiency and durability of the organic compound are further improved.

A more preferred example of such a bulky substituent includes the structure of Ar ⁵ represented by the following general formula (5).

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

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

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

Further, from the viewpoint of controlling the fluorescence wavelength and absorption wavelength, and increasing the compatibility with the solvent, r is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group or a halogen. , A methyl group, an ethyl group, a tert-butyl group, and a methoxy group are more preferable. From the viewpoint of dispersibility, a tert-butyl group and a methoxy group are particularly preferable. When r is a tert-butyl group or a methoxy group, it is more effective for preventing quenching due to aggregation between molecules.

Compared to the 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, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group It shows better thermal stability and light stability.

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

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

In the general formula (4) representing the organic compound, all of Ar ¹ to Ar ⁴ may be the same or different and each is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. Is preferred. This is because it shows better thermal stability and light stability. In the phosphor composition and the like according to the present embodiment, when the organic compound converts light emitted from the light emitter into light having a longer wavelength than the inorganic phosphor combined therewith, the general formula (5) All of Ar ¹ to Ar ⁴ represented by may be the same or different, 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 light emitter is blue light, the inorganic phosphor converts the blue light to green light, and the organic compound converts the blue light to the color of the inorganic phosphor. Longer wavelength light, that is, red light.

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

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

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

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

In the general formula (6), n is preferably an integer of 1 to 3, and more preferably 1 or 2 from the viewpoint of raw material availability and ease of synthesis.

On the other hand, in the general formula (4) representing the organic compound, Ar ¹ ≠ Ar ² or Ar ³ ≠ Ar ⁴ is particularly preferable because dispersibility in the film is improved and high-efficiency light emission is obtained. . Here, “≠” indicates a group having a different structure. For example, Ar ¹ ≠ Ar ² indicates that Ar ¹ and Ar ² are groups having different structures. Ar ³ ≠ Ar ⁴ indicates that Ar ³ and Ar ⁴ are groups having different structures. In other words, Ar ¹ ≠ Ar ² or Ar ³ ≠ Ar ⁴ means that “Ar ¹ = Ar ² and Ar ³ = Ar ⁴ ” is not satisfied. That is, among arbitrary combinations of Ar ¹ to Ar ⁴ , (1) Ar ¹ = Ar ² = Ar ³ = Ar ⁴ and (2) Ar ¹ = Ar ² and Ar ³ = Ar ⁴ , Ar ¹ ≠ Ar ³ is excluded.

The aryl group represented by the general formula (6) affects various properties and physical properties such as light emission efficiency, color purity, heat resistance and light resistance of the organic compound represented by the general formula (4). Some aryl groups improve multiple properties, but none have sufficient performance in all. In particular, it is difficult to achieve both high luminous efficiency and high color purity. Therefore, if a plurality of types of aryl groups can be introduced into the organic compound represented by the general formula (4), it is expected to obtain an organic compound balanced in light emission characteristics and color purity.

An organic compound in which Ar ¹ = Ar ² = Ar ³ = Ar ⁴ can have only one kind of aryl group. Further, 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 to one pyrrole ring. In this case, it is difficult to maximize the physical properties of each aryl group as will be described later in relation to the luminous efficiency and color purity.

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

This effect is particularly excellent in that the luminous efficiency and color purity are improved in a balanced manner. It is preferable that at least one aryl group that affects the color purity is present in each of the pyrrole rings on both sides, from the viewpoint that the conjugated system is expanded and light emission with high color purity is obtained. However, when Ar ¹ = Ar ² and Ar ³ = Ar ⁴ and Ar ¹ ≠ Ar ³ , for example, when an aryl group that affects color purity is introduced into one pyrrole ring, the other When an aryl group that affects the luminous efficiency is introduced into the pyrrole ring, the aryl group that affects the color purity is biased to the pyrrole ring on one side, so that the conjugated system is not sufficiently expanded and the color purity is not sufficiently improved. In addition, if an aryl group having a different structure that similarly affects the color purity is introduced into the other pyrrole ring, the light emission efficiency cannot be improved.

On the other hand, the organic compound according to the embodiment of the present invention introduces one or more aryl groups that affect the color purity into each of the pyrrole rings on both sides, and the aryl group that affects the luminous efficiency at other positions. Can be introduced. For this reason, the organic compound which concerns on embodiment of this invention can improve the property of both color purity and luminous efficiency to the maximum, and is therefore preferable. Note that it is preferable to introduce an aryl group that affects the color purity at the positions of Ar ² and Ar ³ because the conjugated system is most expanded.

When at least one of Ar ¹ to Ar ⁴ is a substituted or unsubstituted alkyl group, examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert group An alkyl group having 1 to 6 carbon atoms such as a butyl group, a pentyl group or a hexyl group is preferred. Further, the alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group from the viewpoint of excellent thermal stability. Further, from the viewpoint of preventing concentration quenching and improving the emission quantum yield, this alkyl group is more preferably a sterically bulky tert-butyl group. On the other hand, from the viewpoint of ease of synthesis and availability of raw materials, a methyl group is also preferably used as the alkyl group.

On the other hand, in the general formula (4) representing the organic compound, all of Ar ¹ to Ar ⁴ may be the same or different, and when they are substituted or unsubstituted alkyl groups, they are soluble in a binder resin or a solvent. Is preferable. In this case, the alkyl group is preferably a methyl group from the viewpoints of ease of synthesis and availability of raw materials. For example, in the phosphor composition according to the present embodiment, when the organic compound converts light emitted from a light emitter into light having a shorter wavelength than an inorganic phosphor combined therewith, a general formula ( Ar ¹ to Ar ⁴ represented by 4) may all be the same or different and each represents a substituted or unsubstituted alkyl group, preferably a methyl group. 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 the color of the inorganic phosphor. Shorter wavelength light, that is, green light.

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

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

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

As another embodiment of the organic compound represented by the general formula (4), it is preferable that at least one of R ⁵ , R ⁶ , and Ar ¹ to Ar ⁵ is an electron withdrawing group. In particular, (1) at least one of R ¹ , R ² , 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 to Ar ⁴ are preferably electron withdrawing groups, and Ar ⁵ is preferably an electron withdrawing group. Thus, by introducing an electron withdrawing group into the pyromethene skeleton of the organic compound, the electron density of the pyromethene skeleton can be significantly reduced. Thereby, the stability with respect to oxygen of the organic compound is further improved, and as a result, the durability of the organic compound can be further improved.

The electron-withdrawing group is also called an electron-accepting group, and is an atomic group that attracts electrons from a substituted atomic group by an induced effect or a resonance effect in organic electron theory. Examples of the electron-withdrawing group include those that take a positive value as the Hammett's rule substituent constant (σp (para)). The Hammett's rule substituent constant (σp (para)) can be cited from the Chemical Handbook, Basic Revision 5 (II-380). In addition, although a phenyl group also has the example which takes the above positive values, in this invention, a phenyl group is not contained in an electron withdrawing group.

Examples of electron withdrawing groups include, for example, -F (σp: +0.06), -Cl (σp: +0.23), -Br (σp: +0.23), -I (σp: +0.18),- CO ₂ R ¹² (σp: when R ¹² is an ethyl group +0.45), —CONH ² (σp: +0.38), —COR ¹² (σp: when R ¹² is a methyl group +0.49), —CF _{_{3 (σp: +0.50), -}} SO 2 R 12 (σp: when ^{R 12} is a methyl group _{+0.69), - 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 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, substituted or unsubstituted A substituted alkyl group having 1 to 30 carbon atoms and a substituted or unsubstituted cycloalkyl group having 1 to 30 carbon atoms are represented. Specific examples of these groups include the same examples as described above.

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

More preferred electron withdrawing groups include fluorine-containing alkyl groups, substituted or unsubstituted acyl groups, substituted or unsubstituted ester groups, and cyano groups. This is because these lead to effects of preventing concentration quenching and improving the emission 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) 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. Because it can.

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

As one of preferable examples of the organic compound represented by the general formula (4), Ar ¹ to Ar ⁴ may all be the same or different and each is a substituted or unsubstituted alkyl group, and Ar ^The case where 5 is group represented by General formula (5) is mentioned. In this case, Ar ⁵ is particularly preferably a group represented by the general formula (5) in which r is included as a substituted or unsubstituted phenyl group.

As another preferred example of the organic compound represented by the general formula (4), all of Ar ¹ to Ar ⁴ may be the same or different and are selected from the above general formula (6). And Ar ⁵ is a group represented by the general formula (5). In this case, Ar ⁵ is more preferably a group represented by the general formula (5) in which r is a tert-butyl group or methoxy group, and represented by the general formula (5) in which r is a methoxy group. It is particularly preferred that

Hereinafter, an example of the organic compound represented by the general formula (4) is shown, but the organic compound according to the present embodiment is not limited to these.

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

Also, for the synthesis of pyromethene-boron fluoride complex, see J.H. Org. Chem. , Vol. 64, no. 21, pp 7813-7819 (1999), Angew. Chem. , Int. Ed. Engl. , Vol. 36, pp 1333-1335 (1997) and the like, an organic compound represented by the general formula (4) can be produced.

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

Hereinafter, examples of organic light-emitting materials other than the organic compound represented by the general formula (4) will be shown, but the present invention is not particularly limited thereto.

The content of the organic compound represented by the general formula (4) in the phosphor composition according to the embodiment of the present invention includes the molar absorption coefficient of the organic compound, the fluorescence quantum yield, the absorption intensity at the excitation wavelength, and the production. Depending on the thickness and transmittance of the film, it is usually 10 ⁻⁵ weight percent to 10 weight percent, more preferably 10 ⁻⁴ weight percent to 5 weight percent, based on the total weight of the phosphor composition. Preferably, it is 10 ⁻³ weight percent to 2 weight percent.

(solvent)
The phosphor sheet according to the embodiment of the present invention may contain a solvent. A solvent will not be specifically limited if the viscosity of resin of a fluid state can be adjusted. Examples of the solvent include toluene, methyl ethyl ketone, methyl isobutyl ketone, hexane, acetone, terpineol, texanol, methyl cellosolve, butyl carbitol, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and the like.

(Other ingredients)
The phosphor sheet according to the embodiment of the present invention contains a dispersing agent and a leveling agent for stabilizing the coating film, an adhesion assistant such as a silane coupling agent as a surface modifier of the phosphor sheet, and the like. May be.

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

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

The average particle diameter of the silicone fine particles can be measured by the above-described method, similarly to the average particle diameter of the phosphor. The average particle diameter of the silicone fine particles is more preferably 0.5 μm or more as the lower limit. Moreover, as an upper limit, it is more preferable that it is 1.0 micrometer or less.

The silicone fine particles are preferably fine particles made of silicone resin and / or silicone rubber. In particular, silicone fine particles obtained by a method of hydrolyzing organosilane such as organotrialkoxysilane, organodialkoxysilane, organotriacetoxysilane, organodiacetoxysilane, organotrioxime silane, organodioxime silane, and then condensing them. preferable. Among these, the reaction as reported in Japanese Patent Application Laid-Open No. 2003-342370 is carried out in the production of spherical organopolysilsesquioxane fine particles by hydrolyzing and condensing organosilane and / or a partial hydrolyzate thereof. It is preferable to use silicone fine particles obtained by a method of adding a polymer dispersant in the solution.

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

The content of the silicone fine particles in the phosphor sheet is preferably 0.5% by weight or more of the whole 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 defined, but from the viewpoint of good mechanical properties, it is preferably 20% by weight or less of the entire phosphor sheet, and more preferably 10% by weight or less. .

(Base material)
A base material is an example of the support body of the fluorescent substance sheet in this invention. There is no restriction | limiting in particular as a base material, For example, a well-known metal, a film, glass, ceramic, paper etc. can be used. Specifically, metal plates and foils such as aluminum (including aluminum alloys), zinc, copper, and iron; cellulose acetate, polyethylene terephthalate (PET), polyethylene, polyester, polyamide, polyimide, polyphenylene sulfide, polystyrene, polypropylene, Plastic film such as polycarbonate, polyvinyl acetal, aramid, silicone, polyolefin, thermoplastic fluororesin, copolymer of tetrafluoroethylene and ethylene (ETFE); α-polyolefin resin, polycaprolactone resin, acrylic resin, silicone resin and these Film made of a copolymer resin of ethylene and ethylene; paper laminated with the plastic, paper coated with the plastic, gold There laminated or vapor-deposited papers, the metals and plastic film laminated or deposited. Moreover, when the base material is a metal plate, the surface of the metal plate may be subjected to a plating treatment or ceramic treatment such as chromium or nickel.

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

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

(Other layers)
The phosphor sheet according to the embodiment of the present invention may include a barrier layer. The barrier layer is appropriately used in the case where the gas barrier property is improved with respect to the phosphor sheet.

Examples of the barrier layer having a barrier function against oxygen include, for example, silicon oxide, aluminum oxide, tin oxide, indium oxide, yttrium oxide, magnesium oxide, or a mixture thereof, or metal oxide obtained by adding other elements thereto. Or a film made of various resins such as nylon, polyvinylidene chloride, and a copolymer of ethylene and vinyl alcohol.

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

In addition, the phosphor sheet according to the embodiment of the present invention has an antireflection function, an antiglare function, an antireflection antiglare function, a light diffusion function, a hard coat function (anti-resistance) according to the function required for the phosphor sheet. A friction layer), an antistatic function, an antifouling function, an electromagnetic wave shielding function, an infrared cut function, an ultraviolet cut function, a polarization function, and a toning function may be further provided.

<Method for producing phosphor sheet>
Below, an example of the preparation method of the fluorescent substance sheet which concerns on embodiment of this invention is demonstrated. In addition, the manufacturing method demonstrated below is an example, and the manufacturing method of a fluorescent substance sheet is not limited to this.

First, a composition in which a phosphor is dispersed in a silicone resin (hereinafter referred to as “phosphor composition”) is prepared as a coating solution for forming a phosphor sheet. A predetermined amount of the above-described silicone resin, phosphor, and additives such as silicone fine particles and a solvent are mixed as required. After mixing the above components so as to have a predetermined composition, the mixture is uniformly mixed and dispersed by a homogenizer, a revolving stirrer, a three-roller, a ball mill, a planetary ball mill, a bead mill or the like. A phosphor composition is obtained.

Defoaming is preferably carried out under vacuum or reduced pressure conditions after mixing / dispersing or in the course of mixing / dispersing. Moreover, you may mix a specific component in advance, and you may process processes, such as aging, with respect to the completed fluorescent substance composition. It is also possible to remove the solvent from the mixture after mixing and dispersion by an evaporator to obtain a desired solid content concentration.

The phosphor composition produced by the method described above is applied on a substrate and dried to produce a phosphor sheet. Application is reverse roll coater, blade coater, slit die coater, direct gravure coater, offset gravure coater, kiss coater, natural roll coater, air knife coater, roll blade coater, two stream coater, rod coater, wire bar coater, applicator, dip It can be performed by a coater, curtain coater, spin coater, knife coater or the like. In order to obtain the film thickness uniformity of the phosphor sheet, it is preferably applied by a slit die coater.

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

It is also possible to change the substrate as necessary after producing the phosphor sheet. In this case, as a simple method, there are a method of replacing the substrate using a hot plate, a method of replacing the substrate using a vacuum laminator or a dry film laminator, and the like.

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

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

Among these LED chips, an LED chip whose light emitting surface is not a single plane is preferable because it can be brightened by using light emitted from the side portion. In particular, a flip chip type LED chip having an upper light emitting surface and a side light emitting surface is preferable because the light emitting area can be increased and the manufacturing process of the LED chip is easy. Further, the surface of the light emitting surface may be textured based on an optical design for improving the light emission efficiency of the LED chip.

The phosphor sheet according to the embodiment of the present invention may be directly attached to the LED chip or may be attached via an adhesive such as a transparent resin. From the viewpoint that the light from the LED chip can be directly incident on the phosphor sheet without being lost due to reflection or the like, the phosphor sheet according to the embodiment of the present invention is directly attached to the LED chip. Is more preferable. Thereby, uniform white light with little color variation and high efficiency can be obtained.

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

FIG. 1 shows a preferred example of an LED package according to an embodiment of the present invention. In FIG. 1A, the LED chip 1 to which the phosphor sheet 2 is attached is placed on a mounting substrate 5 having a reflector 4, and the upper surface portion of the LED chip 1 is sealed with a transparent sealing material 3. Is.

FIG. 1B shows that the LED chip 1 with the phosphor sheet 2 attached is placed on a mounting substrate 5 provided with a reflector 4, and the upper surface portion and the side surface portion of the LED chip 1 are sealed with a transparent sealing material 3. It has been stopped.

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

FIG. 1D shows an LED chip 1 to which a phosphor sheet 2 is attached, which is placed on a mounting substrate 5 that does not have a reflector, and is sealed with a transparent sealing material 3 molded into a lens shape. It is.

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

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

FIG. 1 (g) shows the configuration of the LED chip 1 and the phosphor sheet 2 in the configuration shown in FIG. 1 (d), which is the same as the configuration shown in FIG. 1 (f).

FIG. 1 (h) shows that the LED chip 1 is installed so as to fit the portion of the mounting substrate 5 having the reflector 4 that does not have the reflector 4, and has the same width as the interval between the reflectors 4 on the LED chip 1. The phosphor sheet 2 is affixed via an adhesive 8 and further sealed with a transparent sealing material 3.

FIG. 1 (i) shows that the phosphor sheet 2 with the substrate 9 is used as the phosphor sheet 2 in the configuration shown in FIG. 1 (h), and the substrate 9 is not peeled off from the phosphor sheet 2. The phosphor sheet 2 is affixed via an adhesive 8.

The LED package according to the embodiment of the present invention is not limited to these configurations. For example, the structure of each part illustrated in FIGS. 1A to 1I may be appropriately combined. Also, the structure of each part illustrated in FIGS. 1 (a) to 1 (i) is replaced with a known part other than the above, or illustrated in FIGS. 1 (a) to 1 (i). The structure which combined the structure and the well-known part may be sufficient.

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

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

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

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

As will be described later, a typical method for manufacturing an LED package using a phosphor sheet according to an embodiment of the present invention is as follows. (1) After the phosphor sheet is cut into individual pieces, it is attached to individual LED chips. A method of attaching (for example, see FIG. 2), (2) a phosphor sheet is affixed to a large number of LED chips (hereinafter referred to as “wafer level LED chips”) formed on a wafer, and then wafer dicing is performed. And a method of collectively cutting the phosphor sheet (for example, see FIG. 3), but is not limited thereto. Hereinafter, these steps will be described with reference to FIGS. 2 and 3 as appropriate.

(Process of attaching the phosphor sheet to the LED chip)
The phosphor sheet according to the embodiment of the present invention is affixed to the LED chip by applying pressure while heating at a desired temperature. This is pasting by thermocompression 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 design for increasing the difference between the storage elastic modulus G ′ of the phosphor sheet at room temperature and the elastic modulus G ′ of the phosphor sheet at the bonding temperature is facilitated by setting the heating temperature to 60 ° C. or higher. It becomes. Moreover, since the thermal expansion or thermal contraction of the phosphor sheet can be reduced by setting the heating temperature to 250 ° C. or less, the positional accuracy of the pasting can be increased.

In particular, when the phosphor sheet is previously perforated and aligned with a predetermined portion on the LED chip, the positional accuracy of the pasting is important. The heating temperature is more preferably 160 ° C. or less from the viewpoint of improving the positional accuracy of the pasting.

As an apparatus for thermocompression bonding the phosphor sheet, any existing apparatus can be used as long as it can be bonded at a desired temperature. As shown in FIGS. 2 (c) to 2 (d), when the singulated phosphor sheet is subjected to thermocompression bonding, for example, a thermocompression bonding tool such as a mounter or a flip chip bonder can be used.

Further, as shown in FIGS. 3A to 3B, when a phosphor sheet is attached to a wafer level LED chip at a time, a vacuum laminator or a heating unit having a heating portion of about 100 to 200 mm square is used. Crimping tools are available.

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

(Process of cutting the phosphor sheet)
There are two methods for cutting the phosphor sheet: a method in which the phosphor sheet is cut in advance before being attached to the LED chip, and a method in which the phosphor sheet is attached to the wafer level LED chip and then the wafer is diced. There is a way to cut.

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

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

When the phosphor sheet in a state of being laminated with the base material is cut, the whole base material may be cut into pieces, or the fluorescent sheet may be cut into pieces and the base material may not be cut. Or the state (what is called a half cut state) in which the cut line which does not penetrate through a base material enters while a fluorescent substance sheet is separated may be sufficient.

When the phosphor sheet is divided into individual pieces together with the base material, each piece of the phosphor sheet can be attached to the LED chip by the above-described method. In that case, peeling of the base material from the phosphor sheet may be performed before being attached to the LED chip or after being attached to the LED chip. Moreover, you may leave a base material as it is, without peeling from a fluorescent substance sheet.

When the phosphor sheet is divided into individual pieces and the substrate is not cut or is in a so-called half-cut state, the individual phosphor chips are separated by the above-mentioned method after the individual phosphor sheets are peeled off from the substrate. Can be pasted on.

As shown in FIG. 3, when a phosphor sheet is bonded to a wafer level LED chip and then the phosphor sheet is cut simultaneously with wafer dicing, it is processed into a predetermined shape by laser processing or cutting with a blade. It can be divided into LED chips with phosphor sheets that have been processed and singulated. Of these cutting methods, cutting with a blade is preferable.

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

FIG. 2A shows a state where the phosphor sheet 2 laminated with the base material 9 is fixed to the temporarily fixing sheet 11. In the process shown in FIG. 2, since both the phosphor sheet 2 and the base material 9 are separated, they are fixed to the temporarily fixing sheet 11 so as to be easy to handle. Next, as shown in FIG.2 (b), the fluorescent substance sheet 2 and the base material 9 are cut | disconnected and separated into pieces.

Subsequently, as shown in FIG. 2C, the separated phosphor sheet 2 and the base material 9 are aligned on the LED chip 1 mounted on the mounting substrate 5. Then, as shown in FIG. 2 (d), the phosphor sheet 2 is crimped to the LED chip 1 at a desired temperature using a thermocompression bonding tool 12. At this time, it is preferable to perform the pressure bonding step under vacuum or reduced pressure so that air is not caught between the phosphor sheet 2 and the LED chip 1. Allow to cool to room temperature after crimping.

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

FIG. 3 shows an example of a series of steps in the case where the phosphor sheet is bonded together on the wafer level LED chip and then the wafer dicing and the phosphor sheet are collectively cut. In the process of FIG. 3, a process of attaching a phosphor sheet to a plurality of LED chips formed on a wafer in a lump, and wafer dicing and separation of LED chips to which the phosphor sheet is attached And a step of collectively performing the above.

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

Next, as shown in FIG. 3 (b), the phosphor sheet 2 is thermocompression bonded to the plurality of LED chips at a desired temperature by the thermocompression bonding tool 12. At this time, it is preferable to perform the thermocompression bonding step under vacuum or reduced pressure so that air is not caught between the phosphor sheet 2 and the LED chip. Allow to cool to room temperature after thermocompression bonding.

Next, as shown in FIG. 3C, after the base material 9 is peeled from the phosphor sheet 2, the wafer 13 is diced and simultaneously the phosphor sheet 2 is cut into individual pieces. And as shown in FIG.3 (d), the LED chip 25 with the fluorescent substance sheet separated into pieces is obtained.

Further, in place of the steps of FIGS. 3C to 3D, as shown in FIG. 3E, the base material 9 is not peeled off from the phosphor sheet 2, and as shown in FIG. The substrate 9 may also be cut into individual pieces together with the phosphor sheet. In this way, the LED chip 26 with the base material and the phosphor sheet obtained in pieces is obtained. In this case, when the base material 9 is glass or the like, it may be used as it is without being peeled off from the phosphor sheet 2. When the substrate 9 is a plastic film, the substrate 9 may be peeled from the phosphor sheet 2 after the LED chip 26 is mounted on the substrate.

2 and 3, when the phosphor sheet is attached to the LED chip having the electrode on the upper surface, it is necessary to remove the phosphor sheet corresponding to the electrode. Therefore, before the phosphor sheet is attached to the LED chip, it is preferable that a hole is formed in advance in a portion corresponding to the electrode in the phosphor sheet. The phosphor sheet according to the embodiment of the present invention can be drilled with high accuracy.

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

The method of drilling is not particularly limited, but known methods such as laser processing and die punching can be suitably used. Laser processing may cause scorching of the resin in the phosphor sheet or deterioration of the phosphor depending on processing conditions. Therefore, punching with a mold is more desirable. When punching is performed, punching cannot be performed after the phosphor sheet is attached to the LED chip. Therefore, it is essential to perform punching before attaching the phosphor sheet to the LED chip.

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

If the size of the hole provided in the phosphor sheet is too large than the size of the electrode, the light emitting surface is exposed and light leakage occurs, which may deteriorate the color characteristics of the LED package. On the other hand, if the size of the electrode is too small, the wire may touch the phosphor sheet at the time of wire bonding, which may cause poor bonding. Therefore, in the hole making process with the phosphor sheet, it is preferable to process a small hole of 50 μm square or more and 500 μm square or less with high accuracy within ± 10%.

When a phosphor sheet that has been subjected to cutting or drilling as necessary is aligned and pasted to a predetermined portion of the LED chip, an affixing device having an optical alignment (alignment) mechanism is used. Necessary. At this time, it is difficult in terms of work to align the phosphor sheet and the LED chip in proximity. Therefore, in practice, alignment is often performed in a state where the phosphor sheet and the LED chip are lightly contacted.

At this time, if the phosphor sheet is sticky, it is very difficult to move the phosphor sheet after contacting the LED chip. On the other hand, since the phosphor sheet according to the embodiment of the present invention is not sticky at room temperature, it is easy to perform alignment while the phosphor sheet and the LED chip are lightly in contact with each other.

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

In addition, the LED chip to which the phosphor sheet is attached can be bonded by thermocompression when bonded to the mounting substrate at once, or can be soldered to the mounting substrate by solder reflow.

As another embodiment of the LED package manufacturing method using the phosphor sheet according to the embodiment of the present invention, a mass production method of the LED package will be described. First, a method for manufacturing an LED chip with a phosphor sheet will be described. As a method of attaching the phosphor sheet to the LED chip, for example, as shown in FIG. 4, a method of attaching the individual phosphor sheet laminates 14 for each LED chip 1 one by one is given. It is done. In addition, as shown in FIG. 5, there is a method in which the phosphor sheet 2 is affixed to a plurality of LED chips 1 in a lump, and after covering these, the package substrate 15 is cut and the LED chips 1 are individualized.

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

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

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

As shown in FIG. 6 (c), after the laminate of FIG. 6 (b) is put into the lower chamber 20 of the vacuum diaphragm mura terminator 22, the upper chamber 19 and the lower chamber 20 are depressurized while being heated. After heating under reduced pressure until the base material 9 flows, the diaphragm 21 is expanded by sucking air into the upper chamber 19 through the air inlet 23. And the fluorescent substance sheet 2 is pressed through the base material 9, and it affixes so that the light emission surface of the LED chip 1 may be followed.

As shown in FIG. 6 (d), after returning the upper and lower chambers to atmospheric pressure, the laminate is taken out from the vacuum diaphragm laminator 22, and after allowing to cool, the substrate 9 is peeled from the phosphor sheet 2. Subsequently, the cut portions 24 between the LED chips are cut with a dicing cutter or the like, and the LED chips 25 with the phosphor sheet that have been separated into pieces are produced.

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

The second production example is shown in FIG. This is another preferable example in the case where the substrate provided in the phosphor sheet has fluidity.

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

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

As shown in FIG.7 (c), after putting the laminated body of FIG.7 (b) in the lower chamber 20 of the vacuum diaphragm laminator 22, by the method similar to the manufacture example of FIG. Affix to 1 light emitting surface.

As shown in FIG. 7 (d), after returning the upper and lower chambers to atmospheric pressure, the laminate is taken out from the vacuum diaphragm laminator 22 and allowed to cool, and then the substrate 9 is peeled from the phosphor sheet 2. Subsequently, the cut portions 24 between the LED packages are cut and separated. Through the above steps, the LED package 10 as shown in FIG. 7E is manufactured.

<Light emitting device, backlight unit, display>
The light emitting device according to the embodiment of the present invention includes the phosphor sheet described above. For example, this light-emitting device includes an LED package including the above-described 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 this light emitting device. For example, the backlight unit includes an LED package having the above-described phosphor sheet or a cured product thereof. The backlight unit configured as described above can be used for displays, lighting, interiors, signs, signboards, and the like, but is particularly suitable for display and lighting applications.

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

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

<Base material>
BX9: Release-treated polyethylene terephthalate (polyethylene terephthalate film) “Therapel” BX9 (manufactured by Toray Film Processing Co., Ltd., average film thickness 50 μm)
<Inorganic phosphor>
-Phosphor 1 (YAG1):
"YAG81003" (YAG phosphor) manufactured by Nemoto Lumi Materials Co., Ltd.
-Phosphor 2 (β1):
“GR-SW532D” (β type sialon 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 Lumimaterial Co., Ltd.
Average particle diameter (D50): 50 μm.

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

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

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

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

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

Next, 357 mg of 2-benzoyl-3,5-bis (4-t-butylphenyl) pyrrole, 250 mg of 4- (4-t-butylphenyl) -2- (4-methoxyphenyl) pyrrole, 138 mg of phosphorus oxychloride, A mixed solution of 10 ml of 1,2-dichloroethane was heated to reflux for 9 hours under a nitrogen stream. Next, 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. 20 ml of water was injected and extracted with 30 ml of dichloromethane. The organic layer was washed twice with 20 ml of water, dried over magnesium sulfate and evaporated. After purification by silica gel column chromatography and vacuum drying, an 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).

(Synthesis Example 2)
Below, the synthesis | combining method of the organic fluorescent substance (T22) of the synthesis example 2 is demonstrated. In the synthesis method of the organic phosphor (T22), a mixed solution of 300 mg of 4- (4-t-butylphenyl) -2- (4-methoxyphenyl) pyrrole, 201 mg of 2-methoxybenzoyl chloride and 10 ml of toluene was placed under a nitrogen stream. Heated at 120 ° C. for 6 hours. Subsequently, it was evaporated after cooling to room temperature. After washing with 20 ml of ethanol and vacuum drying, 260 mg of 2- (2-methoxybenzoyl) -3- (4-tert-butylphenyl) -5- (4-methoxyphenyl) pyrrole was obtained.

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

Next, 305 mg of diisopropylethylamine and 670 mg of boron trifluoride diethyl ether complex were added to the mixed solution of the obtained pyromethene and 10 ml of toluene under a nitrogen stream, and the mixture was stirred at room temperature for 3 hours. Then, 20 ml of water was injected and extracted with 30 ml of dichloromethane. The organic layer was washed twice with 20 ml of water, dried over magnesium sulfate and 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).

(Synthesis Example 3)
Below, the synthesis | combining method of the organic fluorescent substance (T23) of the synthesis example 3 is demonstrated. In the method of synthesizing the organic phosphor (T23), 5.0 g of 2- (2-methoxybenzoyl) -3,5-bis (4-tert-butylphenyl) pyrrole, 2,4 in 30 ml of 1,2-dichloroethane. -3.3 g of bis (4-t-butylphenyl) pyrrole and 1.5 g of phosphorus oxychloride were added and reacted for 12 hours under heating and reflux. Then, 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. 50 ml of water was added, dichloromethane was added, the organic layer was extracted, concentrated, purified by column chromatography using silica gel, and further purified by sublimation to obtain the organic phosphor (T23) shown below. Synthesized.

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

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

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

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

(Synthesis Example 5)
Below, the synthesis | combining method of the organic fluorescent substance (T25) of the synthesis example 5 is demonstrated. The organic phosphor (T25) was synthesized in the same manner as in Synthesis Example 4, except that ethyl 2,4-dimethylpyrrole-3-carboxylate was used instead of 2,4-dimethylpyrrole as the pyrrole raw material. An organic phosphor (T25) was synthesized.

(Synthesis Example 6)
Below, the synthesis | combining method of the organic fluorescent substance (T26) of the synthesis example 6 is demonstrated. The organic phosphor (T26) was synthesized in the same manner as in Synthesis Example 5, except that 4- (methoxycarbonyl) phenylboronic acid was used in place of 4-t-butylphenylboronic acid as the boronic acid raw material. An organic phosphor (T26) was synthesized.

<Silicone resin>
The following were used as silicone resins.

Silicone resin 1 (Si1):
(A) component: 28.5 parts by weight, (B) component: 5.7 parts by weight (C) component: 66.0 parts by weight, (D) component: 0.03 parts by weight, reaction inhibitor: 0.025 Part by weight (A) component (MeViSiO _2/2 ) _0.35 (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
Component (C) “HPM-502” (Phenylmethylsiloxane copolymer) manufactured by Gerest
Component (D) Platinum complex (1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution) Platinum content 5% by weight
Reaction inhibitor 1-Ethynylhexanol * However, Me: methyl group, Vi: vinyl group, Ph: phenyl group.

Silicone resin 2 (Si2):
(A) component: 28.5 parts by weight, (B) component: 5.7 parts by weight (C) component: 66.0 parts by weight, (D) component: 0.03 parts by weight, reaction inhibitor: 0.025 Part by weight (A) component (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
Component (C) (HMe ₂ SiO) ₂ SiPh ₂
Component (D) Platinum complex (1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution) Platinum content 5% by weight
Reaction inhibitor 1-Ethynylhexanol * However, Me: methyl group, Vi: vinyl group, Ph: phenyl group.

Silicone resin 3 (Si3):
(A) component: 28.5 parts by weight, (B) component: 5.7 parts by weight (C) component: 66.0 parts by weight, (D) component: 0.03 parts by weight, reaction inhibitor: 0.025 Part by weight (A) component (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
Component (C) (HMe ₂ SiO) ₂ SiPh ₂
Component (D) Platinum complex (1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution) Platinum content 5% by weight
Reaction inhibitor 1-Ethynylhexanol * However, Me: methyl group, Vi: vinyl group, Ph: phenyl group.

Silicone resin 4 (Si4):
(A) component: 28.5 parts by weight, (B) component: 5.7 parts by weight (C) component: 66.0 parts by weight, (D) component: 0.03 parts by weight, reaction inhibitor: 0.025 Part 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
Component (C) (HMe ₂ SiO) ₂ SiPh ₂
Component (D) Platinum complex (1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution) Platinum content 5% by weight
Reaction inhibitor 1-Ethynylhexanol * However, Me: methyl group, Vi: vinyl group, Ph: phenyl group.

Silicone resin 5 (Si5):
(A) component: 28.5 parts by weight, (B) component: 5.7 parts by weight (C) component: 66.0 parts by weight, (D) component: 0.03 parts by weight, reaction inhibitor: 0.025 Part by weight (A) component (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
Component (C) (HMe ₂ SiO) ₂ SiPh ₂
Component (D) Platinum complex (1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution) Platinum content 5% by weight
Reaction inhibitor 1-Ethynylhexanol * However, Me: methyl group, Vi: vinyl group, Ph: phenyl group.

Silicone resin 6 (Si6):
(A) component: 31.4 parts by weight, (B) component: 2.8 parts by weight (C) component: 66.0 parts by weight, (D) component: 0.03 parts by weight, reaction inhibitor: 0.025 Part by weight (A) component (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
Component (C) (HMe ₂ SiO) ₂ SiPh ₂
Component (D) Platinum complex (1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution) Platinum content 5% by weight
Reaction inhibitor 1-Ethynylhexanol * However, Me: methyl group, Vi: vinyl group, Ph: phenyl group.

Silicone resin 7 (Si7):
(A) Component: 17.4 parts by weight, (B) Component: 16.8 parts by weight (C) Component: 66.0 parts by weight, (D) Component: 0.03 parts by weight, Reaction inhibitor: 0.025 Part by weight (A) component (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
Component (C) (HMe ₂ SiO) ₂ SiPh ₂
Component (D) Platinum complex (1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution) Platinum content 5% by weight
Reaction inhibitor 1-Ethynylhexanol * However, Me: methyl group, Vi: vinyl group, Ph: phenyl group.

Silicone resin 8 (Si8): OE6630 (Toray Dow Corning Silicone)

Silicone resin 9 (Si9):
Resin main component 16.7 parts by weight, hardness adjusting agent 16.7 parts by weight, cross-linking agent 66.7 parts by weight, reaction inhibitor 0.025 parts by weight, platinum catalyst 0.03 parts by weight Ingredients for blending silicone resin Resin main component (MeViSiO _2/2 ) _0.25 (Ph ₂ SiO _2/2 ) _0.3 (PhSiO _3/2 ) _0.45 (HO _1/2 ) _0.03 (corresponding to component (A))
Hardness modifier ViMe ₂ SiO (MePhSiO) _17.5 SiMe ₂ Vi (corresponds to component (B))
Crosslinking agent (HMe ₂ SiO) ₂ SiPh ₂ (corresponds to component (C))
* However, Me: Methyl group, Vi: Vinyl group, Ph: Phenyl group Reaction inhibitor 1-Ethynylhexanol Platinum catalyst Platinum complex (1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution) Contains platinum Amount 5% by weight (corresponding to component (D)).

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

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

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

<Cutting processability evaluation>
The obtained phosphor sheet was cut into 1 mm × 0.3 mm square using a cutting device “GCUT” (manufactured by UHT) to produce 100 individual phosphor sheets. The individual phosphor sheets were observed with an optical microscope, and the number of samples having cracks or chips at the peripheral edge was counted. It shows that it is excellent in cutting workability, so that there are few samples with a peripheral part cracked or missing. If it is more than evaluation B, it is excellent practically.
S: 0 pieces Cutting workability is very good A: 1 piece or more 3 pieces or less Cutting workability is good B: 4 pieces or more and 10 pieces or less No cutting workability is practically problematic C: 11 pieces or more and 30 pieces or less Poor property D: 31 or more Cutting workability is very bad.

<Manufacturing method of LED package>
The obtained phosphor sheet was cut into 1 mm × 0.3 mm square using a cutting device “GCUT” (manufactured by UHT) to produce 100 individual phosphor sheets. Using a flip chip bonding apparatus (manufactured by Toray Engineering Co., Ltd.), the individual phosphor sheets were vacuum-adsorbed with a collet and separated from the substrate. The separated phosphor sheet was attached to the LED chip surface of the LED package on which the flip chip type LED chip was mounted under the following application 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.

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

<Adhesion evaluation>
Using the obtained LED package, tweezers were put at the interface between the LED chip and the phosphor sheet, and then the phosphor sheet was lifted with tweezers to confirm the adhesion between the LED chip and the phosphor sheet. The sample with good adhesion does not peel off the phosphor sheet even when lifted with tweezers. In a sample with poor adhesion, the phosphor sheet is peeled off from the LED chip. Observation with an optical microscope was performed, and the number of samples with peeling was counted. The smaller the number of samples peeled, the better the adhesion. If it is more than evaluation B, it is excellent practically.
S: 0 pieces Adhesiveness is very good A: 1 piece or more and 5 pieces or less Adhesiveness is good B: 6 pieces or more and 10 pieces or less Adhesiveness is not practically problematic C: 11 pieces or more and 30 pieces or less : 31 or more Adhesiveness is very poor.

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

(Example 1) (Effect of silicone composition)
Using a polyethylene container having a volume of 100 ml, 18.0 g of silicone resin 1 (Si1), 42.0 g of phosphor 1 (YAG1) as an inorganic phosphor, and 2.5 g of butyl carbitol were added and mixed. Thereafter, using a planetary stirring / defoaming apparatus, stirring and defoaming was performed at 1000 rpm for 5 minutes, and then mixed and dispersed six times with three rolls to prepare phosphor composition 1.

Using a slit die coater, the phosphor composition 1 is applied onto the release treatment surface of “Therapy” BX9, which is a base material, heated at 120 ° C. for 40 minutes and dried, and has a thickness of 80 μm and a 100 mm square fluorescence. A body sheet was obtained. Dynamic elastic modulus measurement and cutting workability evaluation were performed by the methods described above. Moreover, the LED package was produced by the method mentioned above, adhesiveness evaluation, and total luminous flux measurement were implemented. The results are shown in Table 1. The cutting processability was good, the result that the adhesiveness was improved was obtained, and the relative luminance was also improved.

(Example 2) (Change of silicone resin)
Except that the silicone resin was changed to Si2, a phosphor sheet was prepared in the same manner as in Example 1, and then an LED package was prepared and subjected to each measurement and evaluation. The results are shown in Table 1. As shown in Table 1, from the evaluation results of Example 2, it was found that the cutting property and the adhesiveness were good if the phosphor sheet according to the embodiment of the present invention. It was also found that the relative luminance was improved.

(Comparative Example 1)
A phosphor sheet was prepared in the same manner as in Example 1 except that the silicone resin was changed to Si8, and then an LED package was prepared and subjected to each measurement and evaluation. The results are shown in Table 1. As shown in Table 1, in Comparative Example 1, the cutting workability was not a problem in practice, but the adhesion was not improved.

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

Using a slit die coater, the phosphor composition 3 is applied on the release treatment surface of “Therapy” BX9, which is the base material, heated at 120 ° C. for 40 minutes, dried, and 80 μm thick, 100 mm square fluorescent light A body sheet was obtained. Dynamic elastic modulus measurement and cutting workability evaluation were performed by the methods described above. Moreover, the LED package was produced by the method mentioned above, adhesiveness evaluation, and total luminous flux measurement were implemented. The results are shown in Table 1. Good results were obtained for both cutting processability and adhesion, and the relative luminance was also improved.

(Examples 4 to 8) (Modification of silicone composition)
As shown in Table 1, a phosphor sheet was prepared in the same manner as in Example 3 except that the silicone resin was changed to Si3 to Si7. Thereafter, an LED package was prepared, and each measurement and evaluation was performed. went. The results are shown in Table 1. As shown in Table 1, from the evaluation results of Examples 4 to 8, it was found that the phosphor sheet according to the embodiment of the present invention has good cutting processability and improved adhesion. It was also found that the relative luminance was improved.

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

(Example 9) (Resin content changed to 10.0% by weight)
Using a 100 ml polyethylene container, 5.96 g of silicone resin 2 (Si2), 53.6 g of phosphor 1 (YAG1) as an inorganic phosphor, 0.6 g of silicone fine particles, and 2.5 g of butyl carbitol Added and mixed. Thereafter, using a planetary stirring / defoaming device, stirring and defoaming was performed at 1000 rpm for 5 minutes, and then mixed and dispersed six times with three rolls to prepare phosphor composition 11.

Using a slit die coater, the phosphor composition 11 is applied on the release surface of “Therapy” BX9, which is a base material, heated at 120 ° C. for 40 minutes and dried, and has a thickness of 80 μm and a 100 mm square fluorescence. A body sheet was obtained. Dynamic elastic modulus measurement and cutting workability evaluation were performed by the methods described above. Moreover, the LED package was produced by the method mentioned above, adhesiveness evaluation, and total luminous flux measurement were implemented. The results are shown in Table 2. Good results were obtained for both cutting processability and adhesion, and the relative luminance was also improved.

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

Using a slit die coater, the phosphor composition 12 is applied on the release treatment surface of “Therapy” BX9, which is a base material, heated at 120 ° C. for 40 minutes and dried, and has a thickness of 80 μm and a 100 mm square fluorescence. A body sheet was obtained. Dynamic elastic modulus measurement and cutting workability evaluation were performed by the methods described above. Moreover, the LED package was produced by the method mentioned above, adhesiveness evaluation, and total luminous flux measurement were implemented. The results are shown in Table 2. Good results were obtained for both cutting processability and adhesion, and the relative luminance was also improved.

(Example 11) (Resin content changed to 85.0 wt%)
Using a 100 ml polyethylene container, 52.5 g of silicone resin 2 (Si2), 8.6 g of phosphor 1 (YAG1) as an inorganic phosphor, 0.6 g of silicone fine particles, and 2.5 g of butyl carbitol Added and mixed. Thereafter, using a planetary stirring / defoaming apparatus, stirring and defoaming was performed at 1000 rpm for 5 minutes, and then mixed and dispersed six times with three rolls to prepare phosphor composition 13.

Using a slit die coater, the phosphor composition 13 is applied onto the release treatment surface of “therapeutic” BX9, which is a base material, heated at 120 ° C. for 40 minutes, dried, and fluorescent having a thickness of 80 μm and a 100 mm square. A body sheet was obtained. Dynamic elastic modulus measurement and cutting workability evaluation were performed by the methods described above. Moreover, the LED package was produced by the method mentioned above, adhesiveness evaluation, and total luminous flux measurement were implemented. The results are shown in Table 2. Good results were obtained for both cutting processability and adhesion, and the relative luminance was also improved.

(Example 12) (Change in content of silicone fine particles to 0.5% by weight)
Using a 100 ml polyethylene container, 17.0 g of silicone resin 2 (Si2), 42.0 g of phosphor 1 (YAG1) as an inorganic phosphor, 0.3 g of silicone fine particles, and 2.5 g of butyl carbitol Added and mixed. Thereafter, using a planetary stirring / defoaming apparatus, stirring and defoaming was performed at 1000 rpm for 5 minutes, and then mixed and dispersed six times with three rolls to prepare a phosphor composition 14.

Using a slit die coater, the phosphor composition 14 is applied onto the release treatment surface of “Therapy” BX9, which is a base material, and heated and dried at 120 ° C. for 40 minutes, and has a thickness of 80 μm and a 100 mm square fluorescence. A body sheet was obtained. Dynamic elastic modulus measurement and cutting workability evaluation were performed by the methods described above. Moreover, the LED package was produced by the method mentioned above, adhesiveness evaluation, and total luminous flux measurement were implemented. The results are shown in Table 2. Good results were obtained for both cutting processability and adhesion, and the relative luminance was also improved.

(Example 13) (The silicone fine particle content is changed to 10.0% by weight)
Using a 100 ml polyethylene container, 11.0 g of silicone resin 2 (Si2), 42.0 g of phosphor 1 (YAG1) as an inorganic phosphor, 6 g of silicone fine particles, and 2.5 g of butyl carbitol were added. And mixed. Thereafter, using a planetary stirring / defoaming apparatus, stirring and defoaming was performed at 1000 rpm for 5 minutes, and then mixed and dispersed six times with three rolls to prepare phosphor composition 15.

Using a slit die coater, the phosphor composition 15 is applied onto the release treatment surface of “Therapy” BX9, which is a base material, heated at 120 ° C. for 40 minutes, dried, and fluorescent having a thickness of 80 μm and a 100 mm square. A body sheet was obtained. Dynamic elastic modulus measurement and cutting workability evaluation were performed by the methods described above. Moreover, the LED package was produced by the method mentioned above, adhesiveness evaluation, and total luminous flux measurement were implemented. The results are shown in Table 2. Good results were obtained for both cutting processability and adhesion, and the relative luminance was also improved.

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

Using a slit die coater, the phosphor composition 16 is applied on the release treatment surface of “Therapy” BX9, which is a base material, heated at 120 ° C. for 40 minutes and dried, and has a thickness of 80 μm and a 100 mm square fluorescence. A body sheet was obtained. Dynamic elastic modulus measurement and cutting workability evaluation were performed by the methods described above. Moreover, the LED package was produced by the method mentioned above, adhesiveness evaluation, and total luminous flux measurement were implemented. The results are shown in Table 2. Good results were obtained for both cutting processability and adhesion, and the relative luminance was also improved.

(Example 15) (phosphor content changed to 38.0 wt%)
Using a 100 ml polyethylene container, 36.4 g of silicone resin 2 (Si2), 22.7 g of phosphor 1 (YAG1) as an inorganic phosphor, 0.6 g of silicone fine particles, and 2.5 g of butyl carbitol Added and mixed. Thereafter, using a planetary stirring / defoaming apparatus, stirring and defoaming was performed at 1000 rpm for 5 minutes, and then mixed and dispersed six times with three rolls to prepare phosphor composition 17.

Using a slit die coater, the phosphor composition 17 is applied onto the release treatment surface of “Therapy” BX9, which is a base material, heated and dried at 120 ° C. for 40 minutes, and has a thickness of 80 μm and a 100 mm square fluorescence. A body sheet was obtained. Dynamic elastic modulus measurement and cutting workability evaluation were performed by the methods described above. Moreover, the LED package was produced by the method mentioned above, adhesiveness evaluation, and total luminous flux measurement were implemented. The results are shown in Table 3. Good results were obtained for both cutting processability and adhesion, and the relative luminance was also improved.

(Example 16) (The phosphor content is changed to 40.0% by weight)
Using a 100 ml polyethylene container, 35.2 g of silicone resin 2 (Si2), 23.8 g of phosphor 1 (YAG1) as an inorganic phosphor, 0.6 g of silicone fine particles, and 2.5 g of butyl carbitol Added and mixed. Thereafter, using a planetary stirring / defoaming apparatus, stirring and defoaming was performed at 1000 rpm for 5 minutes, and then mixed and dispersed six times with three rolls to prepare a phosphor composition 18.

Using a slit die coater, the phosphor composition 18 is applied on the release treatment surface of “Therapy” BX9, which is a base material, heated at 120 ° C. for 40 minutes and dried, and has a thickness of 80 μm and a 100 mm square fluorescence. A body sheet was obtained. Dynamic elastic modulus measurement and cutting workability evaluation were performed by the methods described above. Moreover, the LED package was produced by the method mentioned above, adhesiveness evaluation, and total luminous flux measurement were implemented. The results are shown in Table 3. Good results were obtained for both cutting processability and adhesion, and the relative luminance was also improved.

(Example 17) (phosphor content changed to 63.0 wt%)
Using a 100 ml polyethylene container, 21.5 g of silicone resin 2 (Si2), 37.6 g of phosphor 1 (YAG1) as an inorganic phosphor, 0.6 g of silicone fine particles, and 2.5 g of butyl carbitol Added and mixed. Thereafter, using a planetary stirring / defoaming apparatus, stirring and defoaming were performed at 1000 rpm for 5 minutes, and then mixed and dispersed six times with three rolls to prepare phosphor composition 19.

Using a slit die coater, the phosphor composition 19 is applied onto the release treatment surface of “Therapy” BX9, which is a base material, and heated and dried at 120 ° C. for 40 minutes, and has a thickness of 80 μm and a 100 mm square fluorescence. A body sheet was obtained. Dynamic elastic modulus measurement and cutting workability evaluation were performed by the methods described above. Moreover, the LED package was produced by the method mentioned above, adhesiveness evaluation, and total luminous flux measurement were implemented. The results are shown in Table 3. Good results were obtained for both cutting processability and adhesion, and the relative luminance was also improved.

(Example 18) (The phosphor content is changed to 80.0 wt%)
Using a 100 ml polyethylene container, 11.3 g of silicone resin 2 (Si2), 47.7 g of phosphor 1 (YAG1) as an inorganic phosphor, 0.6 g of silicone fine particles, and 2.5 g of butyl carbitol Added and mixed. Thereafter, using a planetary stirring / defoaming apparatus, stirring and defoaming were performed at 1000 rpm for 5 minutes, and then mixed and dispersed six times with three rolls to prepare phosphor composition 20.

Using a slit die coater, the phosphor composition 20 is applied on the release treatment surface of “Therapy” BX9, which is a base material, heated at 120 ° C. for 40 minutes and dried, and has a thickness of 80 μm and a 100 mm square fluorescence. A body sheet was obtained. Dynamic elastic modulus measurement and cutting workability evaluation were performed by the methods described above. Moreover, the LED package was produced by the method mentioned above, adhesiveness evaluation, and total luminous flux measurement were implemented. The results are shown in Table 3. Good results were obtained for both cutting processability and adhesion, and the relative luminance was also improved.

(Comparative Example 3)
A phosphor sheet was prepared in the same manner as in Example 15 except that the silicone resin was changed to Si9, and then an LED package was prepared and subjected to each measurement and evaluation. The results are shown in Table 3. As shown in Table 3, there was no practical problem with the cutting workability, but the adhesiveness was not improved.

(Comparative Example 4)
A phosphor sheet was prepared in the same manner as in Example 16 except that the silicone resin was changed to Si9, and then an LED package was prepared and subjected to each measurement and evaluation. The results are shown in Table 3. As shown in Table 3, there was no practical problem with the cutting workability, but the adhesiveness was not improved.

(Comparative Example 5)
A phosphor sheet was prepared in the same manner as in Example 17 except that the silicone resin was changed to Si9, and then an LED package was prepared and subjected to each measurement and evaluation. The results are shown in Table 3. As shown in Table 3, there was no practical problem with the cutting workability, but the adhesiveness was not improved.

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

(Example 19) (Modification of phosphor-1)
Using a 100 ml polyethylene container, 17.0 g of silicone resin 2 (Si2), 16.8 g of phosphor 2 (β1) as an inorganic phosphor, 25.2 g of phosphor 3 (KSF1), and silicone fine particles 0.6 g and 2.5 g of butyl carbitol were added and mixed. Thereafter, using a planetary stirring / defoaming apparatus, stirring and defoaming was performed at 1000 rpm for 5 minutes, and then mixed and dispersed six times with three rolls to prepare a phosphor composition 25.

Using a slit die coater, the phosphor composition 25 is applied on the release treatment surface of “Therapy” BX9 as a base material, heated at 120 ° C. for 30 minutes and dried, and has a thickness of 80 μm and a 100 mm square fluorescence. A body sheet was obtained. Dynamic elastic modulus measurement and cutting workability evaluation were performed by the methods described above. Moreover, the LED package was produced by the method mentioned above, adhesiveness evaluation, and total luminous flux measurement were implemented. The results are shown in Table 4. Very good results were obtained for both cutting workability and adhesiveness, and the relative luminance was greatly improved.

(Comparative Example 7)
A phosphor sheet was prepared in the same manner as in Example 19 except that the silicone resin was changed to Si9, and then an LED package was prepared and subjected to each measurement and evaluation. The results are shown in Table 4. As shown in Table 4, there was no practical problem with the cutting workability, but the adhesiveness was not improved.

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

Using a slit die coater, the phosphor composition 27 is applied on the release surface of “Therapy” BX9, which is a base material, heated and dried at 120 ° C. for 30 minutes, and has a thickness of 80 μm and a 100 mm square fluorescence. A body sheet was obtained. Dynamic elastic modulus measurement and cutting workability evaluation were performed by the methods described above. Moreover, the LED package was produced by the method mentioned above, adhesiveness evaluation, and total luminous flux measurement were implemented. The results are shown in Table 5. Very good results were obtained for both cutting processability and adhesiveness, and the relative luminance was also improved.

(Examples 21 to 24) (Modification of phosphor-3)
In Examples 21 to 24, a phosphor composition (28 to 32) was prepared in the same manner as in Example 20 except that the organic phosphor was appropriately changed as shown in Table 5, and each of the examples was used. A phosphor sheet was prepared in the same manner as in No. 20. Thereafter, an LED package was produced and evaluated using each of them. The results are shown in Table 5. From the evaluation results of Examples 21 to 24, it was found that very good results were obtained for both cutting processability and adhesiveness, and the relative luminance was improved.

(Comparative Example 8)
A phosphor composition 33 was prepared in the same manner as in Example 20 except that the silicone resin was changed to Si9 and the phosphor was changed to phosphor 4 (type 27) and phosphor 5 (type 28). A sheet was produced. Then, the LED package was produced and each measurement and evaluation were performed. The results are shown in Table 5. As shown in Table 5, there was no practical problem with the cutting processability, but the adhesiveness was not improved.

DESCRIPTION OF SYMBOLS 1 LED chip 2 Phosphor sheet 3 Transparent sealing material 4 Reflector 5 Mounting board 6 Electrode 7 Gold bump 8 Transparent adhesive 9 Base material 10 LED package 11 Temporary fixing sheet 12 Thermocompression bonding tool 13 Wafer 14 on which the LED chip is formed Phosphor sheet laminate 15 Package substrate 16 Package electrode 17 Double-sided adhesive tape 18 Base 19 Upper chamber 20 Lower chamber 21 Diaphragm 22 Vacuum diaphragm muraminator 23 Intake / exhaust port 24 Cut portion 25 LED chip with phosphor sheet 26 Phosphor with substrate LED chip with sheet

Claims

A phosphor sheet containing a phosphor and a silicone resin, having a storage elastic modulus G ′ at 25 ° C. of 0.01 MPa or more, a storage elastic modulus G ′ at 100 ° C. of less than 0.01 MPa, and 140 ° C. A phosphor sheet having a storage elastic modulus G ′ of 0.05 MPa or more.
The phosphor sheet according to claim 1, 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 formula:

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

(In the average unit formula (2), R 3 is a monovalent hydrocarbon group having 1 to 14 carbon atoms, at least one is an aryl group, and at least one is an alkenyl having 2 to 6 carbon atoms. F, g, and h are numbers satisfying 0.1 <f ≦ 0.4, 0.2 ≦ g ≦ 0.5, 0.2 ≦ h ≦ 0.5, and f + g + h = 1. )
(C) Organopolysiloxane having at least two Si—H bonds in one molecule and 12 to 70 mol% of organic groups bonded to silicon atoms being aryl groups Polysiloxane (D) Hydrosilylation catalyst
The phosphor sheet according to claim 2, wherein a content of the component (B) is 10 parts by weight or more and 95 parts by weight or less with respect to 100 parts by weight of the component (A).
Component (C) 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. However, 12 to 70 mol% of R 4 is an aryl group.)
The phosphor sheet according to any one of claims 1 to 3, which is an organopolysiloxane represented by the formula:
The phosphor sheet according to any one of claims 1 to 4, wherein a content of the phosphor is 40 wt% or more and 90 wt% or less.
The phosphor is a β-sialon phosphor and a general formula A 2 MF 6 : Mn (where A is selected from the group consisting of Li, Na, K, Rb and Cs, and includes at least Na and / or K) Mn-activated polyfluoride phosphor represented by the following formula: M is one or more alkali metals, and M is one or more tetravalent elements selected from the group consisting of Si, Ti, Zr, Hf, Ge, and Sn. The phosphor sheet according to any one of claims 1 to 5, comprising:
5. The phosphor sheet according to claim 1, wherein the phosphor is a pyromethene compound.
The phosphor sheet according to claim 7, 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 hydrogen, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, mercapto group, Alkoxy group, alkylthio group, aryl ether group, aryl thioether group, aryl group, heteroaryl group, heterocyclic group, halogen, haloalkane, haloalkene, haloalkyne, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group , An amino group, a nitro group, a silyl group, a siloxanyl group, a condensed ring formed between adjacent substituents and an aliphatic ring, M represents an m-valent metal, boron, beryllium, magnesium, At least one selected from chromium, iron, nickel, copper, zinc, platinum Seeds.)
The phosphor sheet according to claim 8, 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 claim 8 or 9, wherein in the general formula (4), Ar 5 is a group represented by the general formula (5).

(R is hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, thiol group, alkoxy group, alkylthio group, aryl ether group, aryl thioether group, aryl group, hetero It is selected from the group consisting of an aryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, oxycarbonyl group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl group, and phosphine oxide group. Is an integer of 1 to 3. When k is 2 or more, r may be the same or different.
An LED chip comprising the phosphor sheet according to any one of claims 1 to 10 or a cured product thereof.
An LED package comprising the phosphor sheet according to any one of claims 1 to 10 or a cured product thereof.
A method for manufacturing an LED package, comprising: a step of cutting the phosphor sheet according to any one of claims 1 to 10 into individual pieces; and a step of attaching the phosphor sheet cut into the individual pieces to an LED chip.
The manufacturing method of the LED package of Claim 13 which affixes the said fluorescent substance sheet on the part which avoided the electrode of the light emission surface of the said LED chip.
A process of affixing the phosphor sheet according to any one of claims 1 to 10 to a plurality of LED chips formed on a wafer, dicing the wafer, and affixing the phosphor sheet The manufacturing method of an LED package including the process of lump-dividing LED chip collectively.
The method for manufacturing an LED package according to any one of claims 13 to 15, wherein a heating temperature when the phosphor sheet is attached to the LED chip is 60 ° C or higher and 250 ° C or lower.
A light emitting device comprising the LED package according to claim 12.
A backlight unit comprising the LED package according to claim 12.
A display comprising the LED package according to claim 12.