CN110312954B - Phosphor sheet, LED chip and LED package using same, method for manufacturing LED package, and light-emitting device, backlight module, and display each including LED package - Google Patents

Phosphor sheet, LED chip and LED package using same, method for manufacturing LED package, and light-emitting device, backlight module, and display each including LED package Download PDF

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CN110312954B
CN110312954B CN201880012963.XA CN201880012963A CN110312954B CN 110312954 B CN110312954 B CN 110312954B CN 201880012963 A CN201880012963 A CN 201880012963A CN 110312954 B CN110312954 B CN 110312954B
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phosphor sheet
phosphor
led chip
led package
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CN110312954A (en
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石田丰
神崎达也
长濑亮
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Toray Industries Inc
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Abstract

According to the present invention, a phosphor sheet having excellent workability such as cutting and having good adhesiveness to an LED chip can be provided. The present invention is a phosphor sheet comprising a phosphor and a silicone resin, wherein the phosphor sheet has a storage elastic modulus at a temperature of 25 ℃ of 0.01MPa or more, a storage elastic modulus at a temperature of 100 ℃ of less than 0.01MPa, and a storage elastic modulus G' at a temperature of 140 ℃ of 0.05MPa or more.

Description

Phosphor sheet, LED chip and LED package using same, method for manufacturing LED package, and light-emitting device, backlight module, and display each including LED package
Technical Field
The present invention relates to a phosphor sheet, an LED chip and an LED package using the same, a method for manufacturing the LED package, and a light-emitting device, a backlight module, and a display including the LED package.
Background
Light Emitting Diodes (LEDs) have been rapidly expanding in market not only in backlight applications of Liquid Crystal displays (LCDs, Liquid Crystal displays) and in vehicle-mounted fields such as headlights of vehicles but also in general illumination applications, due to their features such as low power consumption, long life, and design, on the background of their remarkable improvement in Light emission efficiency. Since the environmental load of LEDs is also low, it is expected that LEDs will form a huge market in the general illumination field in the future.
The emission spectrum of the LED depends on the semiconductor material forming the LED chip, and thus its emission color is limited. Therefore, in order to obtain white light for use in backlights and general illumination of LCDs using LEDs, it is necessary to arrange inorganic phosphors suitable for the respective chips on the LED chips and convert the emission wavelengths. Specifically, a method of providing a yellow phosphor on a blue light-emitting LED chip, a method of providing a red phosphor and a green phosphor on a blue light-emitting LED chip, and the like have been proposed.
As one of specific methods for providing a phosphor on an LED chip, a method of attaching a phosphor-containing sheet (hereinafter referred to as "phosphor sheet") to an LED chip has been proposed (for example, see patent documents 1 to 4). This method makes it easier to keep the amount of the phosphor disposed on the LED chip constant, compared with a method in which a phosphor composition obtained by dispersing a phosphor in a resin is dispensed onto an LED chip and cured, which has been put into practical use. As a result, the white LED obtained is excellent in that the color and luminance can be made uniform.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2009 and 235368
Patent document 2: japanese patent laid-open publication No. 2010-123802
Patent document 3: japanese patent publication 2011-102004
Patent document 4: japanese patent No. 5287935
Disclosure of Invention
Problems to be solved by the invention
When the method of attaching the phosphor sheet to the LED chip is used, the following processing needs to be performed: cutting processing when the phosphor sheet is cut into the size of the LED chip; drilling of the portion of the phosphor sheet corresponding to the electrode portion or the like on the LED chip; and so on. Therefore, a phosphor sheet having excellent processability is required.
On the other hand, the phosphor sheet is required to have adhesiveness for being stuck on the LED chip. Patent document 4 discloses: by using a silicone composition containing a specific organopolysiloxane, a phosphor sheet having excellent workability before being bonded to an LED chip and excellent adhesiveness when bonded to an LED chip can be obtained. However, this phosphor sheet has insufficient curability after being bonded to the LED chip, and therefore satisfactory adhesiveness is not obtained. Therefore, the LED chip to which the phosphor sheet is attached has a problem that the luminance is reduced due to poor adhesiveness.
In order to solve the above problems, an object of the present invention is to provide a phosphor sheet that achieves both workability such as cutting and adhesiveness to an LED chip.
Means for solving the problems
Specifically, the present invention is a phosphor sheet comprising a phosphor and a silicone resin, wherein the storage elastic modulus G ' at 25 ℃ of the phosphor sheet is 0.01MPa or more, the storage elastic modulus G ' at 100 ℃ is less than 0.01MPa, and the storage elastic modulus G ' at 140 ℃ is 0.05MPa or more.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a phosphor sheet having excellent workability such as cutting and having good adhesiveness to an LED chip can be provided.
Drawings
Fig. 1A shows an example of an LED package using a phosphor sheet according to an embodiment of the present invention.
Fig. 1B shows an example of an LED package using the phosphor sheet according to the embodiment of the present invention.
Fig. 2 shows an example of a method for manufacturing an LED package using a phosphor sheet according to an embodiment of the present invention.
FIG. 3 shows an example of a method for attaching a phosphor sheet according to an embodiment of the present invention.
Fig. 4 shows an example of a method for attaching a phosphor sheet according to an embodiment of the present invention.
Fig. 5 shows an example of a method for attaching a phosphor sheet according to an embodiment of the present invention.
Fig. 6 shows an example of a method for manufacturing an LED package using a phosphor sheet according to an embodiment of the present invention.
Fig. 7 shows an example of a method for manufacturing an LED package using the phosphor sheet according to the embodiment of the present invention.
Detailed Description
Preferred embodiments of the phosphor sheet, the LED chip and the LED package using the same, the method for manufacturing the LED package, and the light-emitting device, the backlight module, and the display including the LED package according to the present invention will be described below in detail. However, the present invention is not limited to the following embodiments, and can be carried out with various modifications according to the purpose and application.
< phosphor sheet >
A phosphor sheet according to an embodiment of the present invention includes a phosphor and a silicone resin, and has a storage elastic modulus G ' at 25 ℃ of 0.01MPa or more, a storage elastic modulus G ' at 100 ℃ of less than 0.01MPa, and a storage elastic modulus G ' at 140 ℃ of 0.05MPa or more.
The phosphor sheet according to the embodiment of the present invention has sufficient elasticity at room temperature (25 ℃) by setting the storage elastic modulus G' at 25 ℃ to 0.01MPa or more. Therefore, the phosphor sheet is cut so that the periphery of the cut portion is not deformed against a rapid shearing stress such as cutting by the blade, and workability with high dimensional accuracy can be obtained.
The upper limit of the storage elastic modulus G' at 25 ℃ is not particularly limited, but is preferably 2.0MPa or less from the viewpoint of ease of handling of the sample.
In the phosphor sheet according to the embodiment of the present invention, the storage elastic modulus G' at 100 ℃ is made smaller than 0.01MPa, whereby the sheet has sufficient viscosity at 100 ℃ and high fluidity. Therefore, by attaching the phosphor sheet having the physical properties to the LED chip while heating at 100 ℃ or higher, the phosphor sheet quickly flows and deforms following the shape of the light emitting surface of the LED chip, and thus high adhesion between the phosphor sheet and the LED chip can be obtained. This improves the light extraction performance of light extracted from the LED chip, thereby improving the luminance.
The lower limit of the storage elastic modulus G' at 100 ℃ is not particularly limited, but when the fluidity of the phosphor sheet is too high when the phosphor sheet is heated and bonded to the LED chip, the shape processed by cutting or punching before bonding cannot be maintained at the time of bonding, and therefore, it is preferably 0.005MPa or more.
The phosphor sheet according to the embodiment of the present invention can stably operate the LED chip finally by setting the storage elastic modulus G' at 140 ℃ to 0.05MPa or more. When the phosphor sheet having the physical properties is heated at 140 ℃ or higher, complete curing of the sheet is rapidly completed, and the entire resin is integrated, so that the adhesiveness between the phosphor sheet and the LED chip is improved. Thereby, the luminance of the LED package is also improved. In addition, since the interface portion between the LED chip and the phosphor sheet is less susceptible to the heat generated when the LED is turned on, the separation of the LED chip and the phosphor sheet is suppressed. Therefore, the reliability of the LED package is improved.
Here, the storage elastic modulus G 'is a storage elastic modulus G' when a dynamic viscoelasticity of the phosphor sheet is measured (temperature dependence) using a rheometer. The dynamic viscoelasticity is a method of analyzing dynamic mechanical properties of a material by expressing shear stress when a material reaches a steady state when shear strain is applied to the material at a certain sinusoidal frequency, decomposing the shear stress into a component (elastic component) in which strain and phase are aligned and a component (viscous component) in which strain and phase are different by 90 °.
For the dynamic viscoelasticity measurement (temperature dependence), the dynamic viscoelasticity measurement can be performed using a general viscosity/viscoelasticity measurement device. In the present invention, the values are values when measurement is performed under the following conditions.
A measuring device: viscosity/viscoelasticity measuring apparatus HAAKE MARSIII
(Thermo Fisher SCIENTIFIC)
The measurement conditions were as follows: OSC temperature dependence determination
Geometry: parallel round plate type (20mm)
Measuring time: 1980 seconds
Angular frequency: 1Hz
Angular velocity: 6.2832 rad/sec
Temperature range: 25 to 200 ℃ (with low temperature control function)
Temperature rise rate: 0.08333 deg.C/sec
Sample shape: circular (diameter 18mm)
Sample thickness: more than 50 μm.
When 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 sheets may be stacked and heated and pressure-bonded on a heating plate at 100 ℃ to produce an integrated film (sheet) and thereby produce a sample having a desired thickness.
The amount of the stress component whose phase matches the shear strain divided by the shear strain is the storage elastic modulus G'. The storage elastic modulus G' represents the elasticity of the material with respect to 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 properties of the phosphor sheet. For example, the storage elastic modulus G' at 25 ℃ affects the processability of the phosphor sheet, the fluidity and adhesiveness of the phosphor sheet at 100 ℃ and the curability and adhesiveness of the phosphor sheet at 140 ℃.
The thickness of the phosphor sheet according to the embodiment of the present invention is not particularly limited, but is preferably 10 μm or more and 1000 μm or less. The lower limit is more preferably 30 μm or more. The upper limit is more preferably 200 μm or less, still more preferably 100 μm or less, and still more preferably 50 μm or less. The phosphor sheet has a thickness of 1000 μm or less, and is particularly excellent in crack resistance, and has a thickness of 200 μm or less, and is particularly excellent in heat resistance.
The phosphor sheet according to the embodiment of the present invention may be a laminate including other layers as necessary. Examples of the other layer include a substrate and a barrier layer.
(Silicone resin)
The phosphor sheet according to the embodiment of the present invention mainly contains a silicone resin from the viewpoint of transparency and heat resistance.
As the silicone resin used in the present invention, a curable silicone resin is preferred. The curable silicone resin may be any of one-pack type and two-pack type (three-pack type). The curable silicone resin includes, as types that undergo condensation reaction by moisture in the air or a catalyst, dealcoholization types, deoximation types, deacetylation types, dehydroxylation types, and the like. There is also an addition reaction type in which a hydrosilylation reaction occurs 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 in terms of no by-product accompanying the curing reaction, small curing shrinkage, and easy acceleration of curing by heating.
For example, the addition reaction type silicone resin is formed by a hydrosilylation reaction of a compound containing an alkenyl group bonded to a silicon atom and a compound having a hydrogen atom bonded to a silicon atom.
Examples of the "compound having an alkenyl group bonded to a silicon atom" include vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, propenyltrimethoxysilane, norbornenyltrimethoxysilane, octenyltrimethoxysilane and the like. Examples of the "compound having a hydrogen atom bonded to a silicon atom" include methylhydrogenpolysiloxane, dimethylpolysiloxane-CO-methylhydrogenpolysiloxane, ethylhydrogenpolysiloxane, methylhydrogenpolysiloxane-CO-methylphenylpolysiloxane, and the like. Examples of the addition reaction type silicone rubber include rubbers formed by hydrosilylation of such materials. Further, as the silicone resin, a known resin such as that described in, for example, japanese patent application laid-open No. 2010-159411 can be used.
In the present invention, the silicone resin is preferably a crosslinked product of a crosslinkable silicone composition (hereinafter referred to as "the present composition") containing at least the following components (a) to (D). In the silicone resin, the crosslinked product of the present composition is preferably 20% by weight or more, more preferably 50% by weight or more, and still more preferably 80% by weight or more.
(A) An organopolysiloxane having a branched structure represented by the average unit formula (1).
[ chemical formula 1]
(R1 3SiO1/2)a(R1 2SiO2/2)b(R1SiO3/2)c(SiO4/2)d(R2O1/2)e (1)
(average unit formula (1) wherein R1Is a monovalent hydrocarbon group having 1 to 14 carbon atoms, at least one of which is an aryl group and at least one of which is an alkenyl group having 2 to 6 carbon atoms. R2Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. a. b, c, d, and e are numbers satisfying 0. ltoreq. a.ltoreq.0.1, 0.2. ltoreq. b.ltoreq.0.9, 0.1. ltoreq. c.ltoreq.0.6, 0. ltoreq. d.ltoreq.0.2, 0. ltoreq. e.ltoreq.0.1, and a + b + c + d + e.ltoreq.1. )
(B) An organopolysiloxane having a branched structure represented by the average unit formula (2).
[ chemical formula 2]
(R3 3SiO1/2)f(R3 2SiO2/2)g(R3SiO3/2)h (2)
(in the average unit formula (2), R3Is a monovalent hydrocarbon group having 1 to 14 carbon atoms, at least one of which is an aryl group and at least one of which is an alkenyl group having 2 to 6 carbon atoms. f. g and h are numbers satisfying 0.1 < f.ltoreq.0.4, 0.2. ltoreq.g.ltoreq.0.5, 0.2. ltoreq.h.ltoreq.0.5, and f + g + h is 1. )
(C) An organopolysiloxane having at least two Si-H bonds in one molecule, wherein 12 to 70 mol% of organic groups bonded to silicon atoms are aryl groups.
(D) A catalyst for hydrosilylation.
(A) The organopolysiloxane of component (B) has an aryl group, so that the compatibility with components (B) to (D) can be improved. The organopolysiloxane of component (A) has an alkenyl group having 2 to 6 carbon atoms, and causes a crosslinking reaction of components (A) to (C). Further, the organopolysiloxane of component (a) has a branched structure, so that curability is improved and good adhesion to the LED chip can be obtained.
The branched structure means the following structure: in the average unit formula, the basic structural unit has a T unit (RSiO)3/2) Q unit (SiO)4/2). In the average unit formula, a trifunctional unit having 1 organic substituent represented by R on a silicon atom is referred to as a T unit, and a tetrafunctional unit having no organic substituent represented by R on a silicon atom is referred to as a Q unit.
By introducing a branched structure into the organopolysiloxane of component (a), the crosslinking reaction rate is increased, and the phosphor sheet can obtain good curability.
The presence of a branched structure in the organopolysiloxane can be confirmed by: the organopolysiloxane is subjected to a treatment such as trimethyl orthoformate decomposition, and then subjected to NMR analysis and GPC-MALS analysis.
In particular, in GPC-MALS analysis, the molecular weight distribution and the radius of rotation of the organopolysiloxane can be determined. Therefore, the presence of a branched structure can be confirmed by specifying a component having a small radius of rotation among the organopolysiloxanes having the same molecular weight component.
In the average unit formula (1), the values of a, b, c, d and e are in the following ranges: the resulting crosslinked material is sufficiently hard at room temperature and sufficiently soft at high temperatures for the practice of the present invention.
(B) The organopolysiloxane of component (a) has an aryl group, and thus is compatible with component (a). This makes it possible to maintain the mechanical strength and transparency of the cured film of the phosphor sheet containing the silicone resin. The organopolysiloxane of component (B) has an alkenyl group having 2 to 6 carbon atoms, and causes a crosslinking reaction of components (A) to (C). The organopolysiloxane of component (B) has a branched structure, and therefore, curability is improved, and good adhesion to the LED chip can be obtained.
In addition, the viscosity of the organopolysiloxane of component (B) at 25 ℃ is preferably 20Pa · s or less from the viewpoint of good workability in the preparation of samples and the like.
(B) The content of the component (a) is preferably in the range of 10 parts by weight or more and 95 parts by weight or less based on 100 parts by weight of the component (a). This is a range for sufficiently softening the obtained crosslinked product at high temperature.
(C) The organopolysiloxane of component (A) has at least two Si-H bonds in one molecule, so that the crosslinking reaction of components (A) to (C) occurs. In addition, 12 to 70 mol% of the organic groups bonded to silicon atoms in the organopolysiloxane of component (C) are aryl groups, so that the obtained crosslinked product is sufficiently softened at high temperature, and the transparency and mechanical strength of the crosslinked product are maintained.
In particular, in the present invention, the organopolysiloxane of component (C) is preferably an organopolysiloxane represented by the average unit formula (3).
[ chemical formula 3]
(HR4 2SiO)2SiR4 2 (3)
(in the average unit formula (3), R4Is aryl, alkyl with 1-6 carbon atoms or cycloalkyl. Wherein R is412 to 70 mol% of the aromatic group is an aromatic group. )
In the average unit formula (3), R4Preferably a phenyl group, an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group. As R4Examples of the alkyl group of (b) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a heptyl group. As R4Examples of the cycloalkyl group of (b) include cyclopentyl and cycloheptyl. In addition, R is4The content of the phenyl group 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.
(C) The content of component (B) is preferably such that the molar ratio of the silicon-bonded hydrogen atoms in component (C) to the total amount of alkenyl groups in component (a) and component (B) is in the range of 0.5 to 2. It is used to obtain sufficient hardness of the resulting crosslinked product at room temperature.
(D) The catalyst for the hydrosilylation reaction of component (a) is a catalyst for promoting the hydrosilylation reaction of the alkenyl groups of component (a) and component (B) with the silicon atom-bonded hydrogen atoms of component (C). Examples of the component (D) include platinum catalysts, rhodium catalysts and palladium catalysts. Among these, a platinum-based catalyst is preferable in that the curing of the present composition can be significantly promoted.
Examples of the platinum-based catalyst include fine platinum 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, alkenylsiloxanes obtained by substituting a part of the methyl groups of these alkenylsiloxanes by ethyl groups, phenyl groups, etc., and alkenylsiloxanes obtained by substituting the vinyl groups of these alkenylsiloxanes by allyl groups, hexenyl groups, etc. In particular, 1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane is preferable because the stability of the platinum-alkenylsiloxane complex is good.
Further, it is preferable to add an organosiloxane oligomer such as 1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane, 1, 3-diallyl-1, 1, 3, 3-tetramethyldisiloxane, 1, 3-divinyl-1, 3-dimethyl-1, 3-diphenyldisiloxane, 1, 3-divinyl-1, 1, 3, 3-tetraphenyldisiloxane, alkenylsiloxane such as 1, 3, 5, 7-tetramethyl-1, 3, 5, 7-tetravinylcyclotetrasiloxane, dimethylsiloxane oligomer, or the like to the platinum-alkenylsiloxane complex, because the stability of the platinum-alkenylsiloxane complex can be improved. In particular, it is preferable to add an alkenylsiloxane to the complex.
The content of the component (D) is not particularly limited as long as it is a sufficient amount for promoting the hydrosilylation reaction between the alkenyl groups in the components (a) and (B) and the silicon atom-bonded hydrogen atoms in the component (C). The content of the component (D) is preferably in a range such that the metal atom in the component (D) is 0.01 to 500ppm in mass unit relative 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 100ppm, and particularly preferably an amount such that the metal atom is in the range of 0.01 to 50 ppm. This is a range in which the present composition can be sufficiently crosslinked and problems such as coloring do not occur.
The present composition may contain, as other optional components: acetylenic alcohols such as ethynylhexanol, 2-methyl-3-butyn-2-ol, 3, 5-dimethyl-1-hexyn-3-ol, and 2-phenyl-3-butyn-2-ol; enyne compounds such as 3-methyl-3-pentene-1-yne and 3, 5-dimethyl-3-hexene-1-yne; 1, 3, 5, 7-tetramethyl-1, 3, 5, 7-tetravinylcyclotetrasiloxane, 1, 3, 5, 7-tetramethyl-1, 3, 5, 7-tetrahexenylcyclotetrasiloxane, benzotriazole and the like. The content of the reaction inhibitor is not particularly limited, but is preferably in the range of 1 to 5,000ppm based on the weight of the present composition. By adjusting the content of the reaction inhibitor, the storage elastic modulus of the obtained silicone resin can also be adjusted.
In the phosphor sheet according to the embodiment of the present invention, the content of the silicone resin is preferably 10% by weight or more, and more preferably 30% by weight or more of the entire phosphor sheet. The content of the silicone resin is preferably 90 wt% or less, more preferably 85 wt% or less, and still more preferably 70 wt% or less.
As will be described in detail later, the phosphor sheet according to the embodiment of the present invention is particularly preferably used for surface coating of LEDs. In this case, by setting the content of the silicone resin in the phosphor sheet within the above range, a light-emitting device exhibiting excellent performance can be obtained.
(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. Thus, part of the light emitted from the LED chip is mixed with part of the light emitted from the phosphor, and a multicolor LED including white is obtained. Specifically, by optically combining a blue LED chip and a phosphor that absorbs light emitted from the LED chip and emits a yellow emission color, white light can be emitted using a single LED chip.
Among the above phosphors, there are various phosphors such as a phosphor emitting green light, a phosphor emitting blue light, a phosphor emitting yellow light, and a phosphor emitting red light. Specific examples of the phosphor used in the present invention include known phosphors such as inorganic phosphors, organic phosphors, and quantum dots. Any of fluorescent pigments and fluorescent dyes can be used as the phosphor.
The inorganic phosphor is not particularly limited as long as a predetermined color can be reproduced at the end, and a known inorganic phosphor can be used.
The organic phosphor preferably has an emission spectrum having a peak in a wavelength region of 500 to 700 nm. The fluorescent substance is excited by excitation light having a wavelength of 400 to 500nm and emits light in a wavelength range of 500 to 700 nm. Examples of the above-mentioned phosphors include a phosphor emitting green light, a phosphor emitting yellow light, and a phosphor emitting red light. Examples of the organic phosphor used in the present invention include a methylene pyrrole compound, a coumarin-based dye, a phthalocyanine-based dye, a stilbene-based dye, a cyanine-based dye, a polyphenylene-based dye, a rhodamine-based dye, a pyridine-based dye, a methylene pyrrole-based dye, a porphyrin-based dye, an oxazine-based dye, a pyrazine-based dye, an arylsulfonamide/melamine formaldehyde cocondensed dye, a perylene-based phosphor, and the like. From the viewpoint of color reproducibility, a methylene pyrrole compound is preferably used, and particularly an organic compound represented by the general formula (4) described later is preferably used.
Quantum dots refer to semiconductor nanoparticles that are excited by excitation light to emit fluorescence.
The quantum dot used in the present invention is preferably a core-shell type semiconductor nanoparticle from the viewpoint of improving durability. As the core, II-VI semiconductor nanoparticles, III-V semiconductor nanoparticles, and multi-component semiconductor nanoparticles can be used. Specific examples thereof include, but are not limited to, CdSe, CdTe, CdS, ZnS, ZnSe, ZnTe, InP, InAs, and InGaP. Among them, CdSe, CdTe, InP, and InGaP are preferable from the viewpoint of efficiently emitting visible light. As the shell, CdS, ZnS, ZnO, GaAs, and a complex thereof can be used, but the shell is not limited thereto. The emission wavelength of a quantum dot can generally be tuned by the composition and size of the particle.
The surface of the quantum dot may be coordinated with a ligand having a Lewis basic coordinating group. Examples of the Lewis basic coordinating group include amino group, carboxyl group, mercapto group, phosphino group, phosphinoxide group and the like. Specific examples thereof include hexylamine, decylamine, hexadecylamine, octadecylamine, oleylamine, tetradecylamine, dodecylamine, oleic acid, mercaptopropionic acid, trioctylphosphine, and trioctylphosphine oxide. Among them, hexadecylamine, trioctylphosphine and trioctylphosphine oxide are preferable, and trioctylphosphine oxide is particularly preferable.
The quantum dots to which these ligands are coordinated can be produced by known synthetic methods. For example, they can be synthesized by The method described in C.B.Murray, D.J.Norris, M.G.Bawendi, Journal American Chemical Society, 1993, 115(19), pp8706-8715, or The Journal Physical Chemistry, 101, pp9463-9475, 1997. In addition, commercially available quantum dots can be used without any limitation for the quantum dots to which the ligands are coordinated. For example, Lumidot (manufactured by Sigma-Aldrich Co.) can be mentioned.
The phosphor particularly preferably used in the present invention includes inorganic phosphors. The inorganic phosphor used in the present invention will be described below.
(inorganic phosphor)
The inorganic phosphor used in the present invention preferably has an emission spectrum having a peak in a wavelength region of 500 to 700 nm. The fluorescent substance is excited by excitation light having a wavelength of 400 to 500nm and emits light in a wavelength range of 500 to 700 nm. Examples of the above-mentioned fluorescent materials include a fluorescent material emitting green light, a fluorescent material emitting yellow light, and a fluorescent material emitting red light.
The shape of the inorganic phosphor is not particularly limited, and various shapes such as a spherical shape and a columnar shape can be used.
Examples of the inorganic phosphor used in the present invention include YAG-based phosphors, TAG-based phosphors, silicate phosphors, nitride phosphors, oxynitride phosphors, Mn-activated complex fluoride complex phosphors, and the like. Preferred examples of the oxynitride phosphor include β -type sialon phosphors.
Among them, a nitride phosphor, an oxynitride phosphor, and a Mn-activated complex fluoride phosphor can be preferably used, and a β -type sialon phosphor and a Mn-activated complex fluoride phosphor are more preferably used. By using these phosphors, a phosphor sheet having high luminance can be obtained.
The phosphor sheet according to the embodiment of the present invention preferably contains a β -type sialon phosphor and an Mn activated complex fluoride complex phosphor.
(beta-sialon phosphor)
The β -sialon is a solid solution of β -type silicon nitride, and is formed by substituting Al in a Si position and O in a N position of a β -type silicon nitride crystal. The unit cell (unit cell) of the beta-sialon has atoms of formula 2,thus, as the general formula, Si can be used6-zAlzOzN8-z. 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. The general process for preparing beta-sialon is as follows: in addition to silicon nitride, silicon oxide and aluminum nitride, or aluminum oxide and aluminum nitride are added and heated.
The beta-sialon phosphor is formed by doping a crystal structure with a light-emitting element such as a rare earth element (Eu, Sr, Mn, Ce, etc.), and is excited by ultraviolet to blue light to emit green light having a wavelength of 520 to 550 nm.
The beta-sialon phosphor used in the present invention preferably has an emission spectrum having a peak in a wavelength range of 535 to 550 nm. When the phosphor sheet according to the embodiment of the present invention is applied to an LED package, favorable light emission characteristics can be obtained within such a range. The average particle size of the β -type sialon phosphor is preferably 1 μm or more, more preferably 10 μm or more, and still more preferably 16 μm or more. Further, it is preferably 100 μm or less, more preferably 50 μm or less, and further preferably 19 μm or less. When the phosphor sheet according to the embodiment of the present invention is applied to an LED package, favorable light emission characteristics can be obtained within such a range.
(KSF phosphor)
The Mn activated complex fluoride complex phosphor is a phosphor having Mn as an activator and a fluoride complex salt of an alkali metal or an alkaline earth metal as a host crystal. In the Mn-activated complex fluoride phosphor, the coordination center of the fluoride complex forming the matrix crystal is preferably a tetravalent metal (Si, Ti, Zr, Hf, Ge, Sn), and the number of fluorine atoms coordinated around it is preferably 6.
The Mn activated complex fluoride complex phosphor is represented by the general formula A2MF6: mn (here, a is one or more alkali metals selected from the group consisting of Li, Na, K, Rb and Cs, and 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). On the upper partIn the general formula, is K2SiF6: the compound of Mn is KSF phosphor. The KSF phosphor is preferable as the Mn activated complex fluoride complex phosphor used in the present invention.
The average particle size of the Mn activated complex fluoride phosphor is preferably 1 μm or more, more preferably 10 μm or more, and still more preferably 20 μm or more. Further, it is preferably 100 μm or less, more preferably 70 μm or less, and further preferably 40 μm or less. When the amount of the fluorescent material is within such a range, favorable light emission characteristics can be obtained when the fluorescent material sheet according to the embodiment of the present invention is applied to an LED package.
In the present invention, the average particle diameter refers to the median particle diameter (D50). The average particle diameter can be measured by observing the phosphor sheet with a Scanning Electron Microscope (SEM). From a two-dimensional image obtained by observing the cross section of the phosphor sheet, the distance at which the maximum value is obtained among the distances between the two intersection points of the straight line intersecting the outer edge of the phosphor particle at 2 points is calculated and defined as the particle diameter of each phosphor particle. The particle size was calculated by this method for 200 of the phosphor particles observed, and in the particle size distribution obtained therefrom, the particle size at which the cumulative percentage of sieving from the small particle size side was 50% was defined as D50.
When an LED light-emitting device having a phosphor sheet mounted thereon is used, the phosphor sheet may be polished by any of a mechanical polishing method, a slicing method, a CP (Cross-cut (I) on Pol (I) sher) method, and a focused ion beam (f (I) B) processing method so that a Cross section of the phosphor sheet can be observed, and then the obtained Cross section may be observed by SEM, and the average particle diameter described above may be calculated from the obtained two-dimensional image.
In the present invention, the content of the inorganic phosphor in the phosphor sheet is preferably 35% by weight or more, more preferably 40% by weight or more, and further preferably 60% by weight or more of the entire phosphor sheet. When the content of the phosphor in the phosphor sheet is in such a range, the luminance of the phosphor sheet can be improved. The upper limit of the content of the phosphor is not particularly limited, and the content of the phosphor in the phosphor sheet is preferably 90 wt% or less, more preferably 85 wt% or less, further preferably 80 wt% or less, and further preferably 70 wt% or less of the entire phosphor sheet, from the viewpoint of ease of production of a phosphor sheet having excellent handling properties.
The phosphor particularly preferably used in the present invention may be an organic phosphor which is an organic compound represented by the general formula (4). The organic compound represented by the general formula (4) used in the present invention is described below.
(organic Compound represented by the general formula (4))
[ chemical formula 4]
Figure BDA0002173187220000151
In the general formula (4) representing the organic compound in the present embodiment, R5、R6、Ar1～Ar5And L, which may be the same or different, is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aralkyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, mercapto, alkoxy, alkylthio, aryl ether, arylthioether, aryl, heteroaryl, heterocyclic, halogen, haloalkyl, haloalkenyl, haloalkynyl, cyano, aldehyde, carbonyl, carboxyl, ester, carbamoyl, amino, nitro, silyl, siloxane, a fused ring formed between adjacent substituents, and an aliphatic ring. M represents a metal having a valence of M and is at least one selected from the group consisting of boron, beryllium, magnesium, chromium, iron, nickel, copper, zinc and platinum. In all of the above groups, hydrogen may be deuterium. This is also the case with the organic compounds or their partial structures described below.
In the following description, for example, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms is an aryl group having 6 to 40 carbon atoms in total including the carbon atoms contained in a substituent group substituted on the aryl group. The same applies to other substituents having a given number of carbon atoms.
In addition, among all the above groups, the substituent to be substituted is preferably an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a hydroxyl group, a thiol group, an alkoxy group, an alkylthio group, an aryl ether group, an aryl thioether group, an aryl group, a heteroaryl group, a halogen group, a cyano group, an aldehyde group, a carbonyl group, a carboxyl group, an oxycarbonyl group, a carbamoyl group, an amino group, a nitro group, a silyl group, a siloxane group, a borane group, or a phosphine oxide group, and further preferably a specific substituent is preferable in the description of each substituent. These substituents may be further substituted with the above-mentioned substituents.
The term "unsubstituted" when it is "substituted or unsubstituted" means that a hydrogen atom or deuterium atom is substituted. In the organic compound or a partial structure thereof described below, the case of "substituted or unsubstituted" is also the same as described above.
In all of the above groups, the alkyl group means a saturated aliphatic hydrocarbon 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. The alkyl group may or may not further have a substituent. The additional substituent to be substituted is not particularly limited, and examples thereof include an alkyl group, an aryl group, and a heteroaryl group, and these are common in the following description. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably in the range of 1 to 20, more preferably 1 to 8, from the viewpoints of availability and cost.
The cycloalkyl group means, for example, a saturated alicyclic hydrocarbon group such as a cyclopropyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like, and may have a substituent or not. The number of carbon atoms of the alkyl moiety is not particularly limited, but is preferably in the range of 3 to 20.
The aralkyl group means an aromatic hydrocarbon group formed via an aliphatic hydrocarbon, such as a benzyl group or a phenethyl group. These aliphatic hydrocarbons and aromatic hydrocarbons may be unsubstituted or substituted.
The alkenyl group means an unsaturated aliphatic hydrocarbon group having a double bond such as a vinyl group, an allyl group, or a butadienyl group, and may or may not have a substituent. The number of carbon atoms of the alkenyl group is not particularly limited, and is usually in the range of 2 to 20.
The cycloalkenyl group means an unsaturated alicyclic hydrocarbon group having a double bond, such as a cyclopentenyl group, a cyclopentadienyl group, or a cyclohexenyl group, and may or may not have a substituent.
The alkynyl group means an unsaturated aliphatic hydrocarbon group having a triple bond such as an ethynyl group, and may or may not have a substituent. The number of carbon atoms of the alkynyl group is not particularly limited, and is usually in the range of 2 to 20.
The alkoxy group means, for example, a functional group in which an aliphatic hydrocarbon group is bonded via an ether bond, such as a methoxy group, an ethoxy group, or a propoxy group, and the aliphatic hydrocarbon group may have a substituent or may have no substituent. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably in the range of 1 to 20.
The alkylthio group means a group in which an oxygen atom of an ether bond of an alkoxy group is replaced with a sulfur atom. The hydrocarbyl group of the alkylthio group may or may not have a substituent. The number of carbon atoms of the alkylthio group is not particularly limited, and is usually in the range of 1 to 20.
The aryl ether group means a functional group in which an aromatic hydrocarbon group is bonded via an ether bond, such as a phenoxy group, and the aromatic hydrocarbon group may have a substituent or may have no substituent. The number of carbon atoms of the aryl ether group is not particularly limited, but is preferably in the range of 6 to 40.
The aryl thioether group is a group in which an oxygen atom of an ether bond of an aryl ether group is replaced with a sulfur atom. The aromatic hydrocarbon group in the aryl sulfide group may have a substituent or may have no substituent. The number of carbon atoms of the aryl thioether group is not particularly limited, but is usually in the range of 6 to 40.
The aryl group represents an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, a phenanthryl group, a triphenylene group, or a terphenyl group. The aryl group may have a substituent or may have no substituent. The number of carbon atoms of the aryl group is not particularly limited, but is preferably in the range of 6 to 40.
The heteroaryl group means a cyclic aromatic group having an atom other than carbon in 1 or more rings, such as furyl, thienyl, pyridyl, quinolyl, pyrazinyl, pyrimidinyl (ピリミニジニル in japanese), triazinyl, naphthyridinyl, benzofuryl, benzothienyl, indolyl, and the like, and 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 to 30.
The heterocyclic group means, for example, an aliphatic ring having an atom other than carbon in the ring, such as a pyran ring, a piperidine ring, or a cyclic amide, and may or may not have a substituent. The number of carbon atoms of the heterocyclic group is not particularly limited, and is usually in the range of 2 to 20.
The carbonyl group, the carboxyl group and the carbamoyl group may have a substituent or may have no substituent. 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.
The amino group is a substituted or unsubstituted amino group. The amino group may have a substituent or may have no substituent, and examples of the substituent at the time of substitution include an aryl group, a heteroaryl group, a straight-chain alkyl group, a branched-chain alkyl group, and the like. As the aryl group and the heteroaryl group, a phenyl group, a naphthyl group, a pyridyl group and a quinolyl group are preferable. These substituents may also be further substituted. The number of carbon atoms is not particularly limited, but is preferably 2 to 50, more preferably 6 to 40, and particularly preferably 6 to 30.
Halogen means fluorine, chlorine, bromine or iodine. The "haloalkyl group", haloalkenyl group and haloalkynyl group "mean, for example, a group in which a part or all of the above alkyl group, alkenyl group and alkynyl group such as trifluoromethyl group is substituted with the above halogen, and the remaining part may be unsubstituted or substituted. The aldehyde group, carbonyl group, ester group, and carbamoyl group also include groups substituted with an aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, heterocyclic ring, or the like, and the aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, and heterocyclic ring may be unsubstituted or substituted.
The silyl group means a functional group having a bond to a silicon atom, such as a trimethylsilyl group, and may or may not have a substituent. The number of carbon atoms of the silyl group is not particularly limited, and is usually in the range of 3 to 20. The number of silicon atoms is usually 1 to 6.
The siloxane group means a silicon compound group formed via an ether bond, such as a trimethylsiloxy group. The substituents on silicon may also be further substituted.
The organic compound represented by the above general formula (4) has a high fluorescence quantum yield and a small half-value width of a peak of an emission spectrum, and therefore, both efficient color conversion and high color purity can be achieved.
Among the metal complexes in the organic compound represented by the general formula (4), a complex in which M is boron is particularly preferable in view of high fluorescence quantum yield. Furthermore, from the viewpoint of ease of obtaining a material and ease of synthesis, a boron fluoride complex in which L is fluorine or a fluorine-containing aryl group and m-1 is 2 is particularly preferable.
In addition, any adjacent 2 substituents (for example, R of the general formula (4))5And Ar2) They may be bonded to each other to form a conjugated or non-conjugated fused ring. The constituent elements of the condensed ring may contain an element selected from nitrogen, oxygen, sulfur, phosphorus, and silicon, in addition to carbon. In addition, the condensed ring may be further condensed with another ring.
The organic compound represented by the above general formula (4) can be adjusted in various properties and physical properties such as luminous efficiency, color purity, thermal stability, light stability, and dispersibility by introducing an appropriate substituent at an appropriate position.
For example, the substituent Ar is a substituent for reducing the durability of the organic compound represented by the general formula (4), that is, the emission intensity of the organic compound with time5The influence is large. Specifically, Ar5In the case of hydrogen, the hydrogen has high reactivity, and therefore, the hydrogen easily reacts with moisture and oxygen in the air. This causes Ar5Decomposition of (3). In addition, Ar5When the substituent group is a substituent group having a large degree of freedom of movement of the molecular chain such as an alkyl group, the reactivity is surely lowered, but the organic compounds are bonded to each other in the sheetAggregation over time results in a decrease in luminescence intensity due to concentration quenching. Therefore, Ar is preferred5Specifically, any of a substituted or unsubstituted aryl group and a substituted or unsubstituted heteroaryl group is preferable.
Ar from the viewpoint of imparting higher fluorescence quantum yield and being less susceptible to thermal decomposition, and from the viewpoint of photostability5Preferably substituted or unsubstituted aryl. As the aryl group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, and an anthracyl group are preferable from the viewpoint of not impairing the emission wavelength.
Furthermore, in order to improve the light stability of the organic compound, it is necessary to appropriately suppress Ar5Distortion of the carbon-carbon bond to the methylene pyrrole backbone. This is because, when the twist is too large, the light stability is lowered, for example, reactivity to excitation light is improved. From the above viewpoint, Ar is5Preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, more preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group. Particularly preferred is a substituted or unsubstituted phenyl group.
In addition, Ar5Substituents with a moderately large volume are preferred. By reacting Ar with5Has a certain large volume, and can prevent the aggregation of molecules. As a result, the organic compound has further improved luminous efficiency and durability.
As a more preferable example of such a bulky substituent, Ar represented by the following general formula (5) may be mentioned5The structure of (1).
[ chemical formula 5]
Figure BDA0002173187220000201
That is, in the general formula (4) representing the above organic compound, Ar5A group represented by the general formula (5) is preferable.In the formula Ar5In the general formula (5), r is selected from the group consisting of hydrogen, alkyl, cycloalkyl, heterocyclic group, alkenyl, cycloalkenyl, alkynyl, hydroxyl, thiol, alkoxy, alkylthio, arylether, arylthioether, aryl, heteroaryl, halogen, cyano, aldehyde, carbonyl, carboxyl, oxycarbonyl, carbamoyl, amino, nitro, silyl, siloxane, boron, and phosphine oxide. k is an integer of 1 to 3. When k is 2 or more, r may be the same or different.
In these groups, for example, the oxycarbonyl group may have a substituent or may have no substituent. Examples of the substituent for the oxycarbonyl group include an alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group, and these substituents may be further substituted.
From the viewpoint of enabling higher fluorescence quantum yield, r is preferably a substituted or unsubstituted aryl group. Among the aryl groups, particularly preferred examples include phenyl and naphthyl groups. When r is an aryl group, k in the general formula (5) is preferably 1 or 2, and from the viewpoint of further preventing molecular aggregation, k is more preferably 2. Further, when k is 2 or more, at least one of r is preferably substituted with an alkyl group. In this case, the alkyl group is particularly preferably a methyl group, an ethyl group or a tert-butyl group from the viewpoint of thermal stability.
In addition, from the viewpoint of controlling the fluorescence wavelength, the absorption wavelength, and improving the compatibility with a solvent, r is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a halogen, and more preferably a methyl group, an ethyl group, a tert-butyl group, or a methoxy group. From the viewpoint of dispersibility, tert-butyl and methoxy are particularly preferable. When r is a tert-butyl group or a methoxy group, it is more effective for preventing quenching caused by aggregation of molecules with each other.
And Ar1～Ar4Ar is compared with Ar when all are hydrogen1～Ar4Shows better thermal stability and light stability when at least one of (A) and (B) is substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.
Ar1～Ar4At least one of is substituted or notIn the case of a substituted aryl group, the aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, or a naphthyl group, and more preferably a phenyl group or a biphenyl group. Phenyl is particularly preferred.
Ar1～Ar4When at least one of (a) and (b) is a substituted or unsubstituted heteroaryl group, the heteroaryl group is preferably a pyridyl group, a quinolyl group or a thienyl group, and more preferably a pyridyl group or a quinolyl group. Particularly preferred is a pyridyl group.
In general formula (4) representing the organic compound, Ar is1～Ar4Each of which may be the same or different and is a substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl is preferred. The reason for this is that better thermal stability and light stability are exhibited. In the phosphor composition and the like of the present embodiment, when the organic compound converts light emitted from the light-emitting body into light having a longer wavelength than the inorganic phosphor combined therewith, Ar represented by general formula (5)1～Ar4Aryl which may be the same or different and which is substituted or unsubstituted is more preferred, with phenyl being particularly preferred. In this case, for example, when the light emitted from the light-emitting body is blue light, the inorganic phosphor converts the blue light into green light, and the organic compound converts the blue light into red light, which is light having a longer wavelength than the color conversion of the inorganic phosphor.
Further, in the general formula (4) representing the above organic compound, Ar1～Ar4At least one of them is preferably a substituent represented by the general formula (6). Thereby, high color purity and durability can be simultaneously achieved.
[ chemical formula 6]
Figure BDA0002173187220000211
In the general formula (6), R7Selected from the group consisting of alkyl, cycloalkyl, alkoxy, and alkylthio. n is an integer of 1 to 3. When n is 2 or more, each R7May be the same or different.
In the aryl group represented by the general formula (6), R7To electron-donating groupThe lump 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. Particularly preferred is an aryl group substituted with an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkylthio group having 1 to 8 carbon atoms. R7The C1-8 alkyl or C1-8 alkoxy, can obtain higher color purity, so more preferably. As the aryl group that mainly affects the light emission efficiency, an aryl group having a large substituent such as a tert-butyl group or an adamantyl group is preferable.
In addition, from the viewpoint of heat resistance and color purity, Ar1And Ar4、Ar2And Ar3Aryl groups each having the same structure are preferred. Further, from the viewpoint of dispersibility, Ar is more preferably1～Ar4At least one of which is a group represented by the general formula (6) and R7Is an alkyl group or alkoxy group having 4 or more carbon atoms. Wherein as Ar1～Ar4Examples of at least one of these include a tert-butyl group, a methoxy group and a tert-butoxy group.
In the general formula (6), n is preferably an integer of 1 to 3, and more preferably 1 or 2 from the viewpoint of easiness of raw material acquisition and synthesis.
On the other hand, in the general formula (4) representing the above organic compound, Ar1≠Ar2Or Ar3≠Ar4In the case of the above, the dispersibility in the film is improved, and high-efficiency light emission can be obtained, which is particularly preferable. Here, "≠" represents a group of a different structure. For example, Ar1≠Ar2Represents Ar1And Ar2Are groups of different structures. Ar (Ar)3≠Ar4Represents Ar3And Ar4Are groups of different structures. Is referred to as Ar1≠Ar2Or Ar3≠Ar4In other words, it means not being "Ar1＝Ar2And Ar3＝Ar4". That is, as shown in Ar1～Ar4Does not include (1) Ar in any combination of (A)1＝Ar2＝Ar3＝Ar4In the case of (2) Ar1＝Ar2And Ar3＝Ar4And Ar1≠Ar3The case (1).
The aryl group represented by the general formula (6) affects the properties and physical properties of the organic compound represented by the general formula (4), such as luminous efficiency, color purity, heat resistance, and light resistance. Although there are also aryl groups that improve a plurality of properties, there is no aryl group that exhibits sufficient performance in all properties. In particular, it is difficult to achieve both high luminous efficiency and high color purity. Therefore, if a plurality of aryl groups can be introduced into the organic compound represented by the general formula (4), it is expected to obtain an organic compound having a balance in light-emitting characteristics, color purity, and the like.
Ar1＝Ar2＝Ar3＝Ar4The organic compound of (a) can have only 1 aryl group. In addition, for Ar1＝Ar2And Ar3＝Ar4And Ar is1≠Ar3The organic compound of (4) has an aromatic group having a specific physical property biased toward one pyrrole ring. In this case, it is difficult to maximize the physical properties of each aryl group as described later in view of the relationship between the luminous efficiency and the color purity.
In contrast, in the organic compound according to the embodiment of the present invention, since the substituents having certain physical properties can be disposed on the right and left pyrrole rings in a well-balanced manner, the physical properties can be exhibited to the maximum extent as compared with the case where one pyrrole ring is biased.
This effect is particularly excellent in that the luminous efficiency and the color purity are improved in a well-balanced manner. When the pyrrole rings on both sides have 1 or more aryl groups affecting color purity, the conjugated system is expanded, and light emission with high color purity can be obtained, which is preferable. However, for Ar1＝Ar2And Ar3＝Ar4And Ar is1≠Ar3In the case where an aryl group affecting color purity is introduced into one pyrrole ring, for example, when an aryl group affecting luminous efficiency is introduced into the other pyrrole ring, the aryl group affecting color purity is biasedThe pyrrole ring on one side does not sufficiently expand the conjugated system, and the color purity is not sufficiently improved. When an aryl group having another structure which affects color purity is introduced into the other pyrrole ring, the luminous efficiency cannot be improved.
In contrast, in the organic compound according to the embodiment of the present invention, 1 or more aryl groups that affect color purity can be introduced into each of the pyrrole rings on both sides, and aryl groups that affect light emission efficiency can be introduced into the positions other than these. Therefore, the organic compound according to the embodiment of the present invention is preferable because both the color purity and the light emission efficiency can be improved to the maximum. In Ar, the following is2And Ar3When an aryl group that affects color purity is introduced into the position of (2), the conjugated system is most expanded, and thus is preferable.
Ar1～Ar4When at least one of (a) and (b) is a substituted or unsubstituted alkyl group, the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, or a hexyl group. 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. In addition, from the viewpoint of preventing concentration quenching and improving the luminescence quantum yield, tertiary butyl with a large steric bulk is more preferable as the alkyl group. On the other hand, from the viewpoint of ease of synthesis and availability of raw materials, it is also preferable to use a methyl group as the alkyl group.
On the other hand, in the general formula (4) representing the above organic compound, Ar1～Ar4When the alkyl group may be the same or different and may be substituted or unsubstituted, the solubility in the binder resin or the solvent is good, which is preferable. In this case, the alkyl group is preferably a methyl group from the viewpoint of ease of synthesis and ease of availability of raw materials. For example, in the phosphor composition and the like of the present embodiment, when the organic compound converts light emitted from the light-emitting body into light having a shorter wavelength than the inorganic phosphor combined therewith, Ar represented by general formula (4) is present1～Ar4Each may be the same or differentWhich may be different, is a substituted or unsubstituted alkyl group, preferably methyl. Specifically, when the light emitted from the light-emitting body is blue light, the inorganic phosphor converts the blue light into red light, and the organic compound converts the blue light into green light, which is light having a shorter wavelength than the color conversion of the inorganic phosphor.
In the general formula (4) representing the above organic compound, R5And R6At least one of which is hydrogen. Namely, R5And R6Any of hydrogen, alkyl, carbonyl, oxycarbonyl and aryl is preferable, and hydrogen or alkyl is preferable from the viewpoint of thermal stability. In particular, R is more preferable from the viewpoint of easily obtaining a narrow half-value width in the emission spectrum5And R6At least one of which is hydrogen.
In addition, 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 fluorine or a fluorine-containing aryl group in terms of stability to excitation light and capability of obtaining a higher fluorescence quantum yield. Further, from the viewpoint of ease of synthesis, it is more preferable that L is fluorine.
The fluorine-containing aryl group is a fluorine-containing aryl group, 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 fluoropyridyl group, trifluoromethylpyridyl group, and trifluoropyridyl group. The fluoroalkyl group is a fluoroalkyl group, and examples thereof include a trifluoromethyl group, a pentafluoroethyl group, and the like.
In addition, as another embodiment of the organic compound represented by the general formula (4), R is preferable5、R6、Ar1～Ar5At least one of which is an electron withdrawing group. In particular, (1) R is preferable1、R2、Ar1～Ar4At least one of them is an electron-withdrawing group, (2) Ar5Is an electron withdrawing group, or (3) R5、R6、Ar1～Ar4At least one of which is an electron withdrawing group and Ar5Are electron withdrawing groups. As described above, by introducing an electron-withdrawing group into the methylene pyrrole skeleton of an organic compound, it is possible to make it largeThe electron density of the methylene pyrrole skeleton is greatly reduced. This further improves the stability of the organic compound to oxygen, 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 a group that, in the organic electron theory, withdraws electrons from a substituted group by induction effect or resonance effect. Examples of the electron-withdrawing group include groups having a positive value in terms of a substituent constant (σ p (para)) according to Hammett's law. The substituent constants (. sigma.p) (para) of the Hammett's Law may be cited from "Handbook of Chemistry, Fundamental Section" 5 th edition (pages II-380). In the present invention, the electron-withdrawing group does not include a phenyl group, although there are examples in which a phenyl group takes the positive value described above.
Examples of the electron-withdrawing group include-F (σ p: +0.06), -Cl (σ p: +0.23), -Br (σ p: +0.23), -I (σ p: +0.18), -CO2R12(σp：R12Ethyl +0.45) and-CONH2(σp：+0.38)、-COR12(σp：R12When it is methyl, +0.49), -CF3(σp：+0.50)、-SO2R12(σp：R120.69) when it is methyl group, -NO2(σ p: +0.81), and the like. R12Each independently represents a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms in the ring, a substituted or unsubstituted heterocyclic group having 5 to 30 carbon atoms in the ring, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms in the ring, or a substituted or unsubstituted cycloalkyl group having 1 to 30 carbon atoms in the ring. Specific examples of the above groups include those similar to the above.
Preferred examples of the electron-withdrawing group include fluorine, a fluorine-containing aryl group, a fluorine-containing heteroaryl group, a fluorine-containing alkyl group, a substituted or unsubstituted acyl group (acyl), a substituted or unsubstituted ester group, a substituted or unsubstituted amide group (amidio), a substituted or unsubstituted sulfonyl group, and a cyano group. The reason for this is that it is not easily chemically decomposed.
More preferred examples of the electron-withdrawing group include a fluoroalkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted ester group, and a cyano group. The reason for this is that they can obtain the effects of preventing concentration quenching and improving the luminescence quantum yield. Particularly preferred electron withdrawing groups are substituted or unsubstituted ester groups.
In the general formula (4) representing the above organic compound, R is preferably5And R6At least one of which is an electron withdrawing group. This is because the stability of the organic compound represented by the general formula (4) with respect to oxygen can be improved without impairing the luminous efficiency and color purity, and as a result, the durability of the organic compound can be improved.
In addition, in Ar representing the organic compound5In the general formula (5), r is more preferably an electron-withdrawing group. This is because the stability of the organic compound represented by the general formula (4) with respect to oxygen is further improved without impairing the light-emitting efficiency and the color purity, and as a result, the durability of the organic compound can be greatly improved.
As a preferred example of the organic compound represented by the general formula (4), Ar is mentioned1～Ar4Each of which may be the same or different and is a substituted or unsubstituted alkyl group, and Ar5In the case of a group represented by the general formula (5). In this case, Ar5Particularly preferred is a group represented by the general formula (5) wherein r is a substituted or unsubstituted phenyl group.
Further, as another preferable example of the organic compound represented by the general formula (4), Ar is mentioned1～Ar4Each of which may be the same or different and is a group selected from the above-mentioned general formula (6), and Ar5In the case of a group represented by the general formula (5). In this case, Ar5More preferably a group represented by the general formula (5) wherein r is a t-butyl group or a methoxy group, and particularly preferably a group represented by the general formula (5) wherein r is a methoxy group.
An example of the organic compound represented by the general formula (4) will be described below, but the organic compound of the present embodiment is not limited thereto.
[ chemical formula 7]
Figure BDA0002173187220000261
[ chemical formula 8]
Figure BDA0002173187220000271
[ chemical formula 9]
Figure BDA0002173187220000281
[ chemical formula 10]
Figure BDA0002173187220000291
[ chemical formula 11]
Figure BDA0002173187220000301
[ chemical formula 12]
Figure BDA0002173187220000311
[ chemical formula 13]
Figure BDA0002173187220000321
[ chemical formula 14]
Figure BDA0002173187220000331
[ chemical formula 15]
Figure BDA0002173187220000341
[ chemical formula 16]
Figure BDA0002173187220000351
[ chemical formula 17]
Figure BDA0002173187220000361
[ chemical formula 18]
Figure BDA0002173187220000371
[ chemical formula 19]
Figure BDA0002173187220000381
[ chemical formula 20]
Figure BDA0002173187220000391
[ chemical formula 21]
Figure BDA0002173187220000401
[ chemical formula 22]
Figure BDA0002173187220000411
[ chemical formula 23]
Figure BDA0002173187220000421
[ chemical formula 24]
Figure BDA0002173187220000431
[ chemical formula 25]
Figure BDA0002173187220000441
[ chemical formula 26]
Figure BDA0002173187220000451
[ chemical formula 27]
Figure BDA0002173187220000461
[ chemical formula 28]
Figure BDA0002173187220000471
[ chemical formula 29]
Figure BDA0002173187220000481
[ chemical formula 30]
Figure BDA0002173187220000491
[ chemical formula 31]
Figure BDA0002173187220000492
The organic compound represented by the general formula (4) can be produced by the methods described in, for example, Japanese patent application laid-open No. 8-509471 and Japanese patent application laid-open No. 2000-208262. That is, the intended methylene-pyrrole metal complex can be obtained by reacting a methylene-pyrrole compound with a metal salt in the presence of a base.
Further, the organic compound represented by the general formula (4) can be produced by the method described in j.org.chem., vol.64, No.21, pp7813-7819(1999), angelw.chem., int.ed.engl, vol.36, pp1333-1335(1997), etc., for the synthesis of the methylene pyrrole-boron fluoride complex.
The phosphor composition according to the embodiment of the present invention may contain other compounds as needed in addition to the organic compound represented by the general formula (4). For example, an auxiliary dopant such as rubrene may be contained in order to further improve the energy transfer efficiency from the excitation light to the organic compound represented by the general formula (4). When a light-emitting color other than the light-emitting color of the organic compound represented by the general formula (4) is to be added, a desired organic light-emitting material, for example, a coumarin-based pigment, a perylene-based pigment, a phthalocyanine-based pigment, a stilbene-based pigment, a Cyanine-based pigment (Cyanine Dyes), a polyphenylene (polyphenylene) -based pigment, a rhodamine-based pigment, a pyridine-based pigment, a methylene-pyrrole-based pigment, a porphyrin-based pigment, an oxazine-based pigment, a pyrazine-based pigment, or the like may 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 may be added in combination.
Examples of organic light-emitting materials other than the organic compound represented by general formula (4) are shown below, but the present invention is not particularly limited to these.
[ chemical formula 32]
Figure BDA0002173187220000511
The content of the organic compound represented by the general formula (4) in the phosphor composition according to the embodiment of the present invention depends on the molar absorption coefficient of the organic compound, the fluorescence quantum yield, the absorption intensity at the excitation wavelength, the thickness of the film to be produced, and the transmittance, but is usually 10% by weight based on the weight of the entire phosphor composition-5The weight percent is 10 weight percent, more preferably 10-4The weight percentage is 5 to 5 weight percentages,particularly preferably 10-3 Weight percent 2 weight percent.
(solvent)
The phosphor sheet according to the embodiment of the present invention may contain a solvent. The solvent is not particularly limited as long as it can adjust the viscosity of the resin in a fluid state. Examples of the solvent include toluene, methyl ethyl ketone, methyl isobutyl ketone, hexane, acetone, terpineol, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate (TEXANOL), methyl cellosolve, butyl carbitol acetate, and propylene glycol monomethyl ether acetate.
(other Components)
The phosphor sheet according to the embodiment of the present invention may contain a dispersant for stabilizing the coating film, a leveling agent, an adhesion aid such as a silane coupling agent as a modifier for the surface of the phosphor sheet, and the like.
The phosphor sheet according to the embodiment of the present invention may contain fine particles. Examples of the fine particles include fine silicone particles, titanium dioxide, silicon dioxide, aluminum oxide, silicone, zirconium oxide, cerium oxide, aluminum nitride, silicon carbide, silicon nitride, barium titanate, and the like. In addition, the phosphor sheet according to the embodiment of the present invention may further contain a methylphenyl silicone resin containing silanol groups as a heating binder in order to lower the storage elastic modulus G' at 100 ℃. From the viewpoint of ease of use, fine silicone particles, fine silica particles, and fine alumina particles are preferably used, and fine silicone particles are particularly preferably used.
The phosphor sheet according to the embodiment of the present invention contains the silicone fine particles, and thus not only adhesiveness and processability are good, but also film thickness uniformity is good. In particular, by using silicone fine particles having an average particle diameter (median diameter: D50) of 0.1 to 2.0 μm, a phosphor sheet having excellent discharge properties and excellent film thickness uniformity when a slit coater is used can be obtained.
The average particle size of the silicone fine particles can be measured by the same method as described above for the average particle size of the phosphor. The lower limit of the average particle diameter of the silicone fine particles is more preferably 0.5 μm or more. Further, the upper limit is more preferably 1.0 μm or less.
The silicone fine particles are preferably fine particles formed of a silicone resin and/or a silicone rubber. In particular, fine silicone particles obtained by a method of hydrolyzing and then condensing organosilanes such as organotrialkoxysilane, organodialkoxysilane, organotriacetoxysilane, organodiacetoxysilane, organotrioxime silane, and organodioxime silane are preferable. Among these, the following silicone fine particles are preferably used: in the case of producing spherical fine organopolysiloxane particles by hydrolyzing and condensing organosilane and/or a partial hydrolysate thereof, fine organosilicon particles obtained by adding a polymer dispersant to a reaction solution as described above are reported in Japanese patent laid-open publication No. 2003-342370.
In addition, silicone microparticles produced by: in the production of fine silicone particles, an organosilane and/or a hydrolysate thereof is hydrolyzed and condensed, and the organosilane and/or the hydrolysate thereof is added in the presence of a polymeric dispersant and a salt which function as a protective colloid in a solvent in an acidic aqueous solution to obtain a hydrolysate, and then a base is added to perform a condensation reaction.
The content of the silicone fine particles in the phosphor sheet is preferably 0.5 wt% or more, and more preferably 1 wt% or more of the entire phosphor sheet. The upper limit of the content of the silicone fine particles in the phosphor sheet is not particularly limited, and is preferably 20 wt% or less, more preferably 10 wt% or less of the entire phosphor sheet, from the viewpoint of good mechanical properties.
(substrate)
The substrate is an example of a support for the phosphor sheet of the present invention. The substrate is not particularly limited, and for example, known metals, films, glasses, ceramics, papers, and the like can be used. Specifically, examples thereof include a metal plate or foil such as aluminum (including aluminum alloy), zinc, copper, iron, etc., a film of a plastic such as cellulose acetate, polyethylene terephthalate (PET), polyethylene, polyester, polyamide, polyimide, polyphenylene sulfide, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, aramid, silicone, polyolefin, thermoplastic fluororesin, copolymer of tetrafluoroethylene and ethylene (ETFE), a film of a plastic formed of an α -polyolefin resin, a polycaprolactone resin, an acrylic resin, a silicone resin, and a copolymer resin thereof with ethylene, a paper on which the plastic is laminated, a paper coated with the plastic, a paper on which the metal is laminated or evaporated, a plastic film on which the metal is laminated or evaporated, and the like. When the substrate is a metal plate, the surface of the metal plate may be subjected to plating treatment such as chromium-based plating or nickel-based plating, or ceramic treatment.
Among these, glass and plastic films are preferably used in view of ease of manufacturing the phosphor sheet and ease of singulation of the phosphor sheet. In particular, the base material is preferably in the form of a flexible film in view of adhesion when the phosphor sheet is attached to the LED chip. In addition, a film having high strength is preferable so that there is no fear of breakage or the like when the film-shaped substrate is handled. From the viewpoints of these required characteristics and economy, a plastic film is preferable. Among the plastic films, plastic films selected from the group consisting of PET, polyphenylene sulfide, and polypropylene are preferable from the viewpoint of economy and workability. In addition, when the phosphor sheet is dried or when a high temperature of 200 ℃ or higher is required for bonding the phosphor sheet to the LED chip, a polyimide film is preferable from the viewpoint of heat resistance. The surface of the base material may be subjected to a mold release treatment in advance from the viewpoint of easiness of peeling the phosphor sheet from the base material.
The thickness of the substrate is not particularly limited, and the lower limit is preferably 25 μm or more, and more preferably 38 μm or more. The upper limit is preferably 5000 μm or less, more preferably 3000 μm or less.
(other layer)
The phosphor sheet according to the embodiment of the present invention may include a barrier layer. The barrier layer can be suitably used in the case of improving gas barrier properties with respect to the phosphor sheet.
Examples of the barrier layer having a barrier function against oxygen include a film formed of silicon oxide, aluminum oxide, tin oxide, indium oxide, yttrium oxide, magnesium oxide, or the like, or a mixture thereof, or a metal oxide obtained by adding another element to the above; or films made of various resins such as nylon, polyvinylidene chloride, and copolymers of ethylene and vinyl alcohol.
Examples of the barrier layer having a barrier function against moisture include films made of various resins such as polyethylene, polypropylene, nylon, polyvinylidene chloride, a copolymer of vinylidene chloride and vinyl chloride, vinylidene chloride and acrylonitrile, and a fluorine-based resin.
The phosphor sheet according to the embodiment of the present invention may further include an auxiliary layer having an antireflection function, an antiglare function, an antireflection and antiglare function, a light diffusion function, a hard coat function (friction resistance function), an antistatic function, an antifouling function, an electromagnetic wave shielding function, an infrared ray blocking function, an ultraviolet ray blocking function, a polarizing function, and a color mixing function, depending on the functions required for the phosphor sheet.
< method for producing phosphor sheet >
An example of a method for producing a phosphor sheet according to an embodiment of the present invention will be described below. The method of producing the phosphor sheet described below is an example, and the method of producing the phosphor sheet is not limited to this.
First, a composition (hereinafter referred to as "phosphor composition") in which a phosphor is dispersed in a silicone resin is prepared as a coating liquid for forming a phosphor sheet. Prescribed amounts of the silicone resin, the phosphor, and, if necessary, an additive such as silicone microparticles, and a solvent are mixed. The phosphor composition can be obtained by mixing the above components so as to have a predetermined composition, and then mixing and dispersing the mixture into a homogeneous state by a stirring/kneading machine such as a homogenizer, a revolution/rotation type stirrer, a three-roll mill, a ball mill, a planetary ball mill, or a bead mill.
It is also preferable to defoam under vacuum or reduced pressure after or during the mixing and dispersing. Further, a specific component may be mixed in advance, or the resultant phosphor composition may be subjected to a treatment such as aging. The solvent may be removed from the mixture after mixing and dispersing by an evaporator to form a desired solid content concentration.
The phosphor composition produced by the above method is coated on a substrate, and dried to produce a phosphor sheet. Coating may be performed with a reverse roll coater, a knife coater, a slot die coater, a direct gravure coater, an offset gravure coater, a kiss coater, a natural roll coater, an air knife coater, a roll knife coater, a dual stream coater, a rod coater, a wire rod coater, an applicator, a dip coater, a curtain coater, a spin coater, a knife coater, and the like. In order to obtain the film thickness uniformity of the phosphor sheet, coating is preferably performed by a slot die coater.
The phosphor sheet can be dried by using a general heating device such as a hot air dryer or an infrared dryer. In this case, the drying is carried out at 40 to 250 ℃ for 1 minute to 5 hours, preferably 60 to 200 ℃ for 2 minutes to 4 hours. Alternatively, the drying may be performed stepwise, such as stepwise curing.
After the phosphor sheet is produced, the base material may be changed as necessary. In this case, as a simple method, there can be mentioned: a method of re-attaching a substrate using a hot plate, a method of re-attaching a substrate using a vacuum laminator or a dry film laminator, and the like.
< example of applying phosphor sheet >
By attaching the phosphor sheet according to the embodiment of the present invention or the cured product thereof to the light emitting surface of the LED chip, an LED chip with a phosphor sheet can be formed in which the phosphor sheet is laminated on the surface of the LED chip. 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 normal structure such as a horizontal, vertical, and flip chip. As such an LED chip, particularly, a vertical type and a flip chip type LED chip having a large light emitting area are preferable. The light-emitting surface of the LED chip is a surface from which light from the LED chip is extracted.
Here, there are a case where the light emitting surface from the LED chip is a single plane and a case where it is not a single plane. As a single plane, an LED chip having only an upper light emitting surface is mainly exemplified. Specifically, the LED chip may be a vertical LED chip, or 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. On the other hand, examples of the LED chip having a curved light emitting surface include an LED chip having an upper light emitting surface and a side light emitting surface.
Among these LED chips, a case where the light-emitting surface is not a single plane is preferable because light emission from the side can be utilized to brighten the light-emitting surface. Particularly, 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. In addition, the surface of the light-emitting surface may be textured (texture) based on optical design for improving the light-emitting efficiency of the LED chip.
The phosphor sheet according to the embodiment of the present invention may be directly attached to the LED chip, or may be attached via an adhesive such as a transparent resin. The case where the phosphor sheet according to the embodiment of the present invention is directly attached to the LED chip is more preferable in terms of that light from the LED chip can be directly incident on the phosphor sheet without loss due to reflection or the like. This makes it possible to efficiently obtain uniform white light with little color variation.
The LED chip with the phosphor-containing sheet obtained in the above manner is mounted on a wiring board provided with metal wiring or the like and packaged, whereby an LED package can be produced. Then, the light-emitting device is assembled into a module, and can be suitably used for various light-emitting devices including 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. 1(a), an LED chip 1 to which a phosphor sheet 2 is attached is mounted on a mounting substrate 5 provided with a reflector 4, and the upper surface portion of the LED chip 1 is sealed with a transparent sealing material 3.
In fig. 1(b), the LED chip 1 to which the phosphor sheet 2 is attached is mounted 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.
In fig. 1(c), in the configuration shown in fig. 1(b), the phosphor sheet 2 is attached not only to the upper surface but also to the side surface of the LED chip 1. In this embodiment, light emission from the side surface of the LED chip is also preferably converted in emission wavelength by the phosphor sheet 2. The upper surface of the transparent sealing material 3 is formed into a lens shape.
In fig. 1(d), the LED chip 1 to which the phosphor sheet 2 is attached is mounted on a mounting substrate 5 having no reflector, and is sealed with a transparent sealing material 3 molded into a lens shape.
In fig. 1(e), in the configuration shown in fig. 1(d), the phosphor sheet 2 is attached not only to the upper surface but also to the side surface of the LED chip 1.
In fig. 1(f), in the configuration shown in fig. 1(c), a flip-chip type LED chip 1 is used as the LED chip, and the phosphor sheet 2 is spread and attached to the upper surface of the mounting substrate 5 as well as the upper surface and the side surface which are the light emitting surface of the LED chip 1. In this configuration, the phosphor sheet 2 may be attached only to the upper surface and the side surfaces which are the light emitting surfaces of the LED chips 1.
In fig. 1(g), in the configuration shown in fig. 1(d), the configuration of the LED chip 1 and the phosphor sheet 2 is the same as that shown in fig. 1 (f).
In fig. 1(h), the LED chip 1 is provided so as to fit a portion of the mounting substrate 5 provided with the reflector 4, which portion does not have the reflector 4, and a phosphor sheet 2 having the same width as the interval between the reflector 4 and the LED chip 1 is attached to the LED chip 1 via an adhesive 8 and sealed with a sealing material 3.
In fig. 1(i), in the configuration shown in fig. 1(h), the phosphor sheet 2 with the base material 9 is used as the phosphor sheet 2, and the phosphor sheet 2 is bonded via the adhesive 8 so that the base material 9 is not peeled off from the phosphor sheet 2.
The LED package according to the embodiment of the present invention is not limited to these configurations. For example, the structures of the respective elements illustrated in fig. 1(a) to 1(i) may be combined as appropriate. In addition, the configuration of each element illustrated in fig. 1(a) to 1(i) may be replaced with a configuration in which known elements other than these elements are used, or a configuration in which known elements are combined with the configuration illustrated in fig. 1(a) to 1 (i).
The transparent sealing material 3 may be any material as long as it is excellent in moldability, transparency, heat resistance, adhesiveness, and the like. For example, known materials such as epoxy resins, silicone resins (including organopolysiloxane cured products (crosslinked products) such as silicone rubbers and silicone gels), urea resins, fluorine resins, and polycarbonate resins can be used.
As the adhesive 8, a material used as the above-described transparent sealing material can be used.
The material constituting the reflector 4 is not particularly limited, and examples thereof include a material obtained by adding fine particles to a material used for the transparent sealing material 3. Examples of the fine particles include titanium dioxide, silicon dioxide, aluminum oxide, silicone, zirconium oxide, cerium oxide, aluminum nitride, silicon carbide, silicon nitride, barium titanate, and the like. Among these fine particles, silica fine particles, alumina fine particles, and titania fine particles are preferably used from the viewpoint of easy availability.
< method of attaching phosphor sheet and method of manufacturing LED Package Using phosphor sheet >
Next, a method of attaching a phosphor sheet according to an embodiment of the present invention to an LED chip and a method of manufacturing an LED package using the phosphor sheet according to the embodiment of the present invention will be described.
As described below, a typical method for manufacturing an LED package using a phosphor sheet according to an embodiment of the present invention includes: a method (1) in which a phosphor sheet is cut into individual pieces and then attached to individual LED chips (see, for example, fig. 2); the method (2) is not limited to the above method, in which the phosphor sheet is collectively bonded to a large number of LED chips formed on the wafer (hereinafter, referred to as "wafer-level LED chips"), and then the wafer is diced and the phosphor sheet is cut collectively (see, for example, fig. 3). Hereinafter, these steps will be described with reference to fig. 2 and 3 as appropriate.
(Process of attaching phosphor sheet to LED chip)
The phosphor sheet according to the embodiment of the present invention is heated and pressurized at a desired temperature, and is attached to an LED chip. It is a bonding based on heat crimping.
The heating temperature is preferably 60 ℃ or more and 250 ℃ or less, and more preferably 60 ℃ or more and 160 ℃ or less. By setting the heating temperature to 60 ℃ or higher, 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 pasting temperature becomes easy. Further, by setting the heating temperature to 250 ℃ or lower, thermal expansion and thermal contraction of the phosphor sheet can be reduced, and therefore the positional accuracy of the bonding can be improved.
In particular, when the phosphor sheet is perforated in advance and aligned with a predetermined portion on the LED chip, the positional accuracy of the bonding is important. The heating temperature is more preferably 160 ℃ or lower from the viewpoint of improving the positional accuracy of the pasting.
As a means for thermally and pressure-bonding the phosphor sheet, any means can be used as long as it can be pressure-bonded at a desired temperature, and any conventional means can be used. As shown in fig. 2(c) to (d), when the singulated phosphor sheets are thermally and pressure bonded, for example, a thermal and pressure bonding tool such as a chip mounter or a flip chip bonder can be used.
In addition, as shown in fig. 3(a) to (b), when the phosphor sheets are collectively attached to the LED chips on the wafer level, a vacuum laminator or a thermocompression bonding tool having a heating portion of about 100 to 200mm square can be used.
In any case, the phosphor sheet with the base material is pressure-bonded to the LED chip at a desired temperature, and the phosphor sheet is heat-welded, and then left to cool to room temperature, and the base material is peeled off from the phosphor sheet. Since the storage elastic modulus G' at 25 ℃ and 100 ℃ of the phosphor sheet according to the embodiment of the present invention is within the above-described relationship, the phosphor sheet after being left to cool to room temperature after heat fusion is firmly adhered to the LED chip and can be easily peeled from the base material.
(Process of cutting phosphor sheet)
A method of cutting a phosphor sheet includes: a method of cutting the LED chip into individual pieces in advance before the LED chip is attached; and a method of cutting the phosphor sheet simultaneously with dicing the wafer after attaching the phosphor sheet to the LED chip on the wafer level.
As shown in fig. 2, when the phosphor sheet is cut before being bonded to the LED chip, the phosphor sheet formed uniformly is processed and divided into predetermined shapes by processing with a laser or cutting with a cutter. Since high energy is applied to the phosphor sheet by processing with a laser, scorching of the resin in the phosphor sheet and deterioration of the phosphor may be caused by the processing conditions. Therefore, cutting with a cutter is preferable as a method for cutting the phosphor sheet.
As a cutting method using a tool, for example, there are a method of cutting by pressing a simple tool and a method of cutting by a rotary tool, and both of them can be suitably used. As an apparatus for cutting with a rotary cutter, an apparatus for cutting (dicing) a semiconductor substrate into individual chips called a dicer is suitably used. When a dicing machine is used, the width of the dividing line of the phosphor sheet can be precisely controlled by setting the thickness and conditions of the rotary cutter, and therefore, high processing accuracy can be obtained as compared with the case where the phosphor sheet is cut by simply pressing the cutter.
When the phosphor sheet laminated on the base material is cut, the phosphor sheet may be singulated together with the base material, or the base material may be not cut at the same time as the phosphor sheet is singulated. Alternatively, the phosphor sheet may be singulated and a cut line that does not penetrate through the base material may be drawn into the base material (so-called half-cut state).
When the phosphor sheet is singulated together with the base material, the individual phosphor sheets can be attached to the LED chip by the above-described method. In this case, the base material may be peeled off from the phosphor sheet before or after the LED chip is attached. Further, the base material may be left as it is without being peeled off from the phosphor sheet.
When the phosphor sheet is singulated without cutting the base material or in a so-called half-cut state, the phosphor sheet of each individual piece may be peeled off from the base material and then attached to the individual LED chips by the above-described method.
As shown in fig. 3, when the phosphor sheet is attached to LED chips on a wafer level and then cut simultaneously with dicing of the wafer, the phosphor sheet can be processed into a predetermined shape by processing with a laser or cutting with a cutter, and divided into LED chips with the phosphor sheet that have been singulated. Among these cutting methods, cutting by a tool is preferable.
(specific example of method for producing LED Package Using phosphor sheet)
Fig. 2 shows an example of a series of steps for separating the phosphor sheet together with the base material and attaching the phosphor sheet to the LED chip. The step of fig. 2 includes a step of cutting the phosphor sheet into individual pieces and a step of attaching the cut phosphor sheet to the LED chip.
Fig. 2(a) is a view of fixing the phosphor sheet 2 stacked on the base material 9 to the temporary fixing sheet 11. In the step shown in fig. 2, since both the phosphor sheet 2 and the base material 9 are singulated, they are fixed to the temporary fixing sheet 11 in advance to facilitate handling. Next, as shown in fig. 2(b), the phosphor sheet 2 and the base material 9 are cut and singulated.
Next, as shown in fig. 2(c), the singulated phosphor sheet 2 is aligned with the base material 9 on the LED chip 1 mounted on the mounting substrate 5. Then, as shown in fig. 2(d), the phosphor sheet 2 is pressure-bonded to the LED chip 1 at a desired temperature using a heat pressure-bonding tool 12. In this case, the pressure bonding step is preferably performed under vacuum or reduced pressure so as not to mix air between the phosphor sheet 2 and the LED chip 1. After crimping, the material was left to cool to room temperature.
Next, as shown in fig. 2(e), the base material 9 is peeled off from the phosphor sheet 2. When the substrate 9 is glass or the like, the substrate 9 may be left as it is without being peeled off as shown in fig. 2 (f).
Fig. 3 shows an example of a series of steps in a case where the phosphor sheet is collectively attached to LED chips on a wafer level, and then dicing of the wafer and cutting of the phosphor sheet are collectively performed. The step of fig. 3 includes a step of collectively bonding a phosphor sheet to a plurality of LED chips formed on a wafer, and a step of collectively dicing the wafer and singulating the LED chips to which the phosphor sheet is bonded.
As shown in fig. 3(a), the phosphor sheet 2 in a state of being laminated with the base material 9 is not subjected to cutting processing in advance. One side of the phosphor sheet 2 is opposed to a wafer 13 having a plurality of LED chips (not shown) formed on the surface thereof, and aligned.
Next, as shown in fig. 3(b), the phosphor sheet 2 is collectively heat-pressure bonded to the plurality of LED chips at a desired temperature using the heat-pressure bonding tool 12. In this case, the heat-pressure bonding step is preferably performed under vacuum or under reduced pressure so as not to mix air between the phosphor sheet 2 and the LED chip. Heating and pressing, standing and cooling to room temperature.
Next, as shown in fig. 3(c), after the base material 9 is peeled off from the phosphor sheet 2, the phosphor sheet 2 is cut and singulated simultaneously with the dicing of the wafer 13. Then, as shown in fig. 3(d), the LED chip 25 is obtained as a singulated phosphor-attached sheet.
Instead of the steps shown in fig. 3(c) to (d), the base material 9 may be cut together with the phosphor sheet and singulated as shown in fig. 3(f) without peeling the base material 9 from the phosphor sheet 2 as shown in fig. 3 (e). Thus, the LED chip 26 with the base material and the phosphor sheet is obtained as a single piece. In this case, the base material 9 may be used as it is without being peeled from the phosphor sheet 2, such as glass. When the base material 9 is a plastic film, the LED chip 26 may be mounted on the substrate, and then the base material 9 may be peeled off from the phosphor sheet 2.
In any of the steps of fig. 2 and 3, when the phosphor sheet is attached to the LED chip having the electrodes on the upper surface, the phosphor sheet in the portion corresponding to the electrodes must be removed. Therefore, it is preferable to perform hole drilling on the portion of the phosphor sheet corresponding to the electrode in advance before the phosphor sheet is attached to the LED chip. The phosphor sheet according to the embodiment of the present invention can be processed by drilling with high accuracy.
That is, in the method for manufacturing an LED package according to the embodiment of the present invention, the phosphor sheet is preferably attached to a portion of the light emitting surface of the LED chip that is away from the electrode.
The method of the hole forming is not particularly limited, and for example, known methods such as laser processing and die punching can be preferably used. Laser processing may cause scorching of the resin in the phosphor sheet and deterioration of the phosphor due to processing conditions. Therefore, the punching process using a die is more preferable. When the punching process is performed, the punching process cannot be performed after the phosphor sheet is attached to the LED chip, and therefore the punching process must be performed before the phosphor sheet is attached to the LED chip.
The punching process using the die can design the die according to the shape, size, and the like of the electrode provided in the LED chip, thereby forming a hole having an arbitrary shape and size. In the LED chip having a size of about 1mm square, the size of the electrode on the upper surface is preferably 500 μm square or less so as not to reduce the area of the light-emitting surface. Therefore, the size of the holes provided in the phosphor sheet is preferably 500 μm or less in square. In the case of wire bonding or the like between the electrode on the upper surface of the LED chip and the mounting board on which the LED chip is mounted, the electrode on the upper surface needs to have a certain size, for example, a size of at least about 50 μm square. Therefore, the size of the holes provided in the phosphor sheet is preferably about 50 μm square.
When the size of the hole formed in the phosphor sheet is too large as compared with the size of the electrode, the light emitting surface is exposed, light leakage occurs, and the color characteristics of the LED package may be degraded. If the electrode size is too small, the lead may contact the phosphor sheet during wire bonding, resulting in poor bonding. Therefore, in the hole forming process in the phosphor sheet, it is preferable to form a hole having a size of 50 μm or more and 500 μm or less with a high accuracy within ± 10%.
When the phosphor sheet subjected to cutting processing and optionally perforated processing is aligned with a predetermined portion of the LED chip and bonded, a bonding apparatus having an optical alignment structure is required. In this case, it is difficult to align the phosphor sheet and the LED chip close to each other. Therefore, in practice, it is often performed as follows: the alignment is performed in a state where the phosphor sheet is lightly contacted with the LED chip.
In this case, if the phosphor sheet has adhesiveness, it is very difficult to move the phosphor sheet in contact with the LED chip. In contrast, in the case of the phosphor sheet according to the embodiment of the present invention, since there is no adhesiveness at room temperature, the phosphor sheet and the LED chip are easily aligned in a state of being lightly in contact with each other.
The phosphor sheet according to the embodiment of the present invention may be further subjected to a heat treatment by an oven or the like as necessary after being attached to the LED chip. By performing the heat treatment, the adhesion between the phosphor sheet and the LED chip can be further strengthened.
In addition, when the LED chip to which the phosphor sheet is attached is bonded to the mounting board at one time, the LED chip may be bonded by thermocompression bonding or soldered by reflow soldering to the mounting board.
As another embodiment of the method for manufacturing an LED package using the phosphor sheet according to the embodiment of the present invention, a method for manufacturing an LED package by mass production will be described. First, a method for manufacturing an LED chip with a phosphor-coated 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 phosphor sheet laminate 14 singulated for each LED chip 1 is given. As shown in fig. 5, there is a method of collectively attaching the phosphor sheet 2 to the plurality of LED chips 1 to cover them, and then cutting the package substrate 15 to singulate the LED chips 1.
Next, as still another embodiment of the method for manufacturing an LED package using the phosphor sheet according to the embodiment of the present invention, two methods are exemplified.
Fig. 6 shows a first example of the production. This is a preferable example when the base material of the phosphor sheet has fluidity.
As shown in fig. 6(a), the LED chip 1 is temporarily fixed to the base 18 via a double-sided adhesive tape 17. As shown in fig. 6(b), the phosphor sheet laminate 14 is laminated such that the phosphor sheet 2 is in contact with the LED chip 1.
As shown in fig. 6(c), the laminate of fig. 6(b) is loaded into the lower chamber 20 of the vacuum diaphragm laminator 22, and then the upper chamber 19 and the lower chamber 20 are depressurized while heating. After the pressure reduction and heating are performed until the base material 9 flows, the air is sucked into the upper chamber 19 through the air inlet 23, whereby the membrane 21 is expanded. Thereby, the fluorescent sheet 2 is pressed by the base material 9 and attached so as to follow the light emitting surface of the LED chip 1.
As shown in fig. 6(d), the upper and lower chambers were returned to atmospheric pressure, and then the laminate was taken out from the vacuum diaphragm laminator 22, left to cool, and the base material 9 was peeled off from the phosphor sheet 2. Subsequently, the cutting portions 24 between the LED chips are cut with a dicing blade or the like, and LED chips 25 with a phosphor sheet are produced as singulated pieces.
As shown in fig. 6(e), the LED chip 25 with the phosphor-coated sheet is bonded to the package electrode 16 on the mounting substrate 15 via the gold bump 7. The LED package 10 as shown in fig. 6(f) is manufactured by the above steps.
Fig. 7 shows a second example of the production. This is another preferable example when the base material of the phosphor sheet has fluidity.
As shown in fig. 7(a), the LED chip 1 is bonded to the package electrode 16 on the mounting substrate 15 via the gold bump 7.
As shown in fig. 7(b), the phosphor sheet laminate 14 is laminated such that the phosphor sheet 2 is in contact with the LED chip 1.
As shown in fig. 7(c), the laminate of fig. 7(b) is placed in the lower chamber 20 of the vacuum diaphragm laminator 22, and then the phosphor sheet 2 is attached to the light emitting surface of the LED chip 1 by the same method as in the manufacturing example of fig. 6.
As shown in fig. 7(d), the upper and lower chambers were returned to atmospheric pressure, and then the laminate was taken out from the vacuum diaphragm laminator 22, left to cool, and the base material 9 was peeled off from the phosphor sheet 2. Subsequently, the cutting portions 24 between the LED packages are cut and singulated. The LED package 10 as shown in fig. 7(e) is manufactured by the above steps.
< light emitting device, backlight module, display >
A light-emitting device according to an embodiment of the present invention includes the above phosphor sheet. For example, the light-emitting device includes an LED package including the phosphor sheet or a cured product thereof on a light-emitting surface of an LED chip.
The backlight module according to the embodiment of the invention is an application example of the light emitting device. For example, the backlight module includes an LED package having the phosphor sheet or a cured product thereof. The backlight module configured in this way can be used for applications such as displays, lighting, interior decoration, signs, and signboards, and is particularly preferably used for applications such as displays and lighting.
The display (for example, a liquid crystal display) according to the embodiment of the invention is an application example of the backlight module. For example, the display includes an LED package having the phosphor sheet or a cured product thereof.
Examples
The present invention will be described in detail with reference to examples. However, the present invention is not limited thereto.
< substrate >
BX 9: polyethylene terephthalate (polyethylene terephthalate film) subjected to mold release treatment "Cerapeel" BX9 (manufactured by Toray film Co., Ltd., average film thickness of 50 μm)
< inorganic phosphor >
Phosphor 1(YAG 1):
"YAG 81003" (YAG phosphor) manufactured by Nemoto Lumi-Materials Company Limited
Phosphor 2(β 1):
"GR-SW 532D" (beta-sialon phosphor) manufactured by Denka corporation
Peak wavelength: 538nm average particle diameter (D50): 16 μm
Phosphor 3(KSF 1):
KSF phosphor sample A manufactured by Nemoto Lumi-Materials Company Limited
Average particle diameter (D50): 50 μm.
< organic phosphor >
Examples of the synthesis of the organic phosphor are shown below.1H-NMR was measured using a deuterated chloroform solution using a superconducting FTNMR EX-270 (manufactured by Nippon electronics Co., Ltd.). HPLC was performed using high performance liquid chromatography LC-10 (manufactured by Shimadzu corporation) using a 0.1g/L chloroform solution. As a developing solvent of the column, a mixed solution of 0.1% phosphoric acid aqueous solution and acetonitrile was used. The absorption spectrum and the fluorescence spectrum were measured at 4X 10 using a U-3200 type spectrophotometer and a F-2500 type fluorescence spectrophotometer (both manufactured by Hitachi Ltd.)-6The measurement was carried out in a methylene chloride solution of mol/L.
(Synthesis example 1)
The following describes a method for synthesizing the organic phosphor (T21) of synthesis example 1. In the method for synthesizing the organic phosphor (T21), a mixed solution of 12.2g of 4-T-butylbenzaldehyde, 11.3g of 4-methoxyacetophenone, 32ml of a 3M aqueous potassium hydroxide solution and 20ml of ethanol was stirred at room temperature under a nitrogen stream for 12 hours. The precipitated solid was collected by filtration and washed 2 times with 50ml of cold ethanol. After vacuum drying, 17g of 3- (4-tert-butylphenyl) -1- (4-methoxyphenyl) propenone was obtained.
Then, under a nitrogen stream, a mixed solution of 17g of 3- (4-tert-butylphenyl) -1- (4-methoxyphenyl) propenone, 21.2g of diethylamine, 17.7g of nitromethane and 580ml of methanol was heated under reflux for 14 hours. The resulting solution was cooled to room temperature and evaporated. Purification by silica gel column chromatography and vacuum drying gave 16g of 3- (4-tert-butylphenyl) -1- (4-methoxyphenyl) -4-nitrobutan-1-one.
Subsequently, a mixed solution of 230ml of methanol and 46ml of concentrated sulfuric acid was stirred at 0 ℃ under a nitrogen stream. 1.12g of potassium hydroxide powder was added to a mixed solution of 1.42g of 3- (4-tert-butylphenyl) -1- (4-methoxyphenyl) -4-nitrobutan-1-one prepared in advance, 40ml of methanol and 80ml of tetrahydrofuran under a nitrogen stream, and the mixture was stirred at room temperature for 1 hour, slowly dropwise added thereto, and further stirred at room temperature for 1 hour. Then, after cooling to 0 ℃, 50ml of water was added, neutralized with a 4M aqueous solution of sodium hydroxide, and extracted with 50ml of dichloromethane. The organic layer was washed 2 times with 30ml water, dried over sodium sulfate and evaporated to give a viscous mass.
Then, the resulting mixed solution of the dope, 1.54g of ammonium acetate and 20ml of acetic acid was heated under reflux at 100 ℃ for 1 hour under a nitrogen stream. Then, after cooling to room temperature, ice water was added, and the mixture was neutralized with a 4M aqueous sodium hydroxide solution and extracted with 50ml of dichloromethane. The organic layer was washed 2 times with 30ml of water, dried over sodium sulfate and evaporated. After washing with 20ml of ethanol and drying in vacuo, 555mg of 4- (4-tert-butylphenyl) -2- (4-methoxyphenyl) pyrrole are obtained.
Subsequently, a mixed solution of 357mg of 2-benzoyl-3, 5-bis (4-tert-butylphenyl) pyrrole, 250mg of 4- (4-tert-butylphenyl) -2- (4-methoxyphenyl) pyrrole, 138mg of phosphorus oxychloride and 10ml of 1, 2-dichloroethane was refluxed under a nitrogen stream for 9 hours. Then, after cooling to room temperature, 847mg of diisopropylethylamine and 931mg of boron trifluoride diethyl ether complex were added thereto, and the mixture was stirred for 3 hours. 20ml of water was poured in and extracted with 30ml of dichloromethane. The organic layer was washed 2 times with 20ml of water, dried over magnesium sulfate and evaporated. The mixture was purified by silica gel column chromatography and dried in vacuo to synthesize an organic phosphor (T21) as shown below.
1H-NMR(CDCl3(d＝ppm))：1.18(s，18H)、1.35(s，9H)、3.85(s，3H)、6.37-6.99(m，17H)、7.45(d，2H)、7.87(d，4H)。
[ chemical formula 33]
Figure BDA0002173187220000671
(Synthesis example 2)
The following describes a method for synthesizing the organic phosphor (T22) of synthesis example 2. In the method for synthesizing the organic phosphor (T22), a mixed solution of 300mg of 4- (4-tert-butylphenyl) -2- (4-methoxyphenyl) pyrrole, 201mg of 2-methoxybenzoyl chloride and 10ml of toluene was heated at 120 ℃ for 6 hours under a nitrogen stream. Next, it was cooled to room temperature and evaporated. After washing with 20ml of ethanol and drying in vacuo, 260mg of 2- (2-methoxybenzoyl) -3- (4-tert-butylphenyl) -5- (4-methoxyphenyl) pyrrole was obtained.
Next, a mixed solution of 260mg of 2- (2-methoxybenzoyl) -3- (4-tert-butylphenyl) -5- (4-methoxyphenyl) pyrrole, 180mg of 4- (4-tert-butylphenyl) -2- (4-methoxyphenyl) pyrrole, 206mg of methanesulfonic anhydride and 10ml of degassed toluene was heated at 125 ℃ for 7 hours under a nitrogen stream. Then, after cooling to room temperature, 20ml of water was poured and extracted with 30ml of dichloromethane. The organic layer was washed 2 times with 20ml of water, evaporated and dried in vacuo.
Then, to a mixed solution of the obtained methylene pyrrole and 10ml of toluene was added 305mg of diisopropylethylamine and 670mg of boron trifluoride diethyl ether complex under a nitrogen stream, and the mixture was stirred at room temperature for 3 hours. Then, 20ml of water was injected and extracted with 30ml of dichloromethane. The organic layer was washed 2 times with 20ml of water, dried over magnesium sulfate and evaporated. The resulting mixture was purified by silica gel column chromatography to synthesize an organic phosphor (T22) shown below.
1H-NMR(CDCl3(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)。
[ chemical formula 34]
Figure BDA0002173187220000681
(Synthesis example 3)
The following describes a method for synthesizing the organic phosphor (T23) of synthesis example 3. In the method for synthesizing the organic phosphor (T23), 5.0g of 2- (2-methoxybenzoyl) -3, 5-bis (4-tert-butylphenyl) pyrrole, 3.3g of 2, 4-bis (4-tert-butylphenyl) pyrrole, and 1.5g of phosphorus oxychloride were added to 30ml of 1, 2-dichloroethane, and the mixture was reacted under reflux for 12 hours. Then, after cooling to room temperature, 5.2g of diisopropylethylamine and 5.6g of boron trifluoride diethyl ether complex were added thereto, and the mixture was stirred for 6 hours. After adding 50ml of water and dichloromethane, the organic layer was extracted, concentrated, and purified by column chromatography using silica gel, and then further purified by sublimation, an organic phosphor (T23) shown below was synthesized.
1H-NMR(CDCl3(d＝ppm))：1.07(s，9H)、2.13(s，6H)、2.39(s，6H)、6.47(t，4H)、6.63(s，8H)、6.75(d，2H)、7.23(d，4H)、7.80(d，4H)。
[ chemical formula 35]
Figure BDA0002173187220000691
(Synthesis example 4)
The following describes a method for synthesizing the organic phosphor (T24) of synthesis example 4. In the method for synthesizing the organic phosphor (T24), 3, 5-dibromobenzaldehyde (3.0g), 4-tert-butylphenyl boronic acid (5.3g), tetrakis (triphenylphosphine) palladium (0) (0.4g) and potassium carbonate (2.0g) were charged into a flask and subjected to nitrogen substitution. Degassed toluene (30mL) and degassed water (10mL) were added thereto, and refluxing was carried out 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, filtered, and the solvent was distilled off. The obtained reaction product was purified by silica gel column chromatography to obtain 3, 5-bis (4-tert-butylphenyl) benzaldehyde (3.5g) as a white solid.
Subsequently, 3, 5-bis (4-tert-butylphenyl) benzaldehyde (1.5g) and 2, 4-dimethylpyrrole (0.7g) were added to the reaction solution, dehydrated dichloromethane (200mL) and trifluoroacetic acid (1 drop) were added, and the mixture was stirred under a nitrogen atmosphere for 4 hours. Next, a solution of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (0.85g) in dehydrated dichloromethane was added thereto, and the mixture was further stirred for 1 hour. After completion of the reaction, boron trifluoride diethyl ether complex (7.0mL) and diisopropylethylamine (7.0mL) were added thereto, and the mixture was stirred for 4 hours, followed by addition of water (100mL) and stirring to separate an organic layer. The organic layer was dried over magnesium sulfate, filtered, and the solvent was distilled off. The obtained reaction product was purified by silica gel column chromatography to synthesize an organic phosphor (T24) shown below.
1H-NMR(CDCl3(d＝ppm))：7.95(s，1H)、7.63-7.48(m，10H)、6.00(s，2H)、2.58(s，6H)、1.50(s，6H)、1.37(s，18H)。
[ chemical formula 36]
Figure BDA0002173187220000701
(Synthesis example 5)
The following describes a method for synthesizing the organic phosphor (T25) of synthesis example 5. An organic phosphor (T25) was synthesized in the same manner as in synthesis example 4, except that ethyl 2, 4-dimethylpyrrole-3-carboxylate was used as the pyrrole raw material instead of 2, 4-dimethylpyrrole in the method for synthesizing an organic phosphor (T25).
[ chemical formula 37]
Figure BDA0002173187220000702
(Synthesis example 6)
The following describes a method for synthesizing the organic phosphor (T26) of synthesis example 6. An organic phosphor (T26) was synthesized in the same manner as in synthesis example 5, except that 4- (methoxycarbonyl) phenylboronic acid was used instead of 4-tert-butylphenyl boronic acid as a boric acid raw material in the synthesis method of the organic phosphor (T26).
[ chemical formula 38]
Figure BDA0002173187220000711
< Silicone resin >
As the silicone resin, the following resins were used.
Silicone resin 1(Si 1):
(A) the components: 28.5 parts by weight of (B): 5.7 parts by weight of (C): 66.0 parts by weight of (D): 0.03 parts by weight, reaction inhibitor: 0.025 parts by weight
(A) Component (MeViSiO)2/2)0.35(Ph2SiO2/2)0.3(PhSiO3/2)0.32(SiO4/2)0.03
(B) Ingredient (Me)3SiO1/2)0.3(PhViSiO2/2)0.4(PhSiO3/2)0.3
(C) Component "HPM-502" (phenylmethylsiloxane copolymer) manufactured by Gelest
(D) Component (1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane solution) platinum content 5% by weight
Reaction inhibitor 1-ethynylhexanol
Wherein, Me: methyl, Vi: vinyl group, Ph: a phenyl group.
Silicone resin 2(Si 2):
(A) the components: 28.5 parts by weight of (B): 5.7 parts by weight of (C): 66.0 parts by weight, component (D): 0.03 part by weight of a reaction inhibitor: 0.025 parts by weight
(A) Ingredient (Me)3SiO1/2)0.01(MeViSiO2/2)0.34(Ph2SiO2/2)0.3(PhSiO3/2)0.32(SiO4/2)0.03
(B) Ingredient (Me)3SiO1/2)0.3(PhViSiO2/2)0.4(PhSiO3/2)0.3
(C) Ingredient (HMe)2SiO)2SiPh2
(D) Component (1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane solution) platinum content 5% by weight
Reaction inhibitor 1-ethynylhexanol
Wherein, Me: methyl, Vi: vinyl group, Ph: a phenyl group.
Silicone resin 3(Si 3):
(A) the components: 28.5 parts by weight of (B): 5.7 parts by weight of (C): 66.0 parts by weight, component (D): 0.03 part by weight of a reaction inhibitor: 0.025 parts by weight
(A) Ingredient (Me)3SiO1/2)0.01(MeViSiO2/2)0.3(Ph2SiO2/2)0.33(PhSiO3/2)0.33(SiO4/2)0.03
(B) Ingredient (Me)3SiO1/2)0.3(PhViSiO2/2)0.4(PhSiO3/2)0.3
(C) Ingredient (HMe)2SiO)2SiPh2
(D) Component (1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane solution) platinum content 5% by weight
Reaction inhibitor 1-ethynylhexanol
Wherein, Me: methyl, Vi: vinyl group, Ph: a phenyl group.
Silicone resin 4(Si 4):
(A) the components: 28.5 parts by weight of (B): 5.7 parts by weight of (C): 66.0 parts by weight, component (D): 0.03 part by weight of a reaction inhibitor: 0.025 parts by weight
(A) Ingredient (Me)3SiO1/2)0.01(MeViSiO2/2)0.2(Ph2SiO2/2)0.38(PhSiO3/2)0.38(SiO4/2)0.03
(B) Ingredient (Me)3SiO1/2)0.3(PhViSiO2/2)0.4(PhSiO3/2)0.3
(C) Ingredient (HMe)2SiO)2SiPh2
(D) Component (1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane solution) platinum content 5% by weight
Reaction inhibitor 1-ethynylhexanol
Wherein, Me: methyl, Vi: vinyl group, Ph: a phenyl group.
Silicone resin 5(Si 5):
(A) the components: 28.5 parts by weight of (B): 5.7 parts by weight of (C): 66.0 parts by weight, component (D): 0.03 part by weight of a reaction inhibitor: 0.025 parts by weight
(A) Ingredient (Me)3SiO1/2)0.01(MeViSiO2/2)0.34(Ph2SiO2/2)0.3(PhSiO3/2)0.32(SiO4/2)0.03
(B) Ingredient (Me)3SiO1/2)0.3(PhViSiO2/2)0.5(PhSiO3/2)0.2
(C) Ingredient (HMe)2SiO)2SiPh2
(D) Component (1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane solution) platinum content 5% by weight
Reaction inhibitor 1-ethynylhexanol
Wherein, Me: methyl, Vi: vinyl group, Ph: a phenyl group.
Silicone resin 6(Si 6):
(A) the components: 31.4 parts by weight of (B): 2.8 parts by weight of (C): 66.0 parts by weight, component (D): 0.03 part by weight of a reaction inhibitor: 0.025 parts by weight
(A) Ingredient (Me)3SiO1/2)0.01(MeViSiO2/2)0.34(Ph2SiO2/2)0.3(PhSiO3/2)0.32(SiO4/2)0.03
(B) Ingredient (Me)3SiO1/2)0.3(PhViSiO2/2)0.4(PhSiO3/2)0.3
(C) Ingredient (HMe)2SiO)2SiPh2
(D) Component (1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane solution) platinum content 5% by weight
Reaction inhibitor 1-ethynylhexanol
Wherein, Me: methyl, Vi: vinyl group, Ph: a phenyl group.
Silicone resin 7(Si 7):
(A) the components: 17.4 parts by weight of (B): 16.8 parts by weight of (C): 66.0 parts by weight, component (D): 0.03 part by weight of a reaction inhibitor: 0.025 parts by weight
(A) Ingredient (Me)3SiO1/2)0.01(MeViSiO2/2)0.34(Ph2SiO2/2)0.3(PhSiO3/2)0.32(SiO4/2)0.03
(B) Ingredient (Me)3SiO1/2)0.3(PhViSiO2/2)0.4(PhSiO3/2)0.3
(C) Ingredient (HMe)2SiO)2SiPh2
(D) Component (1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane solution) platinum content 5% by weight
Reaction inhibitor 1-ethynylhexanol
Wherein, Me: methyl, Vi: vinyl group, Ph: a phenyl group.
Silicone resin 8(Si 8): OE6630(Dow Corning Toray Silicone).
Silicone resin 9(Si 9):
16.7 parts by weight of a resin main component, 16.7 parts by weight of a hardness modifier, 66.7 parts by weight of a crosslinking agent, 0.025 parts by weight of a reaction inhibitor, and 0.03 parts by weight of a platinum catalyst
Ingredients for compounding with silicone resin
Resin principal Components (MeViSiO)2/2)0.25(Ph2SiO2/2)0.3(PhSiO3/2)0.45(HO1/2)0.03(corresponds to the component (A))
Hardness modifier ViMe2SiO(MePhSiO)17.5SiMe2Vi (equivalent to component (B))
Cross-linking agent (HMe)2SiO)2SiPh2(corresponds to component (C))
Wherein, Me: methyl, Vi: vinyl group, Ph: phenyl radical
Reaction inhibitor 1-ethynylhexanol
Platinum catalyst platinum complex (1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane solution) platinum content 5 wt% (corresponding to component (D)).
< Silicone Fine particles >
A2L four-necked round-bottomed flask was equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel. To the flask, 2L of 2.5% aqueous ammonia containing 1ppm of polyether modified siloxane "BYK 333" as a surfactant was added, and the temperature was raised with an oil bath while stirring at 300 rpm. After the internal temperature reached 50 ℃, 200g of a mixture of methyltrimethoxysilane (MTM) and phenyltrimethoxysilane (PhTM) (MTM/PhTM: 23/77 mol%) was added dropwise from the dropping funnel over 30 minutes. At this temperature, stirring was continued for a further 60 minutes, after which about 5g of acetic acid (reagent grade) were added. The mixture was stirred and then filtered to obtain particles on the filter. The particles were washed 2 times with 600mL of water and 1 time with 200mL of methanol, and filtered. The cake on the filter was taken out, pulverized, and freeze-dried over 10 hours, whereby 60g of a white powder was obtained. The obtained white powder was observed by SEM to be monodisperse spherical fine particles. The refractive index of the fine particles was measured by liquid immersion, and the result was 1.54. The microparticles were observed by cross-sectional Transmission Electron Microscopy (TEM) using a TEM. As a result, it was confirmed that the particles were fine particles having a single structure.
< measurement of dynamic elastic modulus >
The obtained phosphor sheet was cut into a circular shape having a diameter of 20mm, and the base material was peeled off, and then the storage elastic modulus was measured using the following apparatus.
A measuring device: viscosity/viscoelasticity measuring apparatus HAAKE MARSIII
(Thermo Fisher SCIENTIFIC)
The measurement conditions were as follows: OSC temperature dependence measurement
Geometry: parallel round plate type (20mm)
Measuring time: 1980 seconds
Angular frequency: 1Hz
Angular velocity: 6.2832 rad/sec
Temperature range: 25 to 200 ℃ (with low temperature control function)
Temperature rise rate: 0.08333 deg.C/sec
Sample shape: circular (diameter 18 mm).
< evaluation of cutting workability >
The obtained phosphor sheet was cut into a square of 1mm × 0.3mm by using a cutting apparatus "GCUT" (manufactured by UHT corporation), and 100 individual phosphor sheets were prepared. The individual phosphor sheets were observed with an optical microscope, and the number of samples having a fracture or a defect in the peripheral portion was counted. The smaller the number of samples having a broken or defective peripheral edge portion, the more excellent the cutting workability. When the value is B or more, the composition is excellent in practical use.
S: 0 cutting workability was very good
A: good cutting workability of 1 to 3 pieces
B: the cutting workability of 4 or more and 10 or less has no problem in practical use
C: cutting workability of 11 or more and 30 or less is poor
D: the cutting workability was very poor for 31 or more.
< method for manufacturing LED Package >
The obtained phosphor sheet was cut into a square of 1mm × 0.3mm by a dicing apparatus "GCUT" (manufactured by UHT corporation), and 100 individual phosphor sheets were prepared. The individual phosphor sheets were vacuum-sucked by a collet using a flip chip bonding apparatus (manufactured by Toray engineering Co., Ltd.) and peeled from the base material. The peeled single phosphor sheet was attached to the LED chip surface of the LED package mounted with the flip-chip LED chip under the following attachment conditions. The obtained package was connected to a dc power supply to light it, and whether or not it was lit was confirmed.
(conditions of pasting)
Heating conditions: 140 deg.C
Pressurizing conditions: 80N
Pressurizing time: for 20 seconds.
< evaluation of adhesion >
Using the obtained LED package, tweezers were placed at the interface between the LED chip and the phosphor sheet, and then the phosphor sheet was held by the tweezers to confirm adhesiveness between the LED chip and the phosphor sheet. The samples having good adhesiveness were not peeled off even when they were gripped with tweezers. In the sample having poor adhesiveness, the phosphor sheet was peeled off from the LED chip. The number of the peeled samples was counted by observation with an optical microscope. The smaller the number of samples peeled off, the more excellent the adhesiveness. When the value is B or more, the composition is excellent in practical use.
S: 0 piece of the adhesive was very good
A: 1 to 5 pieces of the adhesive composition have good adhesiveness
B: adhesion of 6 or more and 10 or less is practically not problematic
C: 11 or more and 30 or less are poor in adhesiveness
D: 31 or more are very poor in adhesion.
< Total Beam measurement >
The LED chip was turned on by applying a power of 1W to the LED package thus produced, and the total luminous flux (1m) was measured by using a total luminous flux measuring system (HM-3000, Otsuka Denshi). The relative brightness was calculated assuming that the total light beam in comparative example 1 was 100.
Example 1 (Effect of Silicone composition)
A polyethylene container having a volume of 100ml was used, and 18.0g of silicone resin 1(Si1), 42.0g of phosphor 1(YAG1) as an inorganic phosphor, and 2.5g of diethylene glycol monobutyl ether were added and mixed. Then, the mixture was stirred and defoamed at 1000rpm for 5 minutes using a planetary stirring and defoaming device, and then mixed and dispersed 6 times by a three-roll mill to prepare a phosphor composition 1.
Using a slot die coater, phosphor composition 1 was coated on the release-treated surface of "Cerapeel" BX9 as a base material, and the resultant was heated at 120 ℃ and dried for 40 minutes to obtain a 100mm square phosphor sheet having a thickness of 80 μm. The dynamic elastic modulus measurement and the evaluation of the cutting processability were carried out by the methods described above. Further, the LED package was produced by the above-described method, and adhesion evaluation and total light beam measurement were performed. The results are shown in Table 1. The result was that the cutting workability was good, the adhesiveness was also improved, and the relative brightness was also improved.
Example 2 modification of Silicone resin
A phosphor sheet was produced in the same manner as in example 1, except that the silicone resin was changed to Si2, and then an LED package was produced, and each measurement and evaluation was performed. The results are shown in Table 1. As shown in table 1, it is understood from the evaluation results of example 2 that the phosphor sheet according to the embodiment of the present invention is excellent in cutting workability and adhesiveness. In addition, it is found that the relative luminance is also improved.
Comparative example 1
A phosphor sheet was produced in the same manner as in example 1, except that the silicone resin was changed to Si8, and then an LED package was produced, and each measurement and evaluation was performed. The results are shown in Table 1. As shown in table 1, in comparative example 1, although there was no practical problem in the cutting workability, the adhesiveness was not improved.
Example 3 modification of Silicone resin with Silicone microparticles added
A polyethylene container having a volume of 100ml was used, and 17.0g of silicone resin 2(Si2), 42.0g of phosphor 1(YAG1) as an inorganic phosphor, 0.6g of silicone fine particles, and 2.5g of diethylene glycol monobutyl ether were added and mixed. Then, the mixture was stirred and defoamed at 1000rpm for 5 minutes using a planetary stirring and defoaming device, and then mixed and dispersed 6 times using a three-roll mill to prepare a phosphor composition 3.
The phosphor composition 3 was applied to the release-treated surface of "Cerapeel" BX9 as a base material by using a slot die coater, and heated and dried at 120 ℃ for 40 minutes to obtain a 100mm square phosphor sheet having a thickness of 80 μm. The dynamic elastic modulus measurement and the evaluation of the cutting processability were carried out by the methods described above. Further, the LED package was produced by the above-described method, and adhesion evaluation and total light beam measurement were performed. The results are shown in Table 1. The result was that both the cutting workability and the adhesiveness were good, and the relative brightness was also improved.
Examples 4 to 8 (modification of Silicone composition)
As shown in table 1, phosphor sheets were produced in the same manner as in example 3 except that the silicone resin was changed to Si3 to Si7, respectively, and then LED packages were produced and subjected to the respective measurements and evaluations. The results are shown in Table 1. As shown in Table 1, it is understood from the evaluation results of examples 4 to 8 that the phosphor sheet according to the embodiment of the present invention has good cutting workability and improved adhesiveness. In addition, it is found that the relative luminance is also improved.
Comparative example 2
As shown in table 1, a phosphor sheet was produced in the same manner as in example 3 except that the silicone resin was changed to Si9, and then LED packages were produced and subjected to the respective measurements and evaluations. The results are shown in Table 1. In comparative example 2, the cutting workability was not practically problematic, but the adhesiveness was not improved. In addition, the brightness was not improved.
Example 9 (resin content was changed to 10.0% by weight)
Using a polyethylene container having a volume of 100ml, 5.96g of silicone resin 2(Si2), 53.6g of phosphor 1(YAG1) as an inorganic phosphor, 0.6g of silicone fine particles, and 2.5g of diethylene glycol monobutyl ether were added and mixed. Then, the mixture was stirred and defoamed at 1000rpm for 5 minutes using a planetary stirring and defoaming device, and then mixed and dispersed 6 times using a three-roll mill to prepare a phosphor composition 11.
Using a slot die coater, phosphor composition 11 was coated on the release-treated surface of "Cerapeel" BX9 as a base material, and the resultant was heated at 120 ℃ and dried for 40 minutes to obtain a 100mm square phosphor sheet having a thickness of 80 μm. The dynamic elastic modulus measurement and the evaluation of the cutting processability were carried out by the methods described above. Further, the LED package was produced by the above-described method, and adhesion evaluation and total light beam measurement were performed. The results are shown in Table 2. The result was that both the cutting workability and the adhesiveness were good, and the relative brightness was also improved.
Example 10 (resin content was changed to 70.0% by weight)
42.4g of silicone resin 2(Si2), 17.5g of phosphor 1(YAG1) as an inorganic phosphor, 0.6g of silicone fine particles, and 2.5g of diethylene glycol monobutyl ether were added to a polyethylene container having a volume of 100ml, and mixed. Then, the mixture was stirred and defoamed at 1000rpm for 5 minutes using a planetary stirring and defoaming device, and then mixed and dispersed 6 times using a three-roll mill to prepare a phosphor composition 12.
Phosphor composition 12 was applied to the release-treated surface of "Cerapeel" BX9 as a base material using a slot die coater, and heated and dried at 120 ℃ for 40 minutes to obtain a 100mm square phosphor sheet having a thickness of 80 μm. The dynamic elastic modulus measurement and the evaluation of the cutting processability were carried out by the methods described above. Further, the LED package was produced by the above-described method, and adhesion evaluation and total light beam measurement were performed. The results are shown in Table 2. The result was that both the cutting workability and the adhesiveness were good, and the relative brightness was also improved.
Example 11 (resin content was changed to 85.0% by weight)
Using a polyethylene container having a volume of 100ml, 52.5g of silicone resin 2(Si2), 8.6g of phosphor 1(YAG1) as an inorganic phosphor, 0.6g of silicone fine particles, and 2.5g of diethylene glycol monobutyl ether were added and mixed. Then, the mixture was stirred and defoamed at 1000rpm for 5 minutes using a planetary stirring and defoaming device, and then mixed and dispersed 6 times using a three-roll mill to prepare a phosphor composition 13.
The phosphor composition 13 was applied to the release-treated surface of "Cerapeel" BX9 as a base material by using a slot die coater, and heated and dried at 120 ℃ for 40 minutes to obtain a 100mm square phosphor sheet having a thickness of 80 μm. The dynamic elastic modulus measurement and the evaluation of the cutting processability were carried out by the methods described above. Further, the LED package was produced by the above-described method, and adhesion evaluation and total light beam measurement were performed. The results are shown in Table 2. The result was that both the cutting workability and the adhesiveness were good, and the relative brightness was also improved.
Example 12 (changing the content of the fine silicone particles to 0.5 wt%)
A polyethylene container having a volume of 100ml was used, and 17.0g of silicone resin 2(Si2), 42.0g of phosphor 1(YAG1) as an inorganic phosphor, 0.3g of silicone fine particles, and 2.5g of diethylene glycol monobutyl ether were added and mixed. Then, the mixture was stirred and defoamed at 1000rpm for 5 minutes using a planetary stirring and defoaming device, and then mixed and dispersed 6 times using a three-roll mill to prepare a phosphor composition 14.
The phosphor composition 14 was applied to the release-treated surface of "Cerapeel" BX9 as a base material by using a slot die coater, and heated and dried at 120 ℃ for 40 minutes to obtain a 100mm square phosphor sheet having a thickness of 80 μm. The dynamic elastic modulus measurement and the evaluation of the cutting processability were carried out by the methods described above. Further, the LED package was produced by the above-described method, and adhesion evaluation and total light beam measurement were performed. The results are shown in Table 2. The result was that both the cutting workability and the adhesiveness were good, and the relative brightness was also improved.
Example 13 (the content of silicone fine particles was changed to 10.0 wt%)
Using a polyethylene container having a volume of 100ml, 11.0g of silicone resin 2(Si2), 42.0g of phosphor 1(YAG1) as an inorganic phosphor, 6g of silicone fine particles, and 2.5g of diethylene glycol monobutyl ether were added and mixed. Then, the mixture was stirred and defoamed at 1000rpm for 5 minutes using a planetary stirring and defoaming device, and then mixed and dispersed 6 times using a three-roll mill to prepare a phosphor composition 15.
Using a slot die coater, phosphor composition 15 was applied to the release-treated surface of "Cerapeel" BX9 as a base material, and the resultant was heated at 120 ℃ and dried for 40 minutes to obtain a 100mm square phosphor sheet having a thickness of 80 μm. The dynamic elastic modulus measurement and the evaluation of the cutting processability were carried out by the methods described above. Further, the LED package was produced by the above-described method, and adhesion evaluation and total light beam measurement were performed. The results are shown in Table 2. The result was that both the cutting workability and the adhesiveness were good, and the relative brightness was also improved.
Example 14 (the content of fine silicone particles was changed to 20.0 wt%)
6g of silicone resin 2(Si2), 42.0g of phosphor 1(YAG1) as an inorganic phosphor, 12g of fine silicone particles, and 2.5g of diethylene glycol monobutyl ether were added and mixed to a polyethylene container having a volume of 100 ml. Then, the mixture was stirred and defoamed at 1000rpm for 5 minutes using a planetary stirring and defoaming device, and then mixed and dispersed 6 times using a three-roll mill to prepare a phosphor composition 16.
The phosphor composition 16 was applied to the release-treated surface of "Cerapeel" BX9 as a base material by using a slot die coater, and heated and dried at 120 ℃ for 40 minutes to obtain a 100mm square phosphor sheet having a thickness of 80 μm. The dynamic elastic modulus measurement and the evaluation of the cutting processability were carried out by the methods described above. Further, the LED package was produced by the above-described method, and adhesion evaluation and total light beam measurement were performed. The results are shown in Table 2. The result was that both the cutting workability and the adhesiveness were good, and the relative brightness was also improved.
Example 15 (phosphor content was changed to 38.0 wt%)
A polyethylene container having a volume of 100ml was used, and 36.4g of silicone resin 2(Si2), 22.7g of phosphor 1(YAG1) as an inorganic phosphor, 0.6g of silicone fine particles, and 2.5g of diethylene glycol monobutyl ether were added and mixed. Then, the mixture was stirred and defoamed at 1000rpm for 5 minutes using a planetary stirring and defoaming device, and then mixed and dispersed 6 times using a three-roll mill to prepare a phosphor composition 17.
The phosphor composition 17 was applied to the release-treated surface of "Cerapeel" BX9 as a base material by using a slot die coater, and heated and dried at 120 ℃ for 40 minutes to obtain a 100mm square phosphor sheet having a thickness of 80 μm. The dynamic elastic modulus measurement and the evaluation of the cutting processability were carried out by the methods described above. Further, the LED package was produced by the above-described method, and adhesion evaluation and total light beam measurement were performed. The results are shown in Table 3. The result was that both the cutting workability and the adhesiveness were good, and the relative brightness was also improved.
Example 16 (phosphor content was changed to 40.0 wt%)
A polyethylene container having a volume of 100ml was used, and 35.2g of silicone resin 2(Si2), 23.8g of phosphor 1(YAG1) as an inorganic phosphor, 0.6g of silicone fine particles, and 2.5g of diethylene glycol monobutyl ether were added and mixed. Then, the mixture was stirred and defoamed at 1000rpm for 5 minutes using a planetary stirring and defoaming device, and then mixed and dispersed 6 times using a three-roll mill to prepare a phosphor composition 18.
The phosphor composition 18 was applied to the release-treated surface of "Cerapeel" BX9 as a base material by using a slot die coater, and heated and dried at 120 ℃ for 40 minutes to obtain a 100mm square phosphor sheet having a thickness of 80 μm. The dynamic elastic modulus measurement and the evaluation of the cutting processability were carried out by the methods described above. Further, the LED package was produced by the above-described method, and adhesion evaluation and total light beam measurement were performed. The results are shown in Table 3. The result was that both the cutting workability and the adhesiveness were good, and the relative brightness was also improved.
Example 17 (phosphor content was changed to 63.0 wt%)
A polyethylene container having a volume of 100ml was used, and 21.5g of silicone resin 2(Si2), 37.6g of phosphor 1(YAG1) as an inorganic phosphor, 0.6g of silicone fine particles, and 2.5g of diethylene glycol monobutyl ether were added and mixed. Then, the mixture was stirred and defoamed at 1000rpm for 5 minutes using a planetary stirring and defoaming device, and then mixed and dispersed 6 times using a three-roll mill to prepare a phosphor composition 19.
The phosphor composition 19 was applied to the release-treated surface of "Cerapeel" BX9 as a base material by using a slot die coater, and heated and dried at 120 ℃ for 40 minutes to obtain a 100mm square phosphor sheet having a thickness of 80 μm. The dynamic elastic modulus measurement and the evaluation of the cutting processability were carried out by the methods described above. Further, the LED package was produced by the above-described method, and adhesion evaluation and total light beam measurement were performed. The results are shown in Table 3. The result was that both the cutting workability and the adhesiveness were good, and the relative brightness was also improved.
Example 18 (phosphor content was changed to 80.0 wt%)
Using a polyethylene container having a volume of 100ml, 11.3g of silicone resin 2(Si2), 47.7g of phosphor 1(YAG1) as an inorganic phosphor, 0.6g of silicone fine particles, and 2.5g of diethylene glycol monobutyl ether were added and mixed. Then, the mixture was stirred and defoamed at 1000rpm for 5 minutes using a planetary stirring and defoaming device, and then mixed and dispersed 6 times using a three-roll mill to prepare a phosphor composition 20.
The phosphor composition 20 was applied to the release-treated surface of "Cerapeel" BX9 as a base material by using a slot die coater, and heated and dried at 120 ℃ for 40 minutes to obtain a 100mm square phosphor sheet having a thickness of 80 μm. The dynamic elastic modulus measurement and the evaluation of the cutting processability were carried out by the methods described above. Further, the LED package was produced by the above-described method, and adhesion evaluation and total light beam measurement were performed. The results are shown in Table 3. The result was that both the cutting workability and the adhesiveness were good, and the relative brightness was also improved.
Comparative example 3
A phosphor sheet was produced in the same manner as in example 15, except that the silicone resin was changed to Si9, and then an LED package was produced, and each measurement and evaluation was performed. The results are shown in Table 3. As shown in table 3, the cutting workability was practically no problem, but the adhesiveness was not improved.
Comparative example 4
A phosphor sheet was produced in the same manner as in example 16, except that the silicone resin was changed to Si9, and then an LED package was produced, and each measurement and evaluation was performed. The results are shown in Table 3. As shown in table 3, the cutting workability was practically no problem, but the adhesiveness was not improved.
Comparative example 5
A phosphor sheet was produced in the same manner as in example 17, except that the silicone resin was changed to Si9, and then an LED package was produced, and each measurement and evaluation was performed. The results are shown in Table 3. As shown in table 3, the cutting workability was practically no problem, but the adhesiveness was not improved.
Comparative example 6
A phosphor sheet was produced in the same manner as in example 18, except that the silicone resin was changed to Si9, and then an LED package was produced, and each measurement and evaluation was performed. The results are shown in Table 3. As shown in Table 3, the cutting processability was lowered and the adhesiveness was not improved.
Example 19 (modification of phosphor-1)
A polyethylene container having a volume of 100ml was used, and 17.0g of silicone resin 2(Si2), 16.8g of phosphor 2 (. beta.1) as an inorganic phosphor, 25.2g of phosphor 3(KSF1), 0.6g of silicone fine particles, and 2.5g of diethylene glycol butyl ether were added and mixed. Then, the mixture was stirred and defoamed at 1000rpm for 5 minutes using a planetary stirring and defoaming device, and then mixed and dispersed 6 times using a three-roll mill to prepare a phosphor composition 25.
Using a slot die coater, phosphor composition 25 was applied to the release-treated surface of "Cerapeel" BX9 as a base material, and the resultant was heated at 120 ℃ and dried for 30 minutes to obtain a 100mm square phosphor sheet having a thickness of 80 μm. The dynamic elastic modulus measurement and the evaluation of the cutting processability were carried out by the methods described above. Further, the LED package was produced by the above-described method, and adhesion evaluation and total light beam measurement were performed. The results are shown in Table 4. The result was that both the cutting workability and the adhesiveness were very good, and the relative brightness was also greatly improved.
Comparative example 7
A phosphor sheet was produced in the same manner as in example 19, except that the silicone resin was changed to Si9, and then an LED package was produced, and each measurement and evaluation was performed. The results are shown in Table 4. As shown in table 4, the cutting workability was practically no problem, but the adhesiveness was not improved.
Example 20 (modification of phosphor-2)
Using a polyethylene container having a volume of 100ml, 60.0g of silicone resin 2(Si2) and 1.24X 10 of fluorescent material 4(21 type) as an organic fluorescent material were added-3g. Phosphor 5(24 type) 1.24X 10-3g. 1.0g of silicone fine particles and 2.5g of diethylene glycol monobutyl ether were mixed. Then, the mixture was stirred and defoamed at 1000rpm for 5 minutes using a planetary stirring and defoaming device, to prepare a phosphor composition 27.
The phosphor composition 27 was applied to the release-treated surface of "Cerapeel" BX9 as a base material by using a slot die coater, and heated and dried at 120 ℃ for 30 minutes to obtain a 100mm square phosphor sheet having a thickness of 80 μm. The dynamic elastic modulus measurement and the evaluation of the cutting processability were carried out by the methods described above. Further, the LED package was produced by the above-described method, and adhesion evaluation and total light beam measurement were performed. The results are shown in Table 5. The result was that both the cutting workability and the adhesiveness were very good, and the relative brightness was also improved.
Examples 21 to 24 (modifications of phosphor-3)
In examples 21 to 24, phosphor compositions (28 to 32) were produced in the same manner as in example 20 except that the organic phosphor was appropriately changed as shown in table 5, and phosphor sheets were produced in the same manner as in example 20 using each phosphor composition. Then, an LED package was produced using each phosphor sheet, and evaluated. The results are shown in Table 5. From the evaluation results of examples 21 to 24, it is clear that the results of cutting workability and adhesiveness were very good, and the relative brightness was improved.
Comparative example 8
A phosphor composition 33 and a phosphor sheet were produced 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(27 type) and phosphor 5(28 type). Then, LED packages were produced, and each measurement and evaluation was performed. The results are shown in Table 5. As shown in table 5, the cutting workability was practically no problem, but the adhesiveness was not improved.
[ chemical formula 39]
Figure BDA0002173187220000841
[ chemical formula 40]
Figure BDA0002173187220000851
Figure BDA0002173187220000861
Figure BDA0002173187220000871
Figure BDA0002173187220000881
[ Table 4]
Figure BDA0002173187220000891
Figure BDA0002173187220000901
Description of the reference numerals
1 LED chip
2 phosphor sheet
3 transparent sealing Material
4 reflector
5 mounting substrate
6 electrode
7 gold bump
8 transparent adhesive
9 base material
10 LED package
11 temporary fixing sheet
12 heating crimping tool
13 wafer having LED chips formed on surface thereof
14 fluorescent 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 laminating machine
23 suction/exhaust port
24 cutting part
25 LED chip with phosphor sheet
26 LED chip with phosphor sheet (with base material thereof)

Claims (18)

1. A phosphor sheet comprising a phosphor and a silicone resin, wherein the phosphor sheet has a storage elastic modulus G ' at 25 ℃ of 0.01MPa or more, a storage elastic modulus G ' at 100 ℃ of less than 0.01MPa, and a storage elastic modulus G ' at 140 ℃ of 0.05MPa or more,
wherein the silicone resin is a crosslinked product of a crosslinkable silicone composition containing at least the following components (A) to (D),
(A) an organopolysiloxane having a branched structure represented by the average unit formula (1),
[ chemical formula 1]
(R1 3SiO1/2)a(R1 2SiO2/2)b(R1SiO3/2)c(SiO4/2)d(R2O1/2)e (1)
In the average unit formula (1), R1A monovalent hydrocarbon group having 1 to 14 carbon atoms, at least one of which is an aryl group, and at least one of which is an alkenyl group having 2 to 6 carbon atoms; r2Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; a. b, c, d and e are numbers satisfying a is 0. ltoreq. a.ltoreq.0.1, b is 0.2. ltoreq. b.ltoreq.0.9, c is 0.1. ltoreq. c.ltoreq.0.6, d is 0. ltoreq. d.ltoreq.0.2, e is 0. ltoreq. e.ltoreq.0.1, and a + b + c + d + e is 1;
(B) an organopolysiloxane having a branched structure represented by the average unit formula (2),
[ chemical formula 2]
(R3 3SiO1/2)f(R3 2SiO2/2)g(R3SiO3/2)h (2)
In the average unit formula (2), R3A monovalent hydrocarbon group having 1 to 14 carbon atoms, at least one of which is an aryl group, and at least one of which is an alkenyl group having 2 to 6 carbon atoms; f. g and h satisfy f is more than 0.1 and less than or equal to 0.4, g is more than or equal to 0.2 and less than or equal to 0.5, h is more than or equal to 0.2 and less than or equal to 0.5, and f+ g + h is a number of 1;
(C) an organopolysiloxane having at least two Si-H bonds in one molecule, wherein 12 to 70 mol% of organic groups bonded to silicon atoms are aryl groups;
(D) a catalyst for hydrosilylation.
2. The phosphor sheet according to claim 1, wherein the 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).
3. The phosphor sheet according to claim 1 or 2, wherein the component (C) is an organopolysiloxane represented by the average unit formula (3),
[ chemical formula 3]
(HR4 2SiO)2SiR4 2 (3)
In the average unit formula (3), R4Is aryl, alkyl with 1-6 carbon atoms or cycloalkyl; wherein R is412 to 70 mol% of the total amount of the aromatic ring-containing compound is an aromatic group.
4. The phosphor sheet according to claim 1 or 2, wherein a content of the phosphor is 40% by weight or more and 90% by weight or less.
5. The phosphor sheet according to claim 1 or 2, wherein the phosphor comprises a β -type sialon phosphor and a general formula A2MF6: mn-activated complex fluoride phosphor represented by Mn,
general formula A2MF6: in Mn, A is one or more alkali metals selected from the group consisting of Li, Na, K, Rb and Cs and containing 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.
6. The phosphor sheet according to claim 1 or 2, wherein the phosphor is a methylene pyrrole compound.
7. The phosphor sheet according to claim 6, wherein the phosphor is a compound represented by general formula (4),
[ chemical formula 4]
Figure FDA0003181854590000021
R5、R6、Ar1～Ar5And L, which may be the same or different, is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aralkyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, mercapto, alkoxy, alkylthio, aryl ether, arylthioether, aryl, heteroaryl, heterocyclic, halogen, haloalkane, haloalkene, haloalkyne, cyano, aldehyde, carbonyl, carboxyl, ester, carbamoyl, amino, nitro, silyl, siloxane, fused rings with adjacent substituents, and aliphatic rings; m represents a metal having a valence of M and is at least one selected from the group consisting of boron, beryllium, magnesium, chromium, iron, nickel, copper, zinc and platinum.
8. The phosphor sheet according to claim 7, wherein M in the general formula (4) is boron, L is fluorine or a fluorine-containing aryl group, and M-1 is 2.
9. The phosphor sheet according to claim 7 or 8, wherein Ar in the general formula (4)5Is a group represented by the general formula (5),
[ chemical formula 5]
Figure FDA0003181854590000031
r is selected from the group consisting of hydrogen, alkyl, cycloalkyl, heterocyclyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, thiol, alkoxy, alkylthio, aryl ether, aryl thioether, aryl, heteroaryl, halogen, cyano, aldehyde, carbonyl, carboxyl, oxycarbonyl, carbamoyl, amino, nitro, silyl, siloxane, borane, phosphine oxide; k is an integer of 1-3; when k is 2 or more, r may be the same or different.
10. An LED chip comprising the phosphor sheet according to any one of claims 1 to 9 or a cured product thereof.
11. An LED package comprising the phosphor sheet according to any one of claims 1 to 9 or a cured product thereof.
12. A method of manufacturing an LED package, comprising:
a step of cutting the phosphor sheet according to any one of claims 1 to 9 into individual pieces; and
and a step of attaching the phosphor sheet cut into individual pieces to an LED chip.
13. The method of manufacturing an LED package according to claim 12, wherein the phosphor sheet is attached to a portion of a light emitting surface of the LED chip that avoids the electrode.
14. A method of manufacturing an LED package, comprising:
collectively attaching the phosphor sheet according to any one of claims 1 to 9 to a plurality of LED chips formed on a wafer; and
and a step of collectively dicing the wafer and singulating the LED chips to which the phosphor sheet is attached.
15. The method for manufacturing an LED package according to any one of claims 12 to 14, wherein a heating temperature when the phosphor sheet is attached to the LED chip is 60 ℃ or higher and 250 ℃ or lower.
16. A light emitting device comprising the LED package of claim 11.
17. A backlight module comprising the LED package of claim 11.
18. A display comprising the LED package of claim 11.
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