TW201518088A - Laminate body and method for producing light-emitting device using the same - Google Patents

Abstract

A purpose of the invention is to provide a laminate body, wherein a fluorescent sheet is formed on a topside surface and a side surface of an LED chip in good followability and uniform film thickness. Besides, a purpose of the invention is to provide a method for producing a light-emitting device, wherein the laminate body is used, a method of high production is used, and the topside surface and the side surface of the LED chip is covered by the fluorescent sheet. The laminate body of the invention includes a support substrate and the fluorescent sheet containing a fluorescent body and a resin. A rupture elongation of the support substrate obtained by a tensile test at 23 DEG C is 200% or more, and Young's modulus of the support substrate at 23 DEG C is 600 MPa or less.

Description

Laminated body and method of manufacturing the same using the same

The present invention relates to a laminate comprising a phosphor sheet containing a phosphor and a resin. More specifically, it relates to a laminate including a phosphor sheet for converting an emission wavelength derived from an upper surface and a side surface of an LED wafer.

Light Emitting Diode (LED) is based on the background of its significant improvement in luminous efficiency. It is characterized by low power consumption, high lifetime, design, etc., and is suitable for backlights for liquid crystal displays (LCDs). Or in the automotive field, not only for headlights for cars, but also for general lighting, they are eager to expand the market.

The LEDs are classified into a lateral type, a vertical type, and a flip chip type according to the mounting type thereof, and flip chip type LEDs have attracted attention in terms of improving brightness and excellent heat dissipation. However, in the sealing using the conventional distribution method in the flip chip type LED, there is a problem in that the thickness of the phosphor layer cannot be made uniform between the upper surface and the side surface of the wafer, and uneven orientation of the luminescent color occurs.

In response to this problem, there has been proposed a technique in which a phosphor sheet, which is a sheet containing a phosphor, has good followability and is uniformly attached to the periphery of the wafer (see, for example, Patent Document 1 to Patent Document 2). Patent Document 1 is a method of attaching a phosphor sheet to a side surface of an LED wafer by using a pressing member formed with a concave portion that is slightly larger than the LED wafer. Further, Patent Document 2 is a first step of attaching a laminate in which a support substrate and a phosphor sheet are placed on an LED wafer and pressurizing the separator in a vacuum state. Then, the support substrate is removed, and the phosphor sheet is attached to the side of the LED wafer via the second stage attachment step by non-contact press.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-138831

[Patent Document 2] International Publication No. 2012/023119

However, in the method of Patent Document 1, since it is necessary to reproduce the mold as the pressing member every time the type of the LED is changed, the economy is poor. In addition, since the pressing member is pressed against the phosphor sheet, there is a problem that the sheet is damaged or the pressing member is contaminated, and the productivity is poor.

Further, in the method of Patent Document 2, only the phosphor sheet is not able to follow the side surface of the wafer due to insufficient flexibility of the support substrate in the first step of the diaphragm pressurization step, so that the support substrate is removed after temporarily returning to atmospheric pressure. Carry out the second phase of non- The contact pressurization step has a problem in terms of productivity.

An object of the present invention is to provide a laminate in which the phosphor sheet is formed on the upper surface and the side surface of the LED wafer with good followability and a uniform film thickness. Further, there is provided a method for producing a light-emitting device, which uses the laminate to cover the upper surface and the side surface of the LED wafer with a phosphor sheet by a method having high productivity.

The invention is as follows.

[1] A laminate comprising a support substrate and a phosphor sheet containing a phosphor and a resin, and the support substrate obtained by a tensile test at 23 ° C The elongation at break is 200% or more, and the Young's modulus at 23 ° C of the support substrate is 600 MPa or less.

[2] The laminate according to [1], wherein the support substrate has a Young's modulus at 23 ° C of 400 MPa or less.

[3] The laminate according to [1], wherein the support substrate has a Young's modulus at 23 ° C of 100 MPa or less.

[4] The laminate according to any one of [1] to [3] wherein the support substrate is polyvinyl chloride or polyurethane.

[5] A method of manufacturing a light-emitting device, comprising the step of coating a light-emitting surface of an LED wafer bonded to a substrate, such as the layered body of any one of [1] to [4] The light body sheet is coated.

[6] A method of manufacturing a light-emitting device, comprising the steps of: coating step: bonding an upper surface and a side surface of an LED wafer bonded to a substrate to any one of [1] to [4] The phosphor sheet of the laminate described in the section is coated.

[7] The method of manufacturing a light-emitting device according to [5] or [6] wherein the LED wafer is in a portion from the surface of the LED wafer in a portion where the phosphor sheet is in contact with the upper surface of the LED wafer a distance a [μm] from the outer surface of the phosphor sheet, and from the side of the LED wafer to the outer surface of the phosphor sheet in a portion where the LED wafer is in contact with the side surface of the phosphor sheet at the LED wafer The distance b [μm] until the following relationship is satisfied: 1.00 < a / b < 1.20.

[8] The method of producing a light-emitting device according to any one of [1] to [4], wherein the step of coating the phosphor sheet of the laminate according to any one of [1] to [4] (the coating step), a distance a from the upper surface of the LED wafer to the outer surface of the phosphor sheet in the portion of the LED wafer that is in contact with the upper surface of the LED wafer in the LED wafer [μm And a distance b [μm] from the side of the LED wafer to the outer surface of the phosphor sheet in the portion of the LED wafer that is in contact with the side surface of the LED wafer in the LED wafer satisfies the following relationship: 1.00 < a/b<1.20.

According to the present invention, the follow-up property of the LED chip upper surface is good A phosphor sheet is attached to the side emitting surface. In addition, it is thereby possible to provide a light-emitting device in which the azimuth unevenness of the luminescent color does not exist.

1‧‧ ‧ laminated body

2‧‧‧Support substrate

3‧‧‧Fuel sheet

4‧‧‧Adhesive material (adhesive layer)

5‧‧‧vacuum chamber

6‧‧‧Upper platen

7‧‧‧Lower pressure plate

8‧‧‧Flexible sheet

9‧‧‧Confined space (for compacting mechanism)

10‧‧‧Air injection. Discharge port (for compacting mechanism)

11‧‧‧Compacting mechanism

12‧‧‧Air injection. Discharge port (for vacuum chamber)

13‧‧‧Substrate

14‧‧‧LED chip

15‧‧‧Lighting device

16‧‧‧covered part of the upper surface and side of the LED chip

17‧‧‧ Coverage of the substrate

18‧‧‧Bumps

a, b‧‧‧ distance

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic view of a laminate of the present invention.

Fig. 2 is a schematic view showing a laminate of the present invention, that is, a laminate having an adhesive.

3a to 3f are examples of a method of manufacturing a light-emitting device using the laminate of the present invention.

4 is a schematic cross-sectional view and a plan view of a light-emitting device covered with a phosphor sheet.

The laminate of the present invention is shown in Fig. 1. The laminate 1 of the present invention comprises a support substrate 2, and a phosphor sheet 3 containing a phosphor and a resin, and the elongation at break in the tensile test of the support substrate is 200% at 23 ° C. The above, and the Young's modulus is 600 MPa or less.

In other words, the laminated body of the present invention refers to a laminated body including a supporting substrate and a phosphor sheet containing a phosphor and a resin, and the support substrate obtained by a tensile test 23 The elongation at break at ° C is 200% or more, and the Young's modulus at 23 ° C of the support substrate is 600 MPa or less.

<Silver sheet>

The phosphor sheet is not particularly limited as long as it mainly contains a resin and a phosphor, and various sheets can be used. Other ingredients may also be included as needed.

(physical properties of phosphor sheets)

From the viewpoints of storage property, handling property, and processability, the phosphor sheet preferably has high elasticity in the vicinity of room temperature. On the other hand, from the viewpoint of deforming and adhering to the LED chip, it is preferable to lower the elasticity under a certain condition, and to exhibit flexibility and adhesion (adhesiveness). From these viewpoints, the phosphor sheet is preferably softened by heating at 60 ° C or higher, and exhibits adhesiveness.

The storage elastic modulus of such a phosphor sheet is preferably 0.1 at 25 ° C. It is MPa or more and less than 0.1 MPa at 100 ° C, more preferably 0.5 MPa or more at 25 ° C and less than 0.05 MPa at 100 ° C.

The storage elastic modulus referred to herein refers to the measurement of dynamic viscoelasticity. Storage elastic modulus in the case. The term "dynamic viscoelasticity" refers to the decomposition of the shear stress expressed in the steady state when the shear strain is applied to the material at a certain sinusoidal frequency, and the composition (elastic component) and the strain which are consistent with the strain and the phase. A method of analyzing the dynamic mechanical properties of a material by a component (viscous component) that is 90° slower in phase. Here, the stress component that matches the phase and the shear strain is divided by the shear strain, and the storage elastic modulus G′ is the deformation and follower of the material for the dynamic strain at each temperature. Therefore, the material is processed. Sex or adhesion is closely related.

Regarding the case of the phosphor sheet of the present invention, by having at 25 ° C The storage elastic modulus of 0.1 MPa or more is cut off in a state where the sheet is not deformed in the vicinity of the sheet due to the rapid shear stress such as the cutting process by the blade at room temperature (25 ° C). Machinability of dimensional accuracy. For the purpose of the present invention, the upper limit of the storage elastic modulus at room temperature is not particularly limited, in consideration of reduction and The necessity of the stress strain after the LED elements are bonded is preferably an upper limit of the storage elastic modulus of 1 GPa or less. In addition, when the storage modulus at 100 ° C is less than 0.1 MPa, when heating is applied at 60 ° C to 150 ° C, the shape of the surface of the LED wafer is rapidly deformed to follow, and high adhesion is obtained. If a phosphor sheet having a storage elastic modulus of less than 0.1 MPa is obtained at 100 ° C, the storage elastic modulus decreases as the temperature is raised from room temperature, and even if it is less than 100 ° C, the adhesion is simultaneously increased with temperature. Good, but in order to obtain practical adhesion, it is preferably 60 ° C or more. In addition, when the phosphor sheet is heated at a temperature exceeding 100 ° C, the storage modulus is further lowered, and the adhesion is improved. However, the stress relaxation is insufficient in a temperature exceeding 150 ° C. The hardening of the resin proceeds rapidly, and cracking or peeling easily occurs. Therefore, the preferred heating and attaching temperature is 60 ° C to 150 ° C, and more preferably 60 ° C to 120 ° C. For the purpose of the present invention, the lower limit of the storage elastic modulus at 100 ° C is not particularly limited, but if the fluidity is too high when the LED element is heated and attached, it cannot be maintained by cutting or opening before attachment. Since the shape is processed, the lower limit of the storage elastic modulus is preferably 0.001 MPa or more.

When the storage elastic modulus is obtained as a phosphor sheet, the resin contained therein may be an unhardened or semi-hardened resin, but the operability of the sheet is considered as follows. The resin contained in the storage property or the like is preferably a resin after curing. When the resin is in an uncured or semi-hardened state, the curing reaction is carried out at room temperature during storage of the phosphor sheet, and the storage elastic modulus is out of the proper range. In order to prevent such a concern, it is preferred that the resin be hardened or stored in a room temperature for a period of about one month, and the hardening is carried out until the storage elastic modulus does not change.

(resin)

The resin contained in the phosphor sheet of the present invention is a resin in which a phosphor is uniformly dispersed inside, and any resin can be used as long as it can form a sheet.

Specific examples thereof include an anthrone resin, an epoxy resin, a polyarylate resin, a polyethylene terephthalate (PET) modified polyarylate resin, a polycarbonate resin, a cyclic olefin, and the like. Polyethylene terephthalate resin, polymethyl methacrylate resin, polypropylene resin, modified acrylic acid, polystyrene resin and acrylonitrile. Styrene copolymer resin and the like. Here, PET means polyethylene terephthalate. In the present invention, in terms of transparency, an anthrone resin or an epoxy resin is preferably used. Further, in terms of heat resistance, it is particularly preferable to use an fluorenone resin.

The fluorenone resin used in the present invention is preferably a hardened fluorenone rubber. It can be composed of one liquid type or two liquid type (three liquid type). In the curable fluorenone rubber, a type which causes a condensation reaction by moisture or a catalyst in the air includes a dealcoholization type, a dehydration type, a deacetation type, and a dehydroxyamine type. Further, as a type which generates a hydrazine hydrogenation reaction by a catalyst, there is an addition reaction type. Any of these types of hardened fluorenone rubbers can be used. In particular, an oxime rubber having an addition reaction type is more preferable because it does not have a by-product accompanying the hardening reaction and has a small hardening shrinkage and is easily accelerated by heating.

As an example, the addition reaction type fluorenone rubber is formed by a hydrogenation reaction of a compound containing an alkenyl group bonded to a ruthenium atom with a compound having a hydrogen atom bonded to a ruthenium atom. Such materials can be exemplified by the following materials, which are borrowed Containing a bond by vinyl trimethoxy decane, vinyl triethoxy decane, allyl trimethoxy decane, propylene trimethoxy decane, norbornene trimethoxy decane, octenyl trimethoxy decane, etc. a compound of an alkenyl group attached to a ruthenium atom, with a methyl hydrogenated polyoxane, a dimethyl polyoxane-CO-methyl hydrogenated polyoxyalkylene, an ethyl hydrogenated polyoxyalkylene, a methyl hydrogenated polymer A hydrazine hydrogenation reaction of a compound having a hydrogen atom bonded to a ruthenium atom such as a siloxane or a CO-methylphenyl polysiloxane. In addition, a known material as described in Japanese Laid-Open Patent Publication No. 2010-159411 can be used.

Control storage at room temperature (25 ° C) by properly designing the resins The elastic modulus and the storage elastic modulus at a high temperature (100 ° C) give a resin useful for the practice of the present invention.

In addition, commercially available resins can also be sealed from fluorenone for general LED applications. A resin having an appropriate storage elastic modulus is selected for use in the material. Specific examples are: Toray. OE-6630A/B, OE-6520A/B, manufactured by Toray Dow Corning.

(fluorescent body)

The phosphor absorbs the blue light, the violet light, and the ultraviolet light emitted from the LED chip to convert the wavelength, and emits light of a wavelength of red, orange, yellow, green, and blue regions different in wavelength from the light of the LED chip. Thereby, a part of the light emitted from the LED wafer is mixed with a part of the light emitted from the phosphor to obtain a multicolor LED including white. Specifically, a single LED can be used by optically combining a phosphor that emits light of a yellow luminescent color by light from the LED in the blue LED. The wafer emits white light.

The phosphor described above includes a plurality of phosphors such as a phosphor that emits green light, a phosphor that emits blue light, a phosphor that emits yellow light, and a phosphor that emits red light. Specific examples of the phosphor used in the present invention include known phosphors such as an organic phosphor, an inorganic phosphor, a fluorescent pigment, and a fluorescent dye. The organic phosphor can be exemplified by allylsulfonamide. A melamine-formaldehyde co-condensation dye or a perylene-based phosphor or the like is preferably used in the long-term use, and a lanthanide-based phosphor is preferably used. The phosphor which is particularly preferably used in the present invention is an inorganic phosphor. The inorganic phosphor used in the present invention will be described below.

The phosphor that emits green light is, for example, SrAl ₂ O ₄ :Eu, Y ₂ SiO ₅ :Ce, Tb, MgAl ₁₁ O ₁₉ :Ce, Tb, Sr ₇ Al ₁₂ O ₂₅ :Eu, (Mg, Ca, Sr At least one or more of Ba) Ga ₂ S ₄ :Eu or the like.

Examples of the phosphor that emits blue light include: Sr ₅ (PO ₄ ) ₃ Cl:Eu, (SrCaBa) ₅ (PO ₄ ) ₃ Cl:Eu, (BaCa) ₅ (PO ₄ ) ₃ Cl:Eu, (Mg, At least one of Ca, Sr, and Ba) ₂ B ₅ O ₉ Cl: Eu, Mn, (at least one of Mg, Ca, Sr, and Ba) (PO ₄ ) ₆ Cl ₂ : Eu, Mn, etc. .

The phosphor that emits green to yellow light is: at least the sputum activated by sputum. Aluminium oxide phosphor, at least activated by strontium. Hey. Aluminium oxide phosphor, at least activated by strontium. aluminum. a garnet oxide phosphor, and a ruthenium activated at least by ruthenium. gallium. Aluminum oxide phosphor or the like (so-called yttrium aluminum garnet (YAG)-based phosphor). Specifically, Ln ₃ M ₅ O ₁₂ : R (Ln is at least one selected from the group consisting of Y, Gd, and La; M includes at least one of Al and Ca; R is a lanthanide); _1-x Ga _x ) ₃ (Al _1-y Ga _y ) ₅ O ₁₂ : R (R is at least one selected from the group consisting of Ce, Tb, Pr, Sm, Eu, Dy, and Ho; 0<x<0.5 , 0 < y < 0.5).

Examples of the phosphor that emits red light include Y ₂ O ₂ S:Eu, La ₂ O ₂ S:Eu, Y ₂ O ₃ :Eu, Gd ₂ O ₂ S:Eu, and the like.

Further, examples of the phosphor that emits light corresponding to the current mainstream blue LED include Y ₃ (Al, Ga) ₅ O ₁₂ :Ce, (Y, Gd) ₃ Al ₅ O ₁₂ :Ce, Lu ₃ Al ₅ O ₁₂ : YAG-based phosphor such as Ce, Y ₃ Al ₅ O ₁₂ :Ce, terbium aluminum garnet (TAG)-based phosphor, Tb ₃ Al ₅ O ₁₂ :Ce, (Ba,Sr) ₂ SiO ₄ :Eu-based phosphor or Ca ₃ Sc ₂ Si ₃ O ₁₂ :Ce-based phosphor, (Sr, Ba, Mg) ₂ SiO ₄ : Eu-based citrate-based phosphor, (Ca, Sr) ₂ Si ₅ N ₈ :Eu, (Ca,Sr)AlSiN ₃ :Eu, a nitride-based phosphor such as CaSiAlN ₃ :Eu, a nitrogen oxide such as Ca _x (Si,Al) ₁₂ (O,N) ₁₆ :Eu Fluorescent body, and (Ba, Sr, Ca)Si ₂ O ₂ N ₂ :Eu-based phosphor, Ca ₈ MgSi ₄ O ₁₆ Cl ₂ :Eu-based phosphor, SrAl ₂ O ₄ :Eu, Sr ₄ Al ₁₄ O ₂₅ : a phosphor such as Eu.

Among these phosphors, a YAG-based phosphor, a TAG-based phosphor, and a citrate-based phosphor are preferably used in terms of luminous efficiency, brightness, and the like.

In addition to the above, a known phosphor can be used depending on the use or the target luminescent color.

The particle size of the phosphor is not particularly limited, and it is preferably such that D50 is 0.05 μm or more, and more preferably 3 μm or more. Further, it is preferable that the D50 is 30 μm or less. Here, D50 is a particle diameter when the cumulative passage rate from the small particle diameter side reaches 50% in the volume-based particle size distribution obtained by the measurement by the laser diffraction scattering particle size distribution measurement method. If D50 is in the range, then in the phosphor sheet The phosphor has good dispersibility and stable luminescence can be obtained.

In the present invention, the content of the phosphor is not particularly limited, but the source is increased. The content of the phosphor is preferably 30% by weight or more, and more preferably 40% by weight or more based on the entire phosphor sheet, from the viewpoint of wavelength conversion efficiency of light emission of the LED wafer. The upper limit of the content of the phosphor is not particularly limited. However, from the viewpoint of easily forming a phosphor sheet having excellent workability, it is preferably 95% by weight or less, and more preferably 90% by weight of the entire phosphor sheet. % or less is particularly preferably 85% by weight or less, particularly preferably 80% by weight or less.

The phosphor sheet of the present invention is particularly preferably used for surface coating of an LED wafer. use. At this time, by the content of the phosphor in the phosphor sheet being in the above range, an LED light-emitting device exhibiting excellent performance can be obtained.

(fluorenone microparticles)

The phosphor sheet in the present invention may contain fluorenone fine particles in order to improve the fluidity of the resin composition for producing a phosphor sheet and to improve the coatability. The fluorenone fine particles contained are preferably fine particles containing an fluorenone resin and/or an anthrone rubber. Particularly preferably, it is hydrolyzed by using an organic decane such as an organic trialkoxy decane or an organic dialkoxy decane, an organic triethoxy decane, an organic diethyl methoxy decane, an organic trioxane or an organic dioxane. The fluorenone microparticles are obtained by a method of condensing them.

The organotrialkoxydecane can be exemplified by methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-propoxydecane, methyltris-isopropoxydecane, and methyltri-n-butylene. Oxy decane, methyl tri-isobutoxy decane, methyl tri-second butoxy decane, methyl tri-tert-butoxy decane, ethyl trimethoxy decane, n-propyl trimethoxy Base decane, isopropyl trimethoxy decane, n-butyl tributoxy decane, isobutyl tributoxy decane, second butyl trimethoxy decane, tert-butyl tributoxy decane, N- β (aminoethyl) γ-aminopropyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, vinyltrimethoxydecane, phenyltrimethoxydecane, and the like.

The organic dialkoxy decane can be exemplified by dimethyl dimethoxy decane, dimethyl diethoxy decane, methyl ethyl dimethoxy decane, methyl ethyl diethoxy decane, and diethyl. Diethoxydecane, diethyldimethoxydecane, 3-aminopropylmethyldiethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethyl Oxydecane, N-(2-aminoethyl)-3-aminoisobutylmethyldimethoxydecane, N-ethylaminoisobutylmethyldiethoxydecane, (phenylaminomethyl) And methyl dimethoxy decane, vinyl methyl diethoxy decane, and the like.

The organic triethoxydecane can be exemplified by methyltriethoxydecane, ethyltriethoxydecane, vinyltriethoxydecane or the like.

The organic diethoxy decane can be exemplified by dimethyldiethoxydecane, methylethyldiethoxydecane, vinylmethyldiethoxydecane, vinylethyldiethoxycarbonyl. Base decane and the like.

The organic trioxane is exemplified by methyl trimethyl ethyl ketone decane and vinyl trimethyl ethyl ketone decane, and the organic dioxane is exemplified by methyl ethyl bismethyl ethyl ketone decane.

Specifically, such a particle can be obtained by the method described in Japanese Laid-Open Patent Publication No. SHO63-77940, the method of Japanese Patent Application Laid-Open No. Hei. -342370 The method reported in the publication, the method reported in Japanese Laid-Open Patent Publication No. Hei-4-88022, and the like. Further, a method is also known: an organic decane such as an organic trialkoxy decane or an organic dialkoxy decane, an organic triethoxy decane, an organic diethyl methoxy decane, an organic trioxane or an organic dioxane. And / or a part of its hydrolyzate is added to the aqueous alkali solution to hydrolyze it. a method of obtaining particles by condensation; or adding an organic decane and/or a partial hydrolyzate thereof to water or an acidic solution to obtain a hydrolyzed partial condensate of the organodecane and/or a partial hydrolyzate thereof, and then adding a base to carry out a condensation reaction, A method for obtaining particles; using an organic decane and/or a hydrolyzate thereof as an upper layer, a mixture of a base or a base and an organic solvent as a lower layer, and hydrolyzing the organodecane and/or its hydrolyzate at the interface of the layers. A method of obtaining a particle by polycondensation, etc.; the particles used in the present invention can be obtained in any of the methods.

Among these methods, it is preferred to utilize the hydrolysis of the organodecane and/or its partial hydrolyzate. When spheroidal fluorenone microparticles are produced by condensation, a method of adding a polymer dispersant such as a water-soluble polymer or a surfactant to the reaction solution is carried out to obtain fluorenone microparticles. Any of a synthetic polymer and a natural polymer can be used as long as it is a polymer which functions as a protective colloid in a solvent. Specific examples thereof include water-soluble polymers such as polyvinyl alcohol and polyvinylpyrrolidone. The surfactant may be used as a protective colloid by having a hydrophilic portion and a hydrophobic portion in the molecule. Specific examples thereof include anionic surfactants such as sodium dodecylbenzenesulfonate, ammonium laurylbenzenesulfonate, sodium lauryl sulfate, ammonium lauryl sulfate, and sodium polyoxyethylene alkyl ether sulfate. a cationic active agent such as lauryl trimethyl ammonium chloride or stearyl trimethyl ammonium chloride, polyoxyethylene alkyl ether, polyoxyethylene distyryl phenyl ether, polyoxyalkylene alkyl alkenyl ether, An ether-based or ester-based nonionic surfactant such as a sorbitan monoalkylate; a polyether modified polydimethyl siloxane, a polyester modified polydimethyl siloxane, an aralkyl group An anthrone-based surfactant such as a polyalkyl siloxane or a fluorine-based surfactant such as a perfluoroalkyl group-containing oligomer or an acrylic surfactant. The method of adding the dispersing agent can be exemplified by a method of previously adding to the initial liquid of the reaction; a method of simultaneously adding with the organic trialkoxy decane and/or a partial hydrolyzate thereof; and hydrolyzing the organotrialkoxy decane and/or a portion thereof A method of adding a portion after condensation of a hydrolysis; any one of the methods may be selected. The amount of the dispersant added is preferably in the range of 5 × 10 ^-7 parts by weight to 0.1 parts by weight based on 1 part by weight of the reaction liquid. When the lower limit is exceeded, the particles easily aggregate with each other to form agglomerates. On the other hand, when the upper limit is exceeded, the amount of the dispersant in the particles increases, which causes coloring.

For the purpose of controlling the dispersibility or wettability in the matrix component, etc. Some anthrone particles can also be modified with a surface modifier to modify the surface of the particles. The surface modifying agent may be modified by physical adsorption, or may be modified by a chemical reaction, and specifically, a decane coupling agent, a thiol coupling agent, a titanate coupling agent, and an aluminate may be mentioned. The salt coupling agent, the fluorine-based coating agent, and the like are particularly preferably modified with a decane coupling agent in terms of high heat resistance and no hardening inhibition.

The organic substituent contained in the fluorenone microparticles is preferably a methyl group or a phenyl group. The refractive index of the fluorenone microparticles is adjusted by the content of the substituents. In the case where the brightness of the LED light-emitting device is not lowered, and it is intended to be used in a state in which light passing through the fluorenone resin as the binder resin is not scattered, the fluorenone fine particles are preferably used. The refractive index d1 is smaller than the refractive index difference of the refractive index d2 caused by the components other than the fluorenone fine particles and the phosphor. The difference between the refractive index d1 of the fluorene ketone fine particles and the refractive index of the refractive index d2 caused by the components other than the fluorenone fine particles and the phosphor is preferably less than 0.10, particularly preferably 0.03 or less. By controlling the refractive index within this range, the reflection of the interface between the fluorenone microparticles and the fluorenone composition. The scattering is reduced, high transparency and light transmittance are obtained, and the brightness of the LED light-emitting device is not lowered.

When measuring the refractive index, as a total reflection method, Abbe can be used. A refractometer, a Pulfrich refractometer, a liquid immersion refractometer, a liquid immersion method, a minimum deflection angle method, etc., an Abbe refractometer can be used for the refractive index measurement of an anthrone composition, and the fluorenone microparticles are refracted. The liquid immersion method can be used for the rate measurement.

In addition, as a method for controlling the refractive index difference, by changing The amount ratio of the raw materials constituting the fluorene ketone fine particles is adjusted. In other words, for example, by adjusting the mixing ratio of methyltrialkoxy decane and phenyltrialkoxy decane as a raw material, the composition ratio of the methyl group can be increased to achieve a low refractive index close to 1.4, and conversely, A relatively high refractive index is obtained by increasing the composition ratio of the phenyl group.

In the present invention, the average particle diameter of the fluorenone microparticles is determined by the median diameter (D50). The lower limit of the average particle diameter is preferably 0.01 μm or more, and particularly preferably 0.05 μm or more. Further, the upper limit is preferably 2.0 μm or less, and particularly preferably 1.0 μm or less. When the average particle diameter is 0.01 μm or more, it is easy to produce particles whose particle diameter is controlled, and when the average particle diameter is 2.0 μm or less, the optical characteristics of the phosphor sheet become good. In addition, by having an average particle diameter of 0.01 μm or more and 2.0 μm or less, a sufficient fluidity improving effect of the resin liquid for producing a phosphor sheet can be obtained. In addition, it is preferred to Use monodisperse and spherical particles. In the present invention, the average particle diameter of the fluorenone microparticles contained in the phosphor sheet, that is, the median diameter (D50) and the particle size distribution can be observed by a Scanning Electron Microscope (SEM) of the sheet cross section. To determine. The measurement image obtained by SEM was subjected to image processing to obtain a particle size distribution, and in the particle size distribution thus obtained, a particle diameter of 50% from the small particle diameter side as a median diameter was determined. D50. In this case, as in the case of the phosphor particles, the average particle diameter of the fluorenone microparticles obtained from the cross-sectional SEM image of the phosphor sheet is theoretically 78.5 as compared with the true average particle diameter. % is actually approximately 70% to 85%, but the average particle diameter of the fluorenone microparticles in the present invention is defined as a value obtained by the above measurement method.

The lower limit of the content of the fluorenone microparticles relative to 100 parts by weight of the fluorenone resin It is preferably 1 part by weight or more, and particularly preferably 2 parts by weight or more. Further, the upper limit is preferably 20 parts by weight or less, and particularly preferably 10 parts by weight or less. When the fluorenone fine particles are contained in an amount of 1 part by weight or more, a particularly good phosphor dispersion stabilizing effect is obtained. On the other hand, when the content is 20 parts by weight or less, the viscosity of the fluorenone composition is not excessively increased.

(other ingredients)

In order to impart effects such as viscosity preparation, light diffusion, and coating property, the phosphor sheet of the present invention may further contain an inorganic fine particle filler. Examples of the inorganic filler include cerium oxide, aluminum oxide, titanium oxide, zirconium oxide, barium titanate, and zinc oxide.

Further, in the present invention, in the fluorenone resin composition used for producing a phosphor sheet, in order to suppress curing at normal temperature and to extend the pot life, it is preferred to prepare a hydrazine hydrogenation reaction retarder such as acetylene alcohol as another ingredient. In addition, as other As the additive, a leveling agent for stabilizing the coating film, a bonding aid such as a decane coupling agent as a modifier for the surface of the sheet, and the like may be added.

(film thickness)

The film thickness of the phosphor sheet of the present invention is determined by the phosphor content and the desired optical characteristics. As described above, the phosphor content is limited in terms of workability, and therefore the film thickness is preferably 10 μm or more. On the other hand, it improves the optical properties of the phosphor sheet. The film thickness of the phosphor sheet is preferably 1000 μm or less, more preferably 200 μm or less, and still more preferably 100 μm or less from the viewpoint of heat dissipation. By setting the phosphor sheet to a film thickness of 1000 μm or less, light absorption or light scattering due to the binder resin or the phosphor can be reduced, and thus the phosphor sheet is excellent in optical properties.

Further, when the film thickness of the sheet is uneven, a difference in the amount of phosphors occurs in each of the LED wafers, and as a result, unevenness occurs in the emission spectrum (color temperature, luminance, and chromaticity). Therefore, the unevenness of the film thickness of the sheet is preferably within ±5%, and particularly preferably within ±3%.

The film thickness of the phosphor sheet of the present invention is a film thickness measured by a method A for measuring the thickness by mechanical scanning in the plastic-film and sheet-thickness measuring method of JIS K7130 (1999). Film thickness). Further, the film thickness unevenness of the phosphor sheet was calculated based on the following mathematical formula using the above-described average film thickness. More specifically, the measurement conditions of the thickness measurement method by the mechanical scanning method are used, and the film thickness is measured using a micrometer such as a commercially available contact thickness meter, and the maximum or minimum thickness of the obtained film thickness is calculated. The difference between the value and the average film thickness, and the value expressed by the fraction of 100, divided by the average film thickness, becomes the film thickness unevenness B (%).

Film thickness unevenness B (%) = {(maximum film thickness deviation - average film thickness) / flat Mean film thickness}×100

Here, the maximum film thickness deviation value is a value at which the difference between the maximum value and the minimum value of the film thickness and the average film thickness is large.

<Support substrate>

The support substrate protects the phosphor sheet which is easily deformed in shape, facilitates storage, handling, and processing, and facilitates handling in the attaching step to the LED wafer to prevent adhesion to the pressurized substrate. Or pollution.

(support the physical properties of the substrate)

The support substrate has an elongation at break of 200% or more at 23 ° C and a Young's modulus of 600 MPa or less. When the elongation at break of the support substrate is less than 200% or the Young's modulus is more than 600 MPa, a gap is formed between the side surface and the phosphor sheet in the LED attaching step, and the followability is deteriorated. From the viewpoint of the followability to the LED wafer, the elongation at break is preferably 300% or more, and more preferably 500% or more. Further, the Young's modulus is preferably 400 MPa or less, more preferably 100 MPa or less, and still more preferably 10 MPa or less. The upper limit of the elongation at break is not particularly limited, but is preferably 1500% or less, more preferably 1,000% or less, still more preferably 800% or less, and particularly preferably 750% or less from the viewpoint of easy cutting. Further, the lower limit of the Young's modulus is not particularly limited, but it is preferably 0.1 MPa or more, more preferably 1 MPa or more, from the viewpoint of supporting the base material without deformation and protecting the phosphor sheet. 1.6MPa or more.

The elongation at break and the Young's modulus can be determined by the method according to ASTM-D882-12. The specific measurement method is to stretch the test piece at a speed of 300 mm/min using a tensile tester while maintaining the temperature at a constant temperature. When the length of the test piece before the test was L ₀ and the length of the test piece at the time of cutting (fracture) was L, the elongation at break was calculated by the following mathematical formula.

Elongation at break (%) = 100 × (LL ₀ ) / L ₀ .

Further, the Young's modulus can be obtained from the maximum inclination of the S-S curve obtained by plotting the maximum elasticity before the test piece is deformed, that is, the elongation of the test piece and the load to be applied thereto. The number of times of measurement of the elongation at break and the Young's modulus is three times in order to improve the accuracy, and the average value thereof is obtained.

The attachment temperature of the phosphor sheet is as described above, preferably 60 to 150 ° C, and more preferably 60 to 120 ° C. Therefore, the thermal properties of the support substrate are preferably such that they do not melt within this temperature range. From this point of view, the melting point of the support substrate is preferably 120 ° C or higher, and particularly preferably 150 ° C or higher.

Further, the peeling force of the support substrate is preferably from the viewpoint of maintaining the adhesion of the phosphor sheet and the peeling property for peeling the support substrate after being attached to the LED wafer. It is in the range of 0.5N/20mm~2.5N/20mm. The so-called peeling force here is the adhesive tape specified in JIS Z 0237 (2009). The value obtained by the 90 degree peel adhesion test method in the adhesive sheet method.

In general, the surface average roughness Ra of the support substrate is preferably 1 μm or less from the viewpoint of uniformity of light emission, but may be embossed for the purpose of improving light extraction. Surface processing such as machining.

(Support material of the substrate)

Specific examples of the material of the support substrate include polyvinyl chloride, polyurethane, fluorenone, low density polyethylene (LDPE), and polyvinyl acetal. The polyvinyl chloride is hard and soft depending on the amount of the plasticizer added, but is preferably soft. Further, the anthrone has a resin and a rubber, but is preferably an anthrone rubber which is excellent in stretchability. Among them, polyvinyl chloride, polyurethane or fluorenone is preferred from the viewpoint of high elongation, low Young's modulus, thermal properties, adhesion, and peelability. More preferably, it is a polyvinyl chloride or a polyurethane, and particularly preferably a soft polyvinyl chloride or a polyurethane, and most preferably a polyurethane (polyurethane film).

The film of the material may be controlled by, for example, low density, no elongation, an increase in the amount of the monomer of the soft component, an increase in the plasticizer, or the like, and the elongation at break and the Young's modulus are controlled as described above. Within the preferred range.

(Support film thickness of substrate)

The film thickness of the support substrate is preferably from 5 μm to 500 μm, more preferably from 20 μm to 200 μm, still more preferably from 40 μm to 100 μm. Further, the film thickness of the support substrate preferably satisfies the following mathematical formula with respect to the film thickness of the phosphor sheet.

1/5 ≦ (film thickness of supporting substrate / film thickness of phosphor sheet) ≦ 3

When it is more than the lower limit, the support substrate can obtain sufficient mechanical strength for protecting the phosphor sheet. In addition, when it is less than the upper limit, sufficient followability can be obtained for the LED wafer in the attachment of the phosphor sheet. In this regard, (support base The lower limit of the film thickness of the material/the film thickness of the phosphor sheet is more preferably 1/2 or more. Further, the upper limit is more preferably 2 or less, and particularly preferably 1 or less.

<Other constitutions in the laminated body>

The laminate of the present invention may also have an adhesive on the support substrate. Fig. 2 is an example of a laminate having an adhesive. In this case, the layered body 1 is formed such that the surface on which the adhesive 4 is applied is in contact with the phosphor sheet 3, and the phosphor sheet 3 is fixed to the support substrate 2 by the adhesive 4. The adhesive force of the adhesive is preferably 0.1 N/20 mm or more from the viewpoint of holding the phosphor sheet on the support substrate. Further, from the viewpoint of coating the LED wafer with the phosphor sheet and peeling the support substrate, it is preferably 1.0 N/20 mm or less.

In addition, for the purpose of protecting the surface of the phosphor sheet, the product of the present invention The layer body may also be provided with a protective substrate on the phosphor sheet. As the protective substrate, a known metal, film, glass, ceramic, paper, or the like can be used. Specific examples include metal sheets or foils such as aluminum (including aluminum alloys), cellulose acetate, polyethylene terephthalate (PET), polyethylene, polyester, polyamide, and polyimide. A film of polyphenylene sulfide, polystyrene, polypropylene, polycarbonate, aromatic polyamide, fluororesin, or the like, and a processed paper such as a resin laminated paper or a resin coated paper. In order to prevent the phosphor sheet from adhering during storage, it is preferable that the protective substrate is subjected to a release treatment in advance on the surface. Further, in order to prevent the phosphor sheet from being bent or the surface from being damaged during storage or transportation, a substrate having high strength is preferable. In terms of satisfying the required characteristics, a film or paper is preferable, and in terms of economy and workability, it is more preferable to peel-treat the PET film or the release paper.

<Method of Manufacturing Laminates>

The method for producing the layered product of the present invention may be any method capable of forming the layered body, and examples thereof include a direct coating method, a transfer method using an adhesive, and a thermal transfer method.

The direct coating method is a method in which a composition for producing a phosphor sheet is coated on a support substrate and then heat-cured. In addition, the "component for producing a phosphor sheet" is a composition used as a coating liquid for forming a phosphor sheet, as described later, "a composition for producing a phosphor sheet". It is a composition in which a phosphor is dispersed in a resin.

The transfer method using an adhesive is a method in which an adhesive surface of a support substrate having an adhesive is bonded to a phosphor sheet produced on a second substrate, from the second substrate to the support substrate. Transfer the phosphor sheet.

The thermal transfer method is a method in which a phosphor sheet produced on a second substrate is heated and pressure-bonded to a support substrate, and transferred onto a support substrate from a second substrate.

From the viewpoint of producing a phosphor sheet having a high film thickness precision, the method for producing a laminate is preferably a transfer method using an adhesive and a thermal transfer method, and further, a support substrate to which the LED wafer is attached From the viewpoint of peelability, a thermal transfer method is preferred.

Here, the production of the phosphor sheet will be described. In addition, the method of producing a phosphor sheet as an example below is not limited to this. First, a composition obtained by dispersing a phosphor in a resin (hereinafter referred to as "a composition for producing a phosphor sheet") is prepared as a coating liquid for forming a phosphor sheet. For the purpose of suppressing sedimentation of the phosphor, fluorenone microparticles may be added, and other additives such as inorganic microparticles, a leveling agent, and an adhesion aid may be added. In addition, in the use of addition reaction type fluorenone resin In the case of a resin, a hydrogenation reaction retarder may also be formulated to extend the pot life. In order to make the fluidity appropriate, if necessary, a solvent may be added to prepare a solution. The solvent is not particularly limited as long as it is a viscosity of a resin in which the flow state can be adjusted. For example, toluene, methyl ethyl ketone, methyl isobutyl ketone, hexane, acetone, terpineol, etc. are mentioned.

After the ingredients are blended into a predetermined composition, the homogenizer and the self-rotating 3. Mixing mixer, three roller machine, ball mill, planetary ball mill, bead mill, etc. The kneader was mixed and dispersed homogeneously, whereby a composition for producing a phosphor sheet was obtained. It is also preferred to carry out the following operations: defoaming under vacuum or reduced pressure during mixing or dispersion or during mixing and dispersion.

Then, the composition for producing a phosphor sheet is applied onto a substrate to dry. Coating can be carried out using a coating machine: a reverse roll coater, a blade coater, a slit die coater, a direct gravure coater (direct Gravure coater), offset gravure coater, reverse roll coater, knife coater, kiss coater, natural roll coater, air knife coating Air knife coater, roll blade coater, vari-bar roll blade coater, two stream coater, bar coating Rod coater, wire bar coater, applicator, dip coater, curtain coater, spin coater ), a knife coater, and the like. In order to obtain uniformity of the film thickness of the phosphor sheet, it is preferably Coating was carried out using a slit die coater. Further, the phosphor sheet of the present invention can also be produced by a printing method such as screen printing, gravure printing or lithography. In the case of using the printing method, it is particularly preferable to use screen printing.

Drying of the phosphor sheet. Use a hot air dryer or infrared dry when hardening A general heating device such as a dryer. The heat-hardening condition is usually from 80 ° C to 200 ° C for 2 minutes to 3 hours, but in order to be softened by heating, a so-called B-stage state in which adhesion is exhibited is preferably carried out at 80 ° C to 120 ° C. Minutes ~ 2 hours.

For the second use of the transfer method by the adhesive and the thermal transfer method In the case of the substrate, it is not particularly limited, and a known metal, film, glass, ceramic, paper, or the like can be used. In order to produce a phosphor sheet having a high film thickness precision, it is preferred that the second substrate has an elongation at break of less than 200% at 23 ° C or a Young's modulus of more than 600 MPa, particularly a Young's modulus. Good is 4000MPa or more. Further, it is preferably a substrate which is less deformed at a temperature of 150 ° C or higher which is rapidly progressed by the curing reaction of the resin.

Specifically, aluminum (also including aluminum alloy), zinc, copper, iron Metal sheets or foils, cellulose acetate, polyethylene terephthalate (PET), polyethylene, polyester, polyamide, polyimide, polyphenylene sulfide, polystyrene, polypropylene, a plastic film of polycarbonate, polyvinyl acetal, aromatic polyamine, or the like, paper laminated with the plastic, or paper coated with the plastic, laminated or vapor-deposited with the metal Paper, laminated or vapor-deposited plastic film of the metal.

Among the substrates, in terms of the required characteristics or economics, A resin film is preferred, and a PET film or a polyphenylene sulfide film is particularly preferred. In addition, when the resin is hardened or the phosphor sheet is attached to the LED, a high temperature of 200 ° C or higher is required. In the case of heat resistance, a polyimide film is preferred.

Moreover, in order to facilitate the transfer of the phosphor sheet, it is preferred that the second substrate be subjected to a release treatment in advance.

The thickness of the second substrate is not particularly limited, and the lower limit is preferably 30 μm or more, and more preferably 50 μm or more. Further, the upper limit is preferably 5,000 μm or less, more preferably 3,000 μm or less.

The transfer from the second substrate to the support substrate by the adhesive is preferably carried out by a laminator equipped with a roll so as not to cause air to enter.

Further, the thermal transfer from the second substrate to the support substrate is preferably carried out by a thermal laminator including a heating mechanism and a pressurizing mechanism. Here, from the viewpoint of softening the phosphor sheet and exhibiting adhesiveness, the thermal transfer is preferably carried out at 60 ° C or higher. Further, from the viewpoint of maintaining the B-stage state (that is, the semi-hardened state) of the phosphor sheet, it is preferably carried out at 120 ° C or lower. Further, from the viewpoint of maintaining the uniformity of the film thickness, the pressurizing pressure is preferably 0.3 MPa or less, and the pressurizing time is preferably 30 seconds or shorter, more preferably 10 seconds or shorter.

<Method of Manufacturing Light Emitting Device>

A method of manufacturing a light-emitting device using the laminate of the present invention will be described.

In the present invention, it is preferable to manufacture a light-emitting device by using a manufacturing method including the following step (coating step): a light-emitting surface of an LED wafer bonded (mounted) on a substrate, and a phosphor sheet of the laminated body of the present invention The step of covering.

Further, in the case where the light-emitting surface of the LED wafer is the upper surface and the side surface of the LED wafer, it is preferable to use a manufacturing method including the following steps (coating step). Manufacturing of a light-emitting device: a step of coating a phosphor sheet of a laminate of the present invention on an upper surface and a side surface of an LED wafer bonded (mounted) on a substrate.

As described above, the light-emitting device using the laminate of the present invention is preferably provided by After the LED wafer is bonded (mounted) to the substrate, the upper light-emitting surface and the side light-emitting surface of the LED wafer are coated with a phosphor sheet using the laminate of the present invention.

The substrate refers to a substrate in which an LED wafer is fixed and connected to a wiring. The substrate may be, for example, a base substrate or a sub-mount substrate. The material of the substrate is not particularly limited, and examples thereof include a polyphthalamide (PPA), a liquid crystal polymer, a resin such as an anthrone, aluminum nitride (AlN), alumina (Al ₂ O ₃ ), and nitrogen. A ceramic such as boron (BN) or a metal such as aluminum.

For example, a person who forms an electrode pattern using silver or the like is used on the substrate. Also An exothermic mechanism can be included.

The LED chip is preferably a wafer that emits blue light or ultraviolet light. Such The LED chip is particularly preferably a gallium nitride-based LED chip.

The type of the LED chip can be either a lateral type, a vertical type, or a flip chip type, but it is particularly preferably a flip chip type from the viewpoint of high luminance and high heat dissipation. In the present invention, the LED wafer is bonded (mounted) on the substrate, and preferably the LED wafer is electrically bonded to the substrate. As for the bonding (mounting) of the flip chip, solder bonding, eutectic bonding, and conductive paste bonding are mentioned.

The LED chips can be individually bonded (mounted) on the substrate, or a plurality of bonded (mounted) on the substrate. In addition, each package can be separately made of a phosphor sheet. In the case of line coating, a plurality of packages may be collectively covered with a phosphor sheet, and then diced by cutting or the like.

The film thickness of the LED wafer is not particularly limited as it is on the upper surface of the LED wafer. The corner portion is preferably 500 μm or less, more preferably 300 μm or less, and even more preferably 200 μm or less from the viewpoint of reducing the pressure applied to the phosphor sheet and maintaining the uniformity of the film thickness.

In addition, the total thickness and fluorescence of the LED chip and the connection portion with the substrate The film thickness of the body sheet preferably satisfies the following relationship.

1≦ (the total film thickness/phosphor of the LED chip and the connection portion with the substrate) The film thickness of the sheet is ≦10.

If it is more than the lower limit, it is easy to suppress the orientation unevenness of the luminescent color. In addition, When it is less than the upper limit, it is easy to maintain the film thickness uniformity of the phosphor sheet. From this point of view, the lower limit is preferably 2 or more. Further, the upper limit is preferably 5 or less, more preferably 4 or less.

In terms of softening the phosphor sheet to exhibit adhesion, the present invention The attachment of the laminate to the LED wafer is preferably carried out under heating. The heating temperature is preferably from 60 ° C to 150 ° C, more preferably from 60 ° C to 120 ° C, insofar as the phosphor sheet is sufficiently softened and hardly hardened.

In addition, in terms of improving the followability to the side of the wafer, the laminated body Attachment to the LED wafer is preferably carried out under pressurized conditions. The pressure sheet is preferably pressed from the side of the LED wafer to the side of the LED wafer, and the pressure is preferably 0.1 MPa to 0.3 MPa.

Specifically, a method of pressurizing and pressing the flexible sheet, a method of injecting a gas such as air, and a method of pressing in a non-contact manner, and a method of pressing the mold along the shape of the LED wafer, Or a method of pressing with a roller. In addition, a plurality of methods can be combined.

Further, in order to prevent air from entering between the phosphor sheet and the LED wafer and the substrate, the adhesion of the laminate to the LED wafer is preferably performed under vacuum conditions.

The apparatus for attaching to the LED wafer by using the laminated body of the present invention is not particularly limited as long as the above conditions are satisfied, and it is preferable to have a vacuum chamber in terms of high versatility and excellent productivity. A vacuum laminating device is provided with a pressing mechanism to which a flexible sheet is attached to a press plate. Such a vacuum laminating apparatus can be exemplified by the apparatus described in Japanese Patent No. 3,664,402.

An example of a method of manufacturing a light-emitting device using such a vacuum lamination device will be described with reference to FIGS. 3a to 3f. The vacuum laminating device comprises a vacuum chamber 5, the vacuum chamber 5 comprises: a pressing mechanism 11 comprising an upper pressing plate 6, a flexible sheet 8 and a closed space 9 surrounded by the members and air injection. Discharge port 10; lower platen 7 with heater; and another air injection. Discharge port 12. The lower platen 7 is provided with a substrate 13 to which the LED chip 14 is bonded (mounted), and further, the support substrate 2 and the phosphor sheet 3 are included in a direction in which the phosphor sheet 3 is in contact with the surface of the LED chip. The laminated bodies 1 are sequentially overlapped (Fig. 3a). Then, inject from the air. Discharge port 10 and air injection. The discharge port 12 discharges (discharges) air in the direction of the arrow indicated by the dotted line in Fig. 3b, thereby making the vacuum chamber 5 and the compactor The inside of the sealed space 9 of the structure 11 becomes a vacuum environment (Fig. 3b). Next, the lower platen 7 is heated by a heater (not shown) and injected from the air. The discharge port 10 injects air in the direction of the arrow of FIG. 3c, thereby injecting air into the sealed space 9 of the pressing mechanism 11, and expanding the flexible sheet 8 to attach the laminated body 1 to the LED wafer 14 (Fig. 3c). Then, inject from the air. The discharge port 12 injects air in the direction of the arrow of Fig. 3d, thereby injecting air into the vacuum chamber 5 to return to normal pressure (Fig. 3d), and taking out the light-emitting device 15 (Fig. 3e). Finally, the support substrate 2 is removed from the laminated body 1 attached to the light-emitting device 15 (Fig. 3f). As described above, the light-emitting device of the present invention preferably has a configuration that does not include a support substrate as shown in Fig. 3f. The reason for this is that the light-emitting device is used in a configuration in which the support substrate is removed from the laminate of the self-luminous device, or it is often used for distribution.

As described above, by using the laminated body of the present invention, one stage can be utilized By pressing the phosphor sheet on the LED wafer, a method of manufacturing a highly efficient light-emitting device can be provided.

Further, for example, the existing two-stage press as described in Patent Document 2 The pressure method, that is, the method of continuously performing the contact pressing by the flexible sheet and the non-contact pressing by the air injection, can also suitably use the laminated body of the present invention.

In particular, a plurality of layers arranged on the substrate at intervals of 1000 μm or less When the LED wafer is covered with a phosphor sheet, even if the two-stage pressing method is used alone, sufficient attaching accuracy (coating accuracy) cannot be obtained. However, even in this case, the two-stage pressing method can be used, and the laminated body of the present invention using a supporting substrate having a small Young's modulus can be used with high precision. Covered.

<Lighting device>

A light-emitting device obtained by using the laminate of the present invention will be described. 4 is a schematic view showing a cross section and an upper surface of a light-emitting device (an example) in which the LED wafer 14 bonded to the substrate 13 via the bump 18 (for example, a bump made of gold) is covered with the phosphor sheet 3 .

A schematic view of the upper surface of the light-emitting device is shown in the lower portion of FIG. Here, 16 denotes a coating portion on the upper surface and the side surface of the LED wafer, and 17 denotes a coating portion of the substrate.

On the other hand, a cross section of the light-emitting device is shown in the upper portion of FIG. The cross-sectional view shown in the upper part of FIG. 4 shows the position of the broken line II in the top view as an example. The cross section of the wafer coated with the phosphor sheet can be confirmed by a mechanical polishing method or an ion polishing method (including a cross section polishing method) to form a cross section (exposing the cross section). A digital microscope or a scanning electron microscope (SEM) to observe the profile; or a cross-section fabrication process without grinding, by X-ray computed tomography (CT) scan in a non-destructive form A method of observing the profile.

The light emitting device includes at least a substrate, an LED chip bonded (mounted) on the substrate, and a phosphor sheet covering the light emitting surface of the LED wafer. The term "light emitting surface" as used herein refers to a surface on which light of an LED is taken out. Depending on the classification of the light-emitting surface, a type in which light is taken out from the upper surface and the side surface such as a flip chip type or a side-type wafer, or a type in which light is taken out from the upper surface only in a vertical type can be exemplified. Furthermore, A type in which a side reflection layer of a flip chip is provided and only light is taken out from the upper surface is exemplified. Further, for the purpose of imparting adhesion or the like, a transparent resin may be present between the phosphor sheet and the light emitting surface of the LED. Here, the transparent resin may, for example, be a thermosetting resin such as acrylic acid, epoxy or fluorenone, and among them, an oxime resin is preferable from the viewpoint of heat resistance and light resistance.

In the above, from the viewpoint of widening the illuminating angle and reducing the unevenness of the orientation, the phosphor sheet preferably covers the upper surface and the side surface of the LED wafer. More preferably, the phosphor sheet is directly adhered to the upper surface and the side surface of the LED wafer. By using the laminate of the present invention, it is possible to produce a luminescence in which the phosphor sheet attached to the laminate is 80% or more of the upper surface area of the LED wafer and 50% or more of the side illuminating area is directly adhered to each other. Device. Finally, a light-emitting device in which the phosphor sheet attached to the laminate is 100% or more of the upper light-emitting surface area of the LED wafer and 50% or more of the side light-emitting area can be directly adhered to each other can be produced.

Here, the term "direct close contact" refers to a phosphor sheet and a LED crystal. A state in which the upper light-emitting surface or the side light-emitting surface of the sheet is bonded to each other without a void or the like. In the coating of the upper surface of the LED chip, if the direct adhesion portion is reduced, the phosphor sheet may be easily peeled off, which may cause a defect in the light-emitting device. In the present invention, when the direct contact portion is substantially 80% or more of the area of the upper surface of the LED wafer, it is difficult to cause peeling of the phosphor sheet, and the defect of the light-emitting device can be suppressed. From this point of view, the direct adhesion portion is more preferably 90% or more of the area of the upper light-emitting surface, and most preferably substantially 100%. The direct adhesion portion is substantially 100%, which means that when a microscope is used, the sheet of the phosphor is observed at a magnification of 500 times. In the cross section of the LED chip to be covered, the region of the phosphor sheet that is in direct contact with the LED chip (light emitting surface) is in a state of 100% with respect to the region of the light emitting surface of the LED chip.

In addition, if there is a light emitting surface between the LED chip and the phosphor sheet When the air layer has a small refractive index, the light extraction efficiency is lowered. Therefore, in the coating of the side surface light-emitting surface of the LED wafer, the direct adhesion portion is substantially smaller than 50% of the side-light-emitting area of the LED wafer, and the light-emitting efficiency from the side surface of the LED wafer is lowered, and the luminance is lowered. In other words, in the coating of the side surface light-emitting surface of the LED wafer, if the direct-contact portion is 50% or more of the side-light-emitting area of the LED wafer, it is possible to suppress a decrease in light extraction efficiency from the side surface of the LED chip. From this point of view, the direct adhesion portion is preferably 70% or more, more preferably 90% or more of the light-emitting area of the side surface of the LED wafer.

In the light-emitting device obtained by using the laminate of the present invention, the emission is suppressed From the viewpoint of uneven orientation of light, it is preferable that the thickness of the phosphor sheet covering the LED wafer is small in any portion, and further, the surface is derived from the side surface compared with the light emitted from the upper surface of the wafer. Since the light emission intensity is weak, it is preferable that the film thickness of the side surface portion of the LED wafer is thinner than the film thickness of the upper surface portion of the wafer. Here, the azimuth unevenness of the light emission means that the light viewing mode of the light-emitting device differs depending on the angle. Such an orientation may not be the color temperature in the distance of 10 cm in the vertical direction (hereinafter, the vertical color temperature) with respect to the upper surface of the LED wafer of the light-emitting device, and the distance of 10 cm above the inclination of 45°. The magnitude of the absolute value of the difference in color temperature (hereinafter, 45° color temperature) is determined. In the present invention, the smaller the absolute value of the difference is, the smaller the orientation unevenness of the light emission is, which is preferable.

In this regard, in the present invention, if the LED chip 14 and the fluorescent film are to be In a portion (region) where the body sheet 3 is in contact with the upper surface of the LED wafer 14, the distance from the upper surface of the LED wafer 14 to the outer surface of the phosphor sheet 3 is set to a distance a [μm], and In a portion (region) where the LED wafer 14 and the phosphor sheet 3 are in contact with the side surface of the LED wafer 14, the distance from the side surface of the LED wafer 14 to the outer surface of the phosphor sheet 3 is set to a distance b [μm] Further, from the viewpoint of suppressing unevenness in light emission, it is preferable to satisfy the relationship of 0.80 < a / b < 1.50, more preferably 1.00 < a / b < 1.20, and particularly preferably 1.00 < a / b < 1.05.

That is, the light-emitting device of the present invention preferably has a relationship of [a/b] satisfying the above-mentioned Wai. Further, when manufacturing the light-emitting device as described above, it is preferable to use a method in which the relationship of [a/b] satisfies the above range in the obtained light-emitting device.

Therefore, in order to satisfy the relationship, a light-emitting device of the present invention is obtained. A preferred manufacturing method includes the following steps (coating step): using the phosphor sheet of the laminate of the present invention, the LED wafer (especially the light emitting surface, or the upper surface and the side surface of the LED wafer) bonded to the substrate Carry out the cover.

As described above, in the step of obtaining the light-emitting device of the present invention, it is preferable to manufacture the light-emitting device that satisfies the relationship in the step of coating the coated phosphor sheet of the present invention (coating step). method.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples.

<Silver sheet>

. Anthrone resin 1: Resin principal component

※ Among them, Me: methyl, Vi: vinyl, Ph: phenyl

. Anthrone resin 2: KER6075 (manufactured by Shin-Etsu Chemical Co., Ltd.)

. Phosphor 1: NYAG-02 (manufactured by Intematix Co., Ltd.: YAG-based phosphor doped with Ce, specific gravity: 4.8 g/cm ³ , D50: 7 μm).

(Method for measuring storage elastic modulus of phosphor sheet)

Measuring device: viscoelasticity measuring device ARES-G2 (manufactured by TA Instruments)

Geometric shape: parallel circular plate type (15mm)

Strain: 1%

Angular frequency: 1Hz

Temperature range: 25 ° C ~ 140 ° C

Heating rate: 5 ° C / min

Measuring environment: in the atmosphere.

16 sheets of phosphor sheets having a film thickness of 50 μm were laminated on a heating plate at 100 ° C The integrated film (sheet) of 800 μm was produced by heating and pressure bonding, and cut into a diameter of 15 mm to prepare a measurement sample. The sample was measured using the conditions described, and the storage elastic modulus at 25 ° C and 100 ° C was measured.

(Manufacturing method of phosphor sheet) [Production Example 1 of Phosphor Sheet]

A polyethylene container having a volume of 300 ml was used, and the mixture was mixed at a ratio of 30% by weight of the fluorenone resin 1 and 70% by weight of the phosphor 1. Then, use planetary mixing. The defoaming device "Mazerustar KK-400" (manufactured by Kurabo) was stirred at 1000 rpm for 20 minutes. Defoaming was carried out to obtain a phosphor dispersion liquid for sheet production. Using a slit die coater, the sheet was applied as a phosphor dispersion liquid to a "Cerapeel" WDS (manufactured by Toray Film Processing Co., Ltd. as a substrate; film thickness was 50 μm, and the film was broken. The peeling surface of the elongation rate of 115% and the Young's modulus of 4500 MPa was heated at 120 ° C for 1 hour, and dried to obtain a phosphor sheet 1 having a film thickness of 50 μm and 100 mm square. The storage elastic modulus of the phosphor sheet was 1.0 MPa at 25 ° C and 0.025 MPa at 100 ° C.

[Production Example 2 of Phosphor Sheet]

A phosphor sheet 2 having a film thickness of 50 μm and 100 mm square was obtained in the same manner as in Production Example 1 except that the fluorenone resin 2 was used instead of the fluorenone resin 1. The storage elastic modulus of the phosphor sheet was 1.1 MPa at 25 ° C and 0.35 MPa at 100 ° C.

<Laminated body> (support substrate)

The elongation at break and the Young's modulus at 23 ° C of the support substrate were determined by using Tensilon RTF-1310 (manufactured by A & D), and were measured three times by the method according to ASTM-D882-12. average value.

Sample size: width 10mm, initial length 30mm

Measurement conditions: a temperature of 23 ° C and a tensile speed of 300 mm / min.

. Supporting substrate 1: Polyurethane film, MG90 (manufactured by Takeda Industry Co., Ltd.)

The film thickness is 50 μm, the elongation at break is 500%, and the Young's modulus is 8 MPa.

. Supporting substrate 2: Polyurethane film, MG90 (manufactured by Takeda Industry Co., Ltd.)

The film thickness is 100 μm, the elongation at break is 750%, and the Young's modulus is 8 MPa.

. Support substrate 3: polyvinyl chloride film (soft), C+ type (manufactured by Achilles)

The film thickness is 50 μm, the elongation at break is 350%, and the Young's modulus is 250 MPa.

. Support substrate 4: Polyvinyl chloride film with adhesive, T-80MW (manufactured by Electrical and Chemical Industry)

The film thickness is 50 μm, the elongation at break is 300%, and the Young's modulus is 300 MPa.

. Support substrate 5: anthrone film, eucalyptus (manufactured by Mitsubishi Resin)

The film thickness is 50 μm, the elongation at break is 450%, and the Young's modulus is 1.6 MPa.

. Supporting substrate 6: ethylene-tetrafluoroethylene (ETFE) film, resistant to fluorocarbon (Neoflon) EF-0050 (manufactured by Daikin)

The film thickness was 50 μm, the elongation at break was 450%, and the Young's modulus was 640 MPa.

[Manufacturing Example 1]

The support substrate 1 was placed on the phosphor sheet 1 formed on the "Cerapeel" WDS, and a roll type thermal laminator was used at a temperature of 80 ° C, a pressurization pressure of 0.3 MPa, and a feed rate of 0.5. m/min is pressed. After leaving to cool to room temperature, the "Cerapeel" WDS was peeled off to obtain a laminate 1.

[Manufacturing Example 2]

The laminate 2 was obtained in the same manner as in Production Example 1 except that the phosphor sheet 2 was used instead of the phosphor sheet 1.

[Manufacturing Example 3]

The laminate 3 was obtained in the same manner as in Production Example 1 except that the support substrate 2 was used instead of the support substrate 1.

[Manufacturing Example 4]

The laminate 4 was obtained in the same manner as in Production Example 1 except that the support substrate 3 was used instead of the support substrate 1.

[Manufacturing Example 5]

On the phosphor sheet 1 formed on the "Cerapeel" WDS, the support substrate 4 is placed in contact with the phosphor layer with the adhesive layer, and a roll laminator is used at a temperature of 25 Pressed at °C, a pressurizing pressure of 0.3 MPa, and a feed rate of 1.0 m/min. After leaving to cool to room temperature, the "Cerapeel" WDS was peeled off to obtain a layered body 5.

[Manufacturing Example 6]

The support substrate 5 was placed on the phosphor sheet 1 formed on the "Cerapeel" WDS, and a roll type heat laminator was used at a temperature of 80 ° C and a press pressure of 0.3. The pressure was MPa and the feed rate was 0.5 m/min. After leaving to cool to room temperature, the "Cerapeel" WDS was peeled off to obtain a layered body 6.

[Manufacturing Example 7]

The laminate 67 was obtained in the same manner as in Production Example 1 except that the support substrate 6 was used instead of the support substrate 1.

In addition, a laminate of "Cerapeel" WDS and the phosphor sheet 1 produced in Production Example 1 of the phosphor sheet is used as the laminate 8.

<Light-emitting element> (attachment device)

This is carried out using a vacuum laminator V130 (manufactured by Nichigo Morton) as shown in Figs. 3a to 3f, which has a vacuum chamber, a lower platen connected to the heater, The upper platen and the pressing mechanism of the flexible fluoroketone rubber sheet.

(Evaluation of the way the light of the light-emitting device is viewed)

The color temperature (hereinafter, the vertical color temperature) in a distance of 10 cm in the vertical direction with respect to the upper surface of the LED wafer of the light-emitting device, and the color temperature in the distance of 10 cm above the inclined 45° (hereinafter, 45°) The absolute value of the difference in color temperature is summarized and judged as follows.

A:|(vertical color temperature)-(45° color temperature)|<500K

B: 500K ≦ | (vertical color temperature) - (45 ° color temperature) | <1000K

C: 1000K ≦ | (vertical color temperature) - (45 ° color temperature) |

(follow-up evaluation method)

The light-emitting device in which the LED wafer is bonded to the substrate and covered with the phosphor sheet is cut at a position perpendicular to the substrate at positions I, II, and III shown in FIG. 4, and then photographed by SEM. Sectional view. The ratio of the portion of the phosphor sheet that is in contact with the upper light-emitting surface of the LED wafer is then calculated from the respective cross-sectional views. Further, in Fig. 4, A/D = 1/10, B/D = 5/10, and C/D = 9/10.

Further, the ratio of the portion where the phosphor sheet is in contact with respect to the side light-emitting surface of the LED wafer is similarly calculated. For each ratio, the average value of the measurement results of the three parts was used as the followability to the upper light-emitting surface and the followability to the side light-emitting surface, and the followability was evaluated by the following criteria.

A: The followability of the upper light-emitting surface of the LED is 100%, and the followability of the side light-emitting surface is 90% or more.

B: The followability of the upper light-emitting surface of the LED is 100%, and the followability of the side light-emitting surface is 70% or more and less than 90%.

C: the followability of the upper light-emitting surface of the LED is 100% and the followability of the side light-emitting surface is 50% or more and less than 70%.

D: the followability of the upper light-emitting surface of the LED is 90% or more and less than 100%, or the followability of the side light-emitting surface is 40% or more and less than 50%.

E: The followability of the upper light-emitting surface of the LED is less than 90%, or the followability of the side light-emitting surface is less than 40%.

(Evaluation of film thickness uniformity)

According to the cross-sectional view obtained by SEM in the follow-up evaluation method, the portion where the LED wafer 14 and the phosphor sheet 3 are in contact with the upper surface of the LED wafer 14 is measured. The distance a from the upper surface of the LED wafer 14 to the outer surface of the phosphor sheet 3 (see FIG. 4). Further, similarly, the distance b from the side surface of the LED chip 14 to the outer surface of the phosphor sheet 3 in the portion where the LED wafer 14 and the phosphor sheet 3 are in contact with the side surface of the LED wafer 14 is measured (refer to Figure 4). When measuring the distance a and the distance b, the measurement is 3 digits of the effective digit. The third digit after the decimal point was rounded off to find the value of a/b, and the film thickness uniformity was evaluated by the following criteria.

A: 1.00 < a / b < 1.05

B: 1.05≦a/b<1.20

C: 0.80 < a / b ≦ 1.00 or 1.20 ≦ a / b < 1.50

D: a / b ≦ 0.80 or 1.50 ≦ a / b, or can not be evaluated.

[Example 1]

On an alumina ceramic substrate provided with an electrode, an LED wafer having a size of 1 mm square and a thickness of 150 μm was bonded via a gold bump having a thickness of 10 μm. Then, the laminated body 1 was cut into 3 mm squares, and the phosphor sheet surface was overlapped with the upper surface of the bonded LED wafer. It was placed on a lower platen located in the vacuum chamber of the vacuum laminator. Then, after heating the lower platen to 80 ° C, the vacuum chamber was sealed. After the vacuum chamber was depressurized to 0.001 MPa by a vacuum pump, it was maintained for 30 seconds. Then, 0.1 MPa of air was fed into the pressing mechanism to expand the fluoroketone rubber sheet, and the laminated body 1 was pressed for 10 seconds along the shape of the LED wafer. Next, the vacuum chamber was opened (that is, air was injected into the vacuum chamber to be at atmospheric pressure (0.1 MPa)), and the phosphor sheet coated with the phosphor sheet was taken out. Among them, in this stage, the coated phosphor sheet is still in the B stage (semi-hardened state).

After the support substrate is removed from the light-emitting device, it is heated to a constant temperature of 150 ° C The phosphor sheet was sufficiently hardened by heating in a temperature oven for 2 hours to obtain a final light-emitting device. The light-emitting device was caused to emit light by applying a current of 30 mA to the obtained light-emitting device, and the vertical color temperature at a position separated from the light-emitting surface of the LED chip by 10 cm in the vertical direction (vertical direction) and the light-emitting surface from the LED chip were measured. The angle formed by the perpendicular line in the direction of 45° (in the direction of 45° inclination) was separated from the 45° color temperature at a position of 10 cm, thereby evaluating the light viewing mode. Then, the light-emitting element in which the light-viewing mode was evaluated was cut into a cross section perpendicular to the substrate, and then a cross-sectional view was taken by SEM. The followability and film thickness uniformity were evaluated based on the cross-sectional view.

[Example 2 to Example 6]

A light-emitting device was obtained in the same manner as in Example 1 except that the laminate described in Table 1 was used. With respect to the obtained light-emitting device, the light viewing mode, the followability, and the film thickness uniformity were evaluated in the same manner as in the first embodiment.

[Comparative Example 1 to Comparative Example 2]

A light-emitting device was obtained in the same manner as in Example 1 except that the laminate described in Table 1 was used. With respect to the obtained light-emitting device, the light viewing mode, the followability, and the film thickness uniformity were evaluated in the same manner as in the first embodiment.

According to the results of the examples, it is understood that the laminate including the support substrate and the phosphor sheet having a elongation at break of 200% or more and a Young's modulus of 600 MPa or less at 23 ° C can be used not only on the LED wafer. The followability and film thickness uniformity are maintained and can be covered by the phosphor sheet.

Further, when the light-emitting devices were caused to emit light, the light-emitting elements of the examples uniformly emitted light from any direction, but the light-emitting elements of the comparative examples were slightly dark when viewed from the oblique direction. It can be seen that uneven orientation is caused thereby.

As described above, in the light-emitting element which is excellent in followability and film thickness uniformity, the difference between the vertical color temperature of the LED wafer and the color temperature in the direction of inclination 45° is small. Therefore, uneven orientation can be suppressed.

1‧‧ ‧ laminated body

2‧‧‧Support substrate

3‧‧‧Fuel sheet

Claims (7)

A laminate comprising a support substrate and a phosphor sheet containing a phosphor and a resin, and an elongation at 23 ° C of the support substrate obtained by a tensile test The rate is 200% or more, and the Young's modulus at 23 ° C of the support substrate is 600 MPa or less. The laminate according to claim 1, wherein the support substrate has a Young's modulus at 23 ° C of 400 MPa or less. The laminate according to claim 1, wherein the support substrate has a Young's modulus at 23 ° C of 100 MPa or less. The laminate according to any one of claims 1 to 3, wherein the support substrate is polyvinyl chloride or polyurethane. A method of manufacturing a light-emitting device, comprising the step of coating a light-emitting surface of an LED chip bonded to a substrate, the phosphor of the laminate according to any one of claims 1 to 4 The light body sheet is coated. A method of manufacturing a light-emitting device, comprising the step of coating a layered body according to any one of claims 1 to 4, wherein the upper surface and the side surface of the LED chip bonded to the substrate are bonded The phosphor sheet is coated. The method of manufacturing a light-emitting device according to claim 5, wherein the LED chip is on the self-LED wafer in a portion of the phosphor sheet that is in contact with the upper surface of the LED wafer. a distance a [μm] from the surface to the outer surface of the phosphor sheet, and the LED wafer and the phosphor sheet on the side of the LED wafer The distance b [μm] from the side of the LED wafer to the outer surface of the phosphor sheet in the surface contact portion satisfies the following relationship: 1.00 < a / b < 1.20.