TWI541128B - Method for manufacturing laminated body and light-emitting diode with wavelength conversion layer - Google Patents

Description

Method for manufacturing laminated body and light-emitting diode with wavelength conversion layer

The present invention relates to a laminate which is a sheet-like material for converting an emission wavelength of a light-emitting diode (LED) chip, and a light-emitting diode having a wavelength conversion layer. method.

Light Emitting Diode (LED) is characterized by its low luminous efficiency, low power consumption, high lifetime, and creativity. It is not only a liquid crystal display (LCD) backlight device ( The back light) is used in the automotive field such as the headlights of the car, and the market for general lighting is also rapidly expanding.

The luminescence spectrum of the LED depends on the semiconductor material forming the LED wafer, and thus its luminescent color is limited. Therefore, in order to obtain white light for LCD backlight or general illumination using an LED, it is necessary to arrange a phosphor suitable for each wafer on the LED wafer, and to convert the emission wavelength. Specifically, a method of disposing a yellow phosphor on a blue-emitting LED wafer, a method of disposing red and green phosphors on a blue-emitting LED wafer, and setting red and green on an ultraviolet-emitting LED wafer are proposed. , the method of blue phosphor, etc. Among these, in terms of luminous efficiency or cost of the LED wafer, a method of providing a yellow phosphor on a blue LED and a method of providing a red and green phosphor on a blue LED are most widely used.

As one of specific methods for providing a phosphor on an LED wafer, it is proposed to laminate an anthrone resin sheet containing phosphor particles on an LED wafer. (hereinafter referred to as a phosphor sheet) (for example, refer to Patent Document 1 to Patent Document 4). This method is easier to arrange a fixed amount of phosphor on the LED wafer than in the conventional method in which the liquid resin in which the phosphor is dispersed is distributed and cured on the LED wafer. The color of the obtained white LED is excellent in that the color or brightness is uniform.

Prior art literature

Patent literature

Patent Document 1: Japanese Patent Laid-Open Publication No. 2009-235368

Patent Document 2: Japanese Patent Laid-Open Publication No. 2010-123802

Patent Document 3: Japanese Patent No. 2011-102004

Patent Document 4: Japanese Patent Laid-Open Publication No. 2010-159411

The method of bonding a phosphor sheet to an LED wafer is as described above, and the color or brightness is more stable than using a liquid phosphor resin, so that it is an excellent method, but it is difficult to disperse the resin in which the phosphor particles are dispersed. Evenly sheeted. Further, such a sheet is usually formed by being applied onto a film-form substrate including polyethylene terephthalate or the like. The phosphor sheet having the fluorenone resin as a main component has a modulus of elasticity which is not so high, and thus may be deformed or broken during handling. Therefore, after the phosphor sheet is applied onto the substrate, it is operated in a state of being integrated with the substrate until it is attached to the LED wafer. The phosphor sheet laminated on the substrate is peeled off after bonding to the LED wafer, and if the adhesion strength between the substrate and the phosphor sheet is high, the phosphor sheet is broken at the time of peeling. .

In order to prevent breakage of the phosphor sheet at the time of peeling of the substrate, a treatment called a mold release treatment is usually performed on the substrate. Demolding treatment is on the surface of the substrate A film of a substance having a very low surface energy such as a ketone-based organic compound or a fluorine-based organic compound, and facilitation of peeling of the phosphor sheet formed thereon. However, the fluorenone resin used for the phosphor sheet has poor coatability, and when applied to a surface treated with such a low surface energy agent, shrinkage or unevenness occurs, so that uniform coating becomes very uniform. difficult.

Further, the laminated body in which the phosphor sheet is formed may be subjected to mechanical processing such as cutting the size of the LED wafer before being attached to the LED wafer, or preliminarily contacting the laminated body with the electrode connection pad of the LED wafer. Part of the drilling process. When the laminated body obtained by forming the phosphor sheet containing the fluorenone resin and the phosphor on the substrate subjected to the release treatment is machined, the phosphor sheet is peeled off from the substrate and causes breakage. Such a situation is also a subject.

In view of the above, the present invention provides a laminate body and a method for producing a light-emitting diode having a wavelength conversion layer, wherein the laminate is a resin liquid for forming an anthrone resin-based sheet having poor coatability. When a phosphor sheet is formed on a substrate, shrinkage or unevenness of the resin liquid for sheet production is not generated in the coating step, and the substrate and the phosphor sheet can be easily removed in the peeling step. Stripped.

The laminate according to the present invention includes a base material containing polyphenylene sulfide and a phosphor sheet containing at least an fluorenone resin and a phosphor laminated on the base material.

When a resin liquid for sheet production containing a phosphor is applied onto a substrate, Since the laminate of the present invention can obtain good coatability, a phosphor sheet having a uniform film thickness can be obtained, and the substrate and the phosphor sheet can be easily peeled off, and the damage of the phosphor sheet can be prevented.

The phosphor sheet of the present invention is not particularly limited as long as it mainly contains an fluorenone resin and a phosphor, and various phosphor sheets can be used. Other ingredients may be included as needed.

The fluorenone resin used in the present invention is a binder resin containing a phosphor inside, and is a component which forms a form of a phosphor sheet. Therefore, there is no particular limitation on the case where the phosphor is uniformly dispersed inside and can be formed into a sheet shape. Further, in terms of durability and reliability when used in an LED light-emitting device, it is required to have excellent mechanical strength, transparency, heat resistance, and light resistance. Further, the fluorenone resin used in the present invention is preferably a hardenable fluorenone rubber. It can be composed of one liquid type or two liquid type (three liquid type). Among the hardened fluorenone rubbers, types of condensation reactions due to moisture or a catalyst in the air include a dealcoholization type, a dehydration type, a deacetic acid type, and a dehydroxyamine type. Further, the type of the hydrazine hydrogenation reaction caused by the catalyst has an addition reaction type. Any of these types of hardened fluorenone rubbers can also be used. In particular, in the case where the by-product which does not accompany the hardening reaction is hardly affected by moisture, and the hardening shrinkage is small, and it is easy to accelerate hardening by heating, it is more preferable to add the reaction type fluorenone rubber for sheet formation. .

An example of the addition reaction type fluorenone rubber is formed by hydrogenation reaction of a compound containing an alkenyl group bonded to a ruthenium atom and a compound having a hydrogen atom bonded to a ruthenium atom. Such materials can be cited: by vinyl three Methoxy decane, vinyl triethoxy decane, allyl trimethoxy decane, propylene trimethoxy decane, norbornene trimethoxy decane, octenyl trimethoxy decane, etc. a compound of an alkenyl group, and a methyl hydrogen polysiloxane, dimethyl polyoxyalkylene-CO-methylhydropolysiloxane, ethyl hydrogen polyoxyalkylene, methyl hydrogen It is formed by a hydrogenation reaction of a compound having a hydrogen atom bonded to a ruthenium atom such as a polyoxyalkylene-CO-methylphenyl polysiloxane.

Further, the fluorenone resin used in the present invention may be, for example, those described in JP-A-2010-159411. The anthrone resin described in Japanese Laid-Open Patent Publication No. 2010-159411 is an anthrone resin which is cured by a condensation reaction and an addition reaction, and can be obtained by including a substituent having a condensation reaction. A composition for an anthracene resin having a ruthenium compound and a ruthenium compound having a substituent capable of undergoing an addition reaction is subjected to a condensation reaction.

The ruthenium compound having a substituent capable of undergoing a condensation reaction is, for example, a ruthenium compound having a substituent such as a hydroxyl group, an amine group, an alkoxy group, a carboxyl group, an ester group or a halogen atom. Preferably, an anthracene compound having a hydroxyl group or an alkoxy group is exemplified. The number of substituents contained in one molecule is not particularly limited.

The ruthenium compound having a substituent capable of undergoing a condensation reaction is, for example, a two-terminal stanol type ruthenium compound represented by the following formula (1).

In the formula, R ¹ is a monovalent hydrocarbon group, for example, 1 to 20 carbon atoms, preferably a monovalent hydrocarbon group having 1 to 10. Listed are: methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, naphthyl, cyclohexyl, cyclopentyl and the like. Among them, from the viewpoint of transparency and light resistance, a methyl group is preferred. Further, the formula (1), all of R ¹ may be the same or different, preferably all of the R ¹ is methyl.

In the above formula (1), n is an integer of 1 or more, and n is from 1 to 10,000, more preferably from 1 to 1,000, from the viewpoint of stability or workability.

The compound represented by the formula (1) may, for example, be a terminal stanol type polydimethyl siloxane, a terminal stanol type polymethylphenyl siloxane, or a terminal stanol type polydiphenyl fluorene oxide. These may be used alone or in combination of two or more. Among these, preferred is ^a R & lt whole is methyl, the compound is an integer of from 1 to 1000 and n is.

The content of the compound represented by the formula (1) in the condensation reaction-based monomer is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 100% by mass.

The proportion of the condensation reaction-based monomer in the fluorenone resin is preferably from 1% by mass to 99% by mass, more preferably from 50% by mass to 99% by mass, even more preferably from 80% by mass to 99% by mass.

The hydrazine compound having a substituent capable of undergoing an addition reaction (hereinafter also referred to as an addition reaction-based monomer) may, for example, be an alkenyl group, a hydrogen atom, an alkynyl group, a carbonyl group, a thiol group, an epoxy group or an amine group. The ruthenium compound having a substituent such as a hydroxyl group or a thioether group is preferably a ruthenium compound having a hydrogen atom or an alkenyl group. The number of substituents contained in one molecule is not particularly limited.

The ruthenium compound having a hydrogen atom or an alkenyl group may be a compound containing an alkenyl group bonded to a ruthenium atom exemplified as the above-described addition reaction type fluorenone rubber, or a compound having a hydrogen atom bonded to a ruthenium atom.

The content of the addition reaction-based monomer in the fluorenone resin is preferably from 0.1% by mass to 99% by mass, more preferably from 0.1% by mass to 90% by mass, even more preferably from 0.1% by mass to 80% by mass.

Further, from the viewpoint of the viscoelasticity at the time of sheet formation, the ratio of the condensation reaction monomer to the addition reaction monomer (condensation reaction monomer/addition reaction monomer) is preferably 99.9/0.1. ~1/99, more preferably 99.9/0.1~50/50, especially 99.9/0.1~90/10.

Further, in addition to the above condensation reaction monomer and addition reaction monomer, the fluorenone resin described in JP-A-2010-159411 further contains a condensation reaction monomer and an addition reaction system. Any one of the monomers is a monomer-reactive compound (hereinafter also referred to as a condensation/addition monomer).

The condensation/addition monomer is a functional group having a functional group reactive with a condensation reaction monomer in one molecule and a functional group reactive with an addition reaction monomer. The functional group which can react with the condensation reaction type monomer is the same as the substituent which can be subjected to the condensation reaction described above, and the number of the functional groups in one molecule is not particularly limited. The functional group which can react with the addition reaction type monomer is the same as the substituent which can be subjected to the addition reaction described above, and the number of the functional groups in one molecule is not particularly limited.

The compound is preferably, for example, an alkenyl group-containing trialkoxy decane. In the above compound, an alkenyl group is subjected to an addition reaction with an addition reaction monomer, and an alkoxy group The condensation reaction is carried out with a condensation reaction monomer.

The alkenyl group of the alkenyl group-containing trialkoxy decane has a carbon number of 1 to 20, preferably 1 to 10, and specific examples thereof include a vinyl group, an allyl group, a propenyl group, a butenyl group and a pentyl group. Alkenyl, hexenyl, heptenyl, octenyl, norbornenyl, cyclohexenyl and the like. Among them, from the viewpoint of reactivity with the hydrogenation reaction, a vinyl group is preferred.

The alkoxy group of the alkenyl group-containing trialkoxy decane is an alkoxy group having a carbon number of 1 to 10, preferably 1 to 6, and specific examples thereof include a methoxy group, an ethoxy group, and a propoxy group. Base, butoxy, pentyloxy, hexyloxy and the like. Among them, from the viewpoint of reactivity to the condensation reaction, a methoxy group is preferred. Further, all of the alkoxy groups may be the same or different, and are preferably all methoxy groups.

Examples of the alkenyl group-containing trialkoxy decane include vinyltrimethoxydecane, vinyltriethoxydecane, allyltrimethoxydecane, allyltrimethoxynonane, norbornene-l-methoxydecane. And octenyltrimethoxydecane, etc., These can be used individually or in combination of 2 or more types. Among these, vinyltrimethoxydecane is preferred.

The content of the alkenyl group-containing trialkoxysilane in the condensation/addition monomer is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 100% by mass.

The content of the condensation/addition monomer in the fluorenone resin is preferably from 0.01% by mass to 90% by mass, more preferably from 0.01% by mass to 50% by mass, even more preferably from 0.01% by mass to 10% by mass.

Further, in the case of using the two-terminal stanol type eucalyptus oil represented by the formula (1) as a condensation reaction-based monomer, an alkenyl group-containing trialkoxy decane is used as the condensation/ When the monomer is added, the ratio of the decyl alcohol group of the decyl alcohol type eucalyptus oil to the alkoxy group of the alkenyl group-containing trialkoxy decane is appropriately reacted, and the preparation of the two is preferable. The molar ratio (stanol group/alkoxy group) of the above functional group is from 20/1 to 0.2/1, more preferably from 10/1 to 0.5/1, and still more preferably substantially equivalent (1/1).

When the fluorenone resin described in Japanese Laid-Open Patent Publication No. 2010-159411 is used, since the fluorenone resin is cured in two stages, it is not necessary to form an adhesive layer on the phosphor sheet.

The phosphor is a phosphor that absorbs light emitted from the LED wafer, converts the wavelength, and discharges light of a wavelength different from that of the LED wafer. Thereby, a part of the light emitted from the LED wafer is mixed with a part of the light released from the phosphor to obtain a multicolor LED including white. Specifically, by combining the blue LED and the phosphor that emits yellow light by the light from the blue LED, a single LED wafer can be used to emit white light.

The phosphor described above includes various phosphors such as a phosphor that emits green light, a phosphor that emits blue light, a phosphor that emits yellow light, and a phosphor that emits red light. Specific examples of the phosphor used in the present invention include known phosphors such as inorganic phosphors, organic phosphors, fluorescent pigments, and fluorescent dyes. The organic phosphor may, for example, be an allylsulfonamide-melamine formaldehyde co-condensation dye or a fluorene-based phosphor. For the long-term use, it is preferred to use a lanthanide-based phosphor. The fluorescent material which can be particularly preferably used in the present invention is an inorganic phosphor. The inorganic phosphor used in the present invention will be described below.

Examples of the phosphor that emits green light include: SrAl ₂ O ₄ :Eu, Y ₂ SiO ₅ :Ce, Tb, MgAl ₁₁ O ₁ 9:Ce, Tb, Sr ₇ Al ₁₂ O ₂₅ :Eu, (Mg, Ca, At least one or more of Sr and 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, or the like.

Phosphors emitting green light to yellow light include: at least a cerium-activated cerium-aluminum oxide phosphor, at least a cerium-activated cerium-lanthanum-aluminum oxide phosphor, at least cerium-activated cerium-aluminum a garnet oxide phosphor, and a yttrium-gallium-aluminum oxide phosphor activated at least by ruthenium (so-called 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 an anthracene system.), (Y _{1-X Ga X) 3 (} Al 1-y Ga y) 5 O 12: R (R is selected from Ce, Tb, Pr, Sm, at least Eu, Dy, Ho species 1 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.

Moreover, the current mainstream blue LED emitting light corresponding to the phosphor _{include: Y 3 (Al, Ga)} 5 O 12: Ce, (Y, Gd) 3 Al 5 O 12: Ce, Lu 3 Al 5 O ₁₂ : Ce, Y ₃ Al ₅ O ₁₂ : Ye, YAG-based phosphor, Tb ₃ Al ₅ O ₁₂ : Ce, etc. TAG-based phosphor, (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 : nitride, nitride-based phosphor such as Eu, CaSiAlN ₃ :Eu, oxynitride phosphor such as Ca _x (Si,Al) ₁₂ (O,N) ₁₆ :Eu, 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 :Eu, etc. .

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

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

The average particle diameter of the phosphor used in the present invention is not particularly limited, but is preferably 1 μm or more. Further, it is preferred that the average particle diameter is 20 μm or less. Here, the average particle diameter in the present invention means a median diameter, that is, D50. The D50 of the phosphor contained in the phosphor sheet is measured by image processing of a measurement image of a Scanning Electron Microscope (SEM) of a sheet cross section. In the particle size distribution, the volume-based particle size distribution thus obtained has a particle diameter of 50% from the small particle size side as a median diameter D50. The value of D50 obtained by this method is smaller than that when the phosphor powder is directly observed. However, the average particle diameter of the phosphor in the present invention is defined as a value obtained by the above-described measurement method. When the average particle diameter is in the above range, the dispersibility of the phosphor in the phosphor sheet is good, and stable luminescence can be obtained.

In addition, the reason why the value of D50 is smaller than the value when the phosphor powder is directly observed is because the diameter of the phosphor sheet can be accurately measured, but the fluorescence of the cross section of the phosphor sheet is measured. In the case of the particle size of the body, the phosphor particles are not necessarily limited to the equatorial plane. If a phosphor is assumed When the particles are spherical and cut at any portion thereof, the apparent diameter is theoretically 78.5% of the true diameter (corresponding to the ratio of the area of the circle having a diameter of 1 to the area of a square having one side). In fact, since the phosphor particles are not spheres, they are empirically about 70% to 85% of the true diameter.

In the present invention, the content of the phosphor is preferably 53% by mass or more, more preferably 57% by mass or more, and particularly preferably 60% by mass or more based on the entire phosphor sheet. By setting the content of the phosphor in the phosphor sheet to the above range, the light resistance of the phosphor sheet can be improved. In addition, from the viewpoint of easiness of production of the phosphor sheet, it is preferably 95% by mass or less, more preferably 90% by mass or less, and particularly preferably 85% by mass or less, particularly preferably 90% by mass or less, of the entire phosphor sheet. Good is 80% by mass or less.

The phosphor sheet of the present invention is formed by coating a resin liquid for forming a sheet of a phosphor sheet on a substrate containing polyphenylene sulfide and coating the same. The sheet is prepared by thermal drying and hardening with a resin liquid. Polyphenylene sulfide is a polymer containing a structure represented by the following formula (2) as an essential repeating unit.

The polyphenylene sulfide used in the present invention is a polymer containing a repeating unit represented by the formula (2), preferably 70 mol% or more, more preferably 90 mol% or more. When the polyphenylene sulfide contains 70 mol% or more of the repeating unit represented by the formula (2), the heat resistance is excellent, which is preferable.

In addition, 30 mol% or less of the repeating unit of the polyphenylene sulfide used in the present invention may be composed of a repeating unit or the like represented by the following structural formula. The polyphenylene sulfide used in the present invention may be at least one random copolymer or block copolymer comprising a repeating unit represented by the above formula (2) and a repeating unit represented by the following structural formula. Alternatively, it may be a mixture of a polymer having a repeating unit represented by the above formula (2) and at least one polymer having a repeating unit represented by the following structural formula.

Further, the polyphenylene sulfide of the present invention may be a crosslinked polyphenylene sulfide in addition to the linear polyphenylene sulfide containing the above repeating unit, but the substrate used in the present invention is preferably provided with flexibility. Since it has a film shape, it is preferable to use a film type containing a linear polyphenylene sulfide.

The substrate may contain components other than polyphenylene sulfide as long as the effects of the present invention are not impaired. For example, it may contain a resin component other than polyphenylene sulfide or inorganic Minute. Examples of the resin component other than the polyphenylene sulfide include polyolefins such as polyethylene, polypropylene, and ethylene copolymer resins, and styrenes such as polystyrene and acrylonitrile butadiene styrene (ABS) resins. Resin, thermoplastic resin such as polyvinyl chloride, vinylidene chloride, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polytetrafluoroethylene, or polyacrylate resin A high heat resistant resin such as polyoxybenzoic acid, polycarbonate, polyacetal, polyphenylene ether or polyimide. A method of mixing polyphenylene sulfide with another resin is a method of mixing and alloying at the time of film formation, and a method of dispersing fine particles of another resin in a polyphenylene sulfide matrix. The use of a molded body is known as a polyphenylene sulfide which is alloyed with polytetrafluoroethylene in order to improve slidability.

Examples of the inorganic component include glass fibers or inorganic fine particles. By including these inorganic components, it is possible to reduce the thermal expansion coefficient, improve the toughness, and improve the mechanical properties such as the elastic modulus. Any one of the glass fibers may be used, and it is preferable to include an alkali-free glass such as quartz glass or E glass or a low alkali glass in terms of difficulty in causing deterioration of mechanical properties. For example, inorganic oxide fine particles such as cerium oxide, aluminum oxide, calcium oxide, boron oxide, zinc oxide, titanium oxide, or zirconium oxide, or glass powder, quartz powder, or barium titanate, calcium carbonate, barium carbonate, sulfuric acid may be mentioned. An inorganic compound powder other than an oxide such as calcium or barium sulfate, or inorganic fine particles derived from natural materials such as talc, montmorillonite or mica, and these inorganic fine particles may be subjected to surface treatment as needed. Specific examples of the surface treatment include hydrophobization treatment using an oil such as eucalyptus oil, hydrophobization treatment using a surface treatment agent such as a decane coupling agent, hydrophilization treatment, or introduction of a hydroxyl group, an amine group, a carboxyl group, or an epoxy group on the surface of the fine particles. An organic functional group such as an acryl group, a vinyl group, an alkyl group or an aryl group can be appropriately selected in order to improve the affinity with the resin to be used, or the adhesion or dispersibility of the interface.

The substrate of the present invention may contain any of the above-mentioned components, and when a resin liquid for producing a phosphor sheet to be described later is applied by containing polyphenylene sulfide as a main component, a coating film having no shrinkage or unevenness can be obtained. Further, after the phosphor sheet is attached to the LED wafer, the substrate can be easily peeled off when the substrate is peeled off.

Further, the substrate of the present invention may be a laminate having a polyphenylene sulfide layer. For example, a layer formed of a layer mainly composed of polyphenylene sulfide as a main component of a polyolefin resin layer having a heat distortion temperature of 70 ° C to 150 ° C disclosed in Japanese Laid-Open Patent Publication No. 2006-21372 The body can also be used as a substrate of the present invention.

In order to improve the fluidity of the resin liquid for producing a phosphor sheet to be described later, the coating property is good, and the phosphor sheet of the present invention may contain an anthrone fine particle. The fluorenone fine particles contained are preferably fine particles containing an fluorenone resin and/or an anthrone rubber. Particularly preferred are fluorenone microparticles obtained by the following methods: an organic trialkoxy decane or an organic dialkoxy decane, an organic triethoxy decane, an organic diethyl methoxy decane, an organic trioxane, The organic decane such as organic dioxane is hydrolyzed, followed by condensation.

The organotrialkoxydecane can be exemplified by methyltrimethoxydecane, methyltriethoxydecane, methyltri-n-propoxydecane, methyltriisopropoxydecane, methyltri-n-butoxydecane. , methyl triisobutoxy decane, methyl tri-tert-butoxy decane, methyl tri-tert-butoxy decane, ethyl trimethoxy decane, n-propyl trimethoxy decane, isopropyl trimethoxy Base decane Tributoxy decane, isobutyl tributoxy decane, second butyl trimethoxy decane, tert-butyl tributoxy decane, N-(2-aminoethyl)-3-amino Propyltrimethoxydecane, 3-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 dimethyl ethyl ketone decane.

Specifically, such a particle can be obtained by the method described in Japanese Laid-Open Patent Publication No. SHO-63-77940, the method of Japanese Patent Application Laid-Open No. Hei. Method reported in the Gazette No. -342370, Japanese Patent Special Open The method and the like reported in the publication No. 4-88022. Further, it is also known to use 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. Or a partial hydrolyzate thereof is added to an alkaline aqueous solution to carry out hydrolysis or condensation to obtain particles; or an organic decane and/or a partial hydrolyzate thereof is added to water or an acidic solution to obtain the organodecane and/or a part thereof. After hydrolyzing a partial condensate of the hydrolyzate, a method of obtaining a particle by adding a base to carry out a condensation reaction; making the organic decane and/or its hydrolyzate an upper layer, and a mixture of a base or a base and an organic solvent as a lower layer, at the interface of these layers The method of obtaining the particles by hydrolyzing and polycondensing the organodecane and/or its hydrolyzate, and the like, can obtain the particles used in the present invention in any of the methods.

Among these, when the organodecane and/or a partial hydrolyzate thereof is hydrolyzed and condensed to produce spherical organic polysilsesquioxane particles, it is preferably used by, for example, Japanese Patent Laid-Open An anthrone fine particle obtained by a method of adding a polymer dispersant to a reaction solution reported in Japanese Laid-Open Patent Publication No. 2003-342370.

Further, in the production of the particles, an anthrone fine particle produced by hydrolyzing and condensing the organic decane and/or a partial hydrolyzate thereof in the presence of an acidic colloid can be used as a protective colloid in a solvent. In the state of the polymer dispersant and the salt to be acted on, an organic decane and/or a hydrolyzate thereof is added to obtain a hydrolyzate, and then a base is added to carry out a condensation reaction.

When the polymer dispersant is a water-soluble polymer and exhibits a role as a protective colloid in a solvent, any of a synthetic polymer and a natural polymer may be used. Specifically, polyvinyl alcohol or poly(poly) can be exemplified. Vinyl pyrrolidone and the like. The method of adding the polymer dispersant may be exemplified by a method of previously adding to the reaction liquid, a method of simultaneously adding an organic trialkoxysilane and/or a partial hydrolyzate thereof, and an organic trialkoxysilane and/or a portion thereof. The method of adding the hydrolyzate to the partial condensation of the hydrolysis may also be selected from any of these methods. Here, the amount of the polymer dispersant to be added is preferably in the range of 5 × 10 ^-7 to 5 × 10 ^-2 parts by mass based on 1 part by mass of the reaction liquid, and when the amount of the polymer dispersant added is in the range, Then particles are hard to cause agglomeration with each other.

The organic substituent contained in the fluorenone microparticles is preferably a methyl group or a phenyl group, and the refractive index of the fluorenone microparticles can be adjusted by the content of these substituents. In order to reduce the brightness of the LED light-emitting device without using the light scattering of the fluorenone resin as the binder resin, the refractive index d1 of the fluorenone fine particles and the fluorenone fine particles and the fluorescent light are preferably used. The refractive index difference of the refractive index d2 of the component other than the body is small. The refractive index difference between the refractive index d1 of the fluorene ketone fine particles and the refractive index d2 of the fluorenone fine particles and the components other than the fluorescent material is preferably less than 0.10, more preferably 0.03 or less. By controlling the refractive index of the fluorenone resin and the fluorenone microparticles in such a range, the reflection and scattering of the interface between the fluorenone microparticles and the fluorenone resin are lowered, and high transparency and light transmittance are obtained without This will reduce the brightness of the LED lighting device.

For the measurement of the refractive index, the total reflection method may use an Abbe refractometer, a Pulfrich refractometer, a liquid immersion refractometer, a liquid immersion method, a minimum deflection angle method, etc., but an anthrone composition. The Abbe refractometer is effectively used for the measurement of the refractive index of the object, and the liquid immersion method is effectively used for the measurement of the refractive index of the fluorenone microparticles.

In addition, the method for controlling the above refractive index difference can be modified by The blending ratio of the raw materials of the ketone ketone fine particles is adjusted. That is, for example, when a mixture of methyl trialkoxy decane and phenyltrialkoxy decane is used as a raw material, the composition ratio of methyl groups is increased, that is, the amount of methyl trialkoxy decane is increased, thereby achieving a ratio of 1.4. Low refractive index. On the other hand, by increasing the composition ratio of the phenyl group, that is, increasing the amount of the phenyltrialkoxydecane, a relatively high refractive index can be achieved.

In the present invention, the average particle diameter of the fluorenone fine particles is represented by a median diameter (D50), and the lower limit of the average particle diameter is preferably 0.01 μm or more, and more preferably 0.05 μm or more. Further, the upper limit is preferably 2.0 μm or less, more preferably 1.0 μm or less. When the average particle diameter is 0.01 μm or more, it is easy to produce particles having a controlled particle diameter, and the average particle diameter is 2.0 μm or less, and the optical characteristics of the phosphor sheet are excellent. In addition, by having an average particle diameter of 0.01 μm or more and 2.0 μm or less, the fluidity improving effect of the resin liquid for producing a phosphor sheet can be sufficiently obtained. Further, it is preferred to use spherical particles in a single dispersion. In the present invention, the average particle diameter of the fluorenone fine particles contained in the phosphor sheet, that is, the median diameter (D50) and the particle size distribution can be measured by SEM observation of the sheet cross section. The measurement image of the SEM was subjected to image processing to obtain a particle size distribution, and in the particle size distribution thus obtained, the particle diameter of 50% of the cumulative throughput rate from the small particle diameter side was determined as the median diameter D50. Out. At this time, also in the same manner 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 a true average compared with the true average particle diameter. The value of 78.5% of the particle diameter is actually about 70% to 85%. However, the average particle diameter of the fluorenone fine particles in the present invention is defined as a value obtained by the above measurement method.

In the phosphor sheet of the present invention, the content of the fluorenone fine particles is preferably 0.5% by mass or more, more preferably 1% by mass or more, and particularly preferably 2% by mass based on the total amount of the fluorenone resin and the fluorenone fine particles. %the above. Further, the upper limit is preferably 20% by mass or less, and more preferably 10% by mass or less. By containing 1% by mass or more of the fluorenone fine particles, a particularly excellent phosphor dispersion stabilizing effect can be obtained, and on the other hand, by containing 20% by mass or less of the fluorenone fine particles, the sheet can be produced. The viscosity of the resin liquid rises excessively.

In the resin liquid for producing a phosphor sheet of the present invention, in order to suppress the hardening of the resin liquid for sheet production at room temperature and to extend the pot life, it is preferable to adjust the hydrogenation reaction delay such as acetylene alcohol. Agent.

In addition, in the resin liquid for sheet production, fine particles such as fumed silica, glass powder, and quartz powder, titanium oxide, zirconium oxide, and titanium can be blended as needed in the range of the effect of the present invention. An inorganic filler or pigment such as strontium or zinc oxide, or an adhesion-imparting agent such as a flame retardant, a heat-resistant agent, an antioxidant, a dispersant, a solvent, a decane coupling agent or a titanium coupling agent.

In particular, in terms of surface smoothness of the phosphor sheet, it is preferred to add a low molecular weight polydimethyl siloxane component, eucalyptus oil, or the like to the resin liquid for producing a phosphor sheet. Such a component is preferably added in an amount of from 100 ppm to 2,000 ppm, more preferably from 500 ppm to 1,000 ppm, in the resin liquid for sheet production (excluding the solvent amount when the solvent is contained).

The film thickness of the phosphor sheet in the present invention is determined in accordance with the phosphor content and the desired optical characteristics. In order to obtain the desired optical characteristics, it is required that the phosphor sheet contains a specific amount of phosphor, but if the phosphor sheet is used When the amount of the phosphor in the medium is too high, there is a limit in terms of workability, and therefore the thickness of the phosphor sheet is preferably 10 μm or more. Further, since the phosphor sheet of the present invention has a large content of the phosphor, the light resistance is excellent even when the film thickness is thick. On the other hand, from the viewpoint of improving the optical characteristics and heat resistance of the phosphor sheet, the thickness of the phosphor sheet is preferably 200 μm or less, and more preferably 100 μm or less. By making the phosphor sheet a film thickness of 200 μm or less, light absorption or light scattering of the binder resin can be reduced, and thus the phosphor sheet is excellent in optical properties.

The film thickness of the phosphor sheet in the present invention is a film thickness measured by the method A for measuring the thickness by mechanical scanning in the plastic-film and sheet-thickness measurement method of JIS K7130 (1999). Film thickness).

The LED is in a small space and generates a lot of heat, especially in high-power LEDs, the heat is obvious. Due to such heat generation, the temperature of the phosphor rises, and the brightness of the LED decreases. Therefore, it is important how to efficiently dissipate the generated heat. In the present invention, by setting the film thickness of the phosphor sheet to the above range, a phosphor sheet excellent in heat resistance can be obtained. Further, when the film thickness of the phosphor sheet varies, the amount of phosphor per LED wafer varies, and as a result, the emission spectrum (color temperature, luminance, and chromaticity) varies. Therefore, the deviation of the film thickness of the sheet is preferably within ±5%, more preferably within ±3%. In addition, the film thickness variation here is measured by the method A of the thickness of the mechanical scanning by the method A of the plastic-film and sheet-thickness measurement method of JIS K7130 (1999), and it is shown below. Calculated by the formula.

More specifically, the measurement conditions of the thickness measurement method by mechanical scanning are used, and a micrometer such as a commercially available contact thickness meter is used. (micrometer) measure the film thickness, calculate the maximum or maximum film thickness The difference between the small value and the average film thickness is divided by the average film thickness, and the value expressed as a percentage is the film thickness deviation B (%).

Film thickness deviation B (%) = {(maximum film thickness deviation value * - average film thickness) / average film thickness} × 100

* 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.

Hereinafter, a method of producing the laminated body of the present invention will be described by way of specific examples. In addition, the following is an example, and the manufacturing method of the laminated body of this invention is not limited to this.

First, a resin liquid obtained by dispersing the phosphor particles and the fluorenone fine particles used as needed in the fluorenone resin material (hereinafter referred to as "resin liquid for sheet production") is prepared as a phosphor sheet. The coating liquid is applied. The resin liquid for sheet production is obtained by mixing the phosphor particles, the fluorenone resin material, and, if necessary, the fluorenone fine particles in a solvent-free manner or in a suitable solvent. When an addition reaction type fluorenone resin is used, if a compound containing an alkenyl group bonded to a ruthenium atom as a fluorene ketone resin material and a compound having a hydrogen atom bonded to a ruthenium atom are mixed, at room temperature Since the hardening reaction is also started, the hydrogenation reaction retarder such as an acetylene compound can be further blended into the resin liquid for sheet production to improve storage stability. Further, in terms of storage stability, it is effective to not have a compound having an alkenyl group bonded to a ruthenium atom, a compound having a hydrogen atom bonded to a ruthenium atom, and The reaction catalyst (platinum-based catalyst) was all mixed, but was separated into two liquids in advance. For example, a siloxane compound having an alkenyl group bonded to a ruthenium atom and a platinum-based catalyst are used as the liquid A, and a compound having a hydrogen group bonded to a ruthenium atom is used as the liquid B, and the fluorination is dispersed in the liquid A. After the bulk particles and the fluorene ketone fine particles, the liquid B is mixed before the sheet is to be formed.

A dispersing agent or a leveling agent for stabilizing the coating film as an additive, a bonding aid such as a decane coupling agent as a modifier of the surface of the sheet, and the like may be mixed in the resin liquid for sheet production.

When the solvent is added to adjust the viscosity of the resin liquid for sheet production, the type of the solvent is not particularly limited as long as the viscosity of the resin in the flow state can be adjusted. For example, toluene, methyl ethyl ketone, methyl isobutyl ketone, hexane, heptane, cyclohexane, acetone, rosinol, butyl carbitol, butyl carbitol acetate, B Diol dimethyl ether, diethylene glycol dimethyl ether, and the like.

After blending these components in a specific composition, the mixture is homogenized and homogenized by a homogenizer, a self-rotating mixer, a three-roller, a ball mill, a planetary ball mill, a bead mill, a kneader, and the like. Thus, a resin liquid for sheet production was obtained. It is also preferred to carry out defoaming under vacuum or reduced pressure after mixing and dispersion, or during mixing and dispersion.

Next, the resin liquid for sheet production is applied onto a polyphenylene sulfide resin film substrate and dried. Coating can be carried out by means of a reverse roll coater, a blade coater, a slit die coater, a direct gravure coater (direct Gravure coater), gravure coater (offset gravure) Coater), kiss coater, screen printing, natural roll coater, air-knife coater, roll coater, adjustable scraper Vor-bar roll blade coater, two-stream coater, rod coater, bar coater, applicator, dip coater, curtain type A coater, a spin coater, a knife coater, and the like. In order to obtain uniformity of the film thickness of the sheet, it is preferred to apply it by a slit 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. It is especially good to use screen printing.

The film thickness of the substrate used in the present invention is not particularly limited, and the lower limit is preferably 40 μm or more, and more preferably 60 μm or more. Further, the upper limit is preferably 5,000 μm or less, more preferably 3,000 μm or less.

The resin liquid for sheet production applied to the substrate is heat-cured, and can be carried out by a usual heating device such as a hot air dryer or an infrared dryer. The heat curing condition of the resin liquid for sheet production is a normal heating device such as a hot air dryer or an infrared dryer, and is usually from 1 minute to 5 hours, preferably from 100 ° C to 200 ° C at 40 ° C to 250 ° C. The next is 2 minutes to 3 hours.

In the laminate of the present invention, an adhesive layer for improving the adhesion to the LED wafer can be provided on the side of the phosphor sheet. The material of the adhesive layer is not particularly limited, and examples thereof include a usual rubber-based, acrylic-based, urethane-based, anthrone-based adhesive. Although any of them can be used, an anthrone-based adhesive is useful as an adhesive suitable for heat resistance, insulation, and transparency.

In addition, in the laminate of the present invention, it can be provided on the side of the phosphor sheet. Protective film. The material of the protective film is not particularly limited, and examples thereof include polyethylene terephthalate (PET), polyethylene, polypropylene, polyvinyl chloride, cellophane, and polyphenylene sulfide. Further, the protective film can be subjected to a release treatment by a known release agent such as an anthrone or a fluorine.

As the LED wafer to which the phosphor sheet of the present invention can be applied, a face up type LED chip or a flip chip type LED chip, etc., particularly preferably a flip chip LED chip. The flip chip type LED wafer has high luminous efficiency and high heat dissipation. Therefore, by using the phosphor sheet of the present invention, it is easy to produce a high-power LED for illumination use having excellent light resistance.

The phosphor sheet of the present invention can be used as a wavelength conversion sheet to be mounted on an LED element. At present, the mainstream white LED for illumination converts a part of the wavelength of the blue light of the blue LED element into yellow, green, or red by using a phosphor material, and mixes with the blue light of the blue LED element to obtain white light. The method of attaching a phosphor material to a blue LED element mainly employs a method of preliminarily containing a phosphor in a liquid transparent sealing material used when resin sealing a blue LED element. Although this method is simple, it is difficult to precisely apply a liquid sealing resin containing a fixed amount of phosphor to individual blue LED elements, resulting in color deviation. On the other hand, according to the present invention, since a phosphor sheet having a uniform film thickness can be obtained, a phosphor sheet having a fixed thickness can be easily attached to the blue LED element, so that the phosphor on the blue LED element can be obtained. The amount of light is fixed. By performing the wavelength conversion of the blue LED element by mounting the phosphor sheet of the present invention, no Excellent white LED light-emitting device with color deviation or brightness deviation.

Next, a method of manufacturing an LED light-emitting device using the laminated body of the present invention will be described. In addition, the following description is an example, and the sealing manufacturing method is not limited to these description.

When the laminate of the present invention is applied to a flip chip type LED wafer, first, the laminate is diced according to the size of the LED wafer to be sealed. The dicing can be performed by cutting. When the laminated body has a protective film, it may be diced after peeling, or may be diced together with the protective film. Further, when the LED wafer has an electrode pad on the light-emitting surface (light-emitting surface) side, it is preferable to perform processing on the laminated body before attaching, and to open a hole in a portion corresponding to the electrode pad in advance.

Next, when the laminated body has a protective film, after the protective film is peeled off, a small-sized laminated body is bonded to the light-emitting surface of the LED chip. At this time, the phosphor sheet of the laminate may be in a semi-hardened state or may be hardened in advance. The bonding is preferably carried out by using an adhesive, and a known die bond agent or an adhesive such as an acrylic resin, an epoxy resin, a urethane resin or an anthranone resin can be used. A modified ketone resin system, a phenol resin system, a polyamidene system, a polyvinyl alcohol system, a polymethacrylate resin system, a melamine resin system, or a urea resin type binder. When the phosphor sheet itself has adhesiveness or has an adhesive layer, it is also possible to use itself. Further, in the case of a semi-cured phosphor sheet, it may be cured by heating. Further, when the phosphor sheet has thermal softening property after curing, it can be bonded by heat fusion.

Next, the polyphenylene sulfide resin film substrate was peeled off from the laminate. If the substrate In the case of polyphenylene sulfide, the phosphor sheet is not damaged or peeled off from the LED wafer, and the substrate can be easily removed. It is also possible to bond the phosphor sheet to the LED wafer after the substrate is peeled off in advance, in accordance with the timing of peeling off the protective film. When the strength of the phosphor sheet is weak, if the substrate is first peeled off, Since the phosphor sheet may be damaged, it is preferable to peel the substrate after bonding to the LED wafer.

Then, the electrode of the LED wafer and the wiring of the circuit board are electrically connected by a known method, whereby a light-emitting device can be obtained. When the LED chip has an electrode on the light-emitting surface side, the LED chip is fixed to the circuit board by a bonding material or the like with the light-emitting surface as the upper surface, and the electrode and the circuit substrate on the LED wafer are bonded by wire bonding. Wiring connection. Further, when the LED chip is a flip chip type having an electrode pad on the opposite surface of the light-emitting surface, the electrode surface of the LED chip is brought into contact with the wiring of the circuit board, and the connection is performed by one-time bonding. When the phosphor sheet is bonded to the LED wafer in a semi-hardened state, it can be cured at an appropriate timing before or after the electrical connection. For example, when the flip chip type is subjected to one-time bonding, the bonding of the thermocompression bonding can simultaneously cure the phosphor sheet by the heating. Further, when a package in which an LED chip and a circuit board are connected is mounted on a surface of a larger circuit board, the phosphor sheet can be cured while being welded by reflow soldering.

The phosphor sheet can also serve as a sealant for the LED wafer, and a well-known fluorenone resin or the like can be further used as the light-transmitting sealing material to seal the LED wafer to which the phosphor sheet is attached. Further, after the LED wafer is sealed by a translucent sealing material, a phosphor sheet may be attached to the sealing material and used.

Further, in the semiconductor wafer on which the LED wafer is mounted on the surface, a laminate which is not small-sized is attached, and then the semiconductor wafer and the laminated body can be individually (cut).

The light-emitting device of the LED chip which can be obtained by using the phosphor sheet of the present invention is not particularly limited, and can be widely applied to a backlight of a display used for a television, a computer, a mobile phone, a game machine, or the like, or Vehicle headlights and other automotive fields, general lighting of buildings, etc.

Example

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

<Measurement of film thickness>

The film thickness of the specific position of the substrate on which the phosphor sheet is formed is measured in advance by a micrometer, and is marked in advance. After the phosphor sheet was laminated, the mark portion was again measured by a micrometer, and the film thickness of the substrate measured in advance was subtracted from the obtained film thickness to obtain the film thickness of the phosphor sheet. In the film thickness, a sheet of 110 mm square was used as a measurement sample, and a grid was formed at intervals of 10 mm, and 100 points were measured. The maximum value, the minimum value, and the average value of each sample were determined, and the film thickness deviation B was obtained by the following formula. .

Film thickness deviation B (%) = {(maximum film thickness deviation value * - average film thickness) / average film thickness} × 100

* The maximum film thickness deviation value is the difference between the maximum value and the minimum value of the selected film thickness and the average film thickness.

<Correlated color temperature deviation>

A current of 400 mA was applied to a light-emitting device in which each of the phosphor sheets was mounted on a blue LED element, and the LED chip was turned on, and an instantaneous multi-photometry system (MCPD-3000, manufactured by Otsuka Electronics Co., Ltd.) was used, and immediately after the start of the measurement test The relevant color temperature. One hundred LED light-emitting devices were produced one by one for each of the phosphor sheets, and the average value, the maximum value, and the minimum value among the 100 samples were obtained, and the variation was evaluated according to the following formula.

Correlated color temperature deviation (K)=correlation color temperature maximum deviation value-average correlation color temperature

* The maximum deviation value of the correlated color temperature is the difference between the maximum value and the minimum value of the selected color temperature and the average value.

<Synthesis Example of Anthrone Microparticles: Anthrone Microparticles 1>

A stirrer, a thermometer, a reflux tube, and a dropping funnel were placed in a 2 L four-neck round bottom flask, and 2 ml of 2.5% ammonia water containing 1 ppm of a polyether modified oxirane "BYK333" as a surfactant was added to the flask. The mixture was stirred at 300 rpm while being heated by an oil bath. After reaching an internal temperature of 50 ° C, a mixture (23 mol% / 77 mol%) of methyltrimethoxydecane and phenyltrimethoxydecane (200 g) was added dropwise from the dropping funnel over 30 minutes. Then, stirring was continued at this temperature for 60 minutes, and then about 5 g of acetic acid (reagent grade) was added thereto, and the mixture was stirred and mixed, followed by filtration. 600 mL of water was added to the generated particles on the filter twice, and 200 mL of methanol was added once, and the mixture was filtered and washed. Remove the filter cake from the filter and disintegrate it for 10 hours. It was freeze-dried, whereby 60 g of a white powder was obtained. The obtained particles were monodisperse spherical fine particles having a median diameter (D50) of 0.5 μm. The refractive index of the fine particles was measured by a liquid immersion method and found to be 1.54. When the particles were observed by a cross-sectional TEM, it was confirmed that particles within a particle have a single structure.

(Example 1)

A container of polyethylene having a volume of 300 ml was used, and a ratio of 40.0% by mass of "OE-6630A/B" (manufactured by TORAY.DOW CORNING, refractive index of 1.53) and a ratio of 60.0% by mass was mixed as a ketone resin. as phosphors "NYAG-02" (Intel US (Intematix) manufactured by: Ce-doped YAG phosphor system, specific ^{gravity: 4.8g / cm 3, D50:} 7μm).

Then, using a planetary stirring-deaerator "Mazerustar (registered trademark)" KK-400 (manufactured by Kurabo), the mixture was stirred at 1000 rpm for 20 minutes, and defoamed to obtain a phosphor sheet preparation liquid. The resin liquid for sheet production was applied to a polyphenylene sulfide film "TORELINA (registered trademark)" (manufactured by Toray Industries, Inc.) using a slit coater, and heated and dried at 130 ° C for 2 hours. A laminate in which a phosphor sheet having an average film thickness of about 100 μm was formed was obtained. The obtained laminated body was such that the phosphor sheet was uniformly applied to the film of the substrate, no pinhole was observed, and the film thickness uniformity was also good.

"SD4580" (anthraquinone adhesive manufactured by Toray Dow Corning Co., Ltd.) was applied to the phosphor sheet, and dried by heating at 100 ° C for 15 minutes to obtain an adhesive layer.

"Cerapeel (registered trademark)" BLK (Toray film) on the adhesive layer The processing (manufactured by TORAY ADVANCED FILM Co., Ltd.) was carried out at room temperature to form a cover film.

Next, in order to test the substrate releasability of the obtained laminated body, transfer lamination was performed on the glass substrate.

The laminate was cut into 100 mm × 50 mm, and the cover film was peeled off. Next, the surface on which the cover film was peeled off and the adhesive layer was peeled off was brought into contact with the glass substrate, and the rubber hand roll was adhered so as not to enter the air bubbles. Then, when the "TORELINA (registered trademark)" film of the substrate is peeled off, the phosphor sheet is always in close contact with the glass substrate without being peeled off or damaged, and the base film can be easily peeled off.

Further, the phosphor sheet is attached to the LED element in the same manner, and the light is emitted and measured, and as a result, the variation in the correlated color temperature is small, and a good white LED can be obtained.

(Example 2 to Example 4)

The fluorenone fine particles 1 were added so as to be in an amount shown in Table 1, and the amount of each component was adjusted so that the content of the phosphor particles in the phosphor sheet was kept at 60.0% by mass, and Example 1 was used. A phosphor sheet was produced in the same manner. "SD4580" (an anthrone adhesive manufactured by Toray Dow Corning Co., Ltd.) was applied to the phosphor sheet, and dried by heating at 100 ° C for 15 minutes to obtain an adhesive layer.

On the adhesive layer, "Cerapeel (registered trademark)" BLK (manufactured by Toray Film Processing Co., Ltd.) was laminated at room temperature as a cover film.

Next, in order to test the substrate releasability of the obtained laminated body, transfer lamination was performed on the glass substrate.

The laminate was cut into 100 mm × 50 mm, and the cover film was peeled off. Next, the surface on which the cover film was peeled off and the adhesive layer was peeled off was brought into contact with the glass substrate, and the rubber hand roll was adhered so as not to enter the air bubbles. Then, when the "TORELINA (registered trademark)" film of the substrate is peeled off, the phosphor sheet is always in close contact with the glass substrate without being peeled off or damaged, and the base film can be easily peeled off.

Further, the phosphor sheet is attached to the LED element in the same manner, and the luminescent color is measured by lighting. As a result, the variation in the correlated color temperature is extremely small, and a good white LED can be obtained.

(Comparative Example 1)

A laminate was produced in the same manner as in Example 1 except that the base film was changed to a polyethylene terephthalate film "Lumirror (registered trademark)" (manufactured by Toray Industries, Inc.), and the sheet was confirmed. The coating property of the resin liquid for material production and the peelability of the substrate. The coating property is good, there is no pinhole, and a phosphor sheet having good film thickness uniformity can be obtained. However, when the laminated body is transferred to a glass substrate, if the base film is peeled off, the phosphor is not obtained. A part of the sheet adhered to the side of the substrate film and peeled off, resulting in damage and peeling from the glass substrate.

Further, the laminate was attached to the LED element in the same manner, and when the substrate was peeled off, most of the phosphor sheet was peeled off from the LED element, and the luminescent color could not be measured by lighting.

(Comparative Example 2)

The base film was changed to a release-treated polyethylene terephthalate film "Cerapeel (registered trademark)" HP2 (Dongli Film Processing Co., Ltd. In the same manner as in Example 1, a phosphor sheet was produced in the same manner as in Example 1, and the coating property of the resin liquid for sheet production and the substrate peeling property were confirmed. At the time of coating, shrinkage of the resin liquid for producing a phosphor sheet is caused, and the thickness of the phosphor sheet obtained by heating and hardening is not uniform. When the laminated body is transferred to the glass substrate, when the base film is peeled off, the phosphor sheet is always in close contact with the glass substrate without being peeled off or damaged, and the base film can be easily peeled off.

The phosphor sheet is attached to the LED element in the same manner, and the luminescent color is measured by lighting. As a result, the variation in the correlated color temperature is larger than that of the first to fourth embodiments, and the white LED is larger. Unable to achieve sufficient uniformity.

(Comparative Example 3, Comparative Example 4)

The fluorenone fine particles 1 were added in an amount as shown in Table 1, and the amount of each component was adjusted so that the content of the phosphor particles in the phosphor sheet was kept at 60.0% by mass, and the comparative example was used. 2 A phosphor sheet was produced in the same manner, and the coating property of the resin liquid for sheet production and the peelability of the substrate were confirmed. At the time of coating, shrinkage of the resin liquid for producing a phosphor sheet is caused, and the thickness of the phosphor sheet obtained by heating and hardening is not uniform. When the laminated body is transferred to the glass substrate, when the base film is peeled off, the phosphor sheet is always in close contact with the glass substrate without being peeled off or damaged, and the base film can be easily peeled off.

In the same manner, the phosphor sheet is attached to the LED element, and the luminescent color is measured by lighting. As a result, since the film thickness variation is large, the variation in the correlated color temperature is larger than that of the first to fourth embodiments, and the white LED cannot be used. Get charged The uniformity of the points.

(Comparative Example 5)

The same as in the first embodiment except that the base film was changed to a release-treated polyethylene terephthalate film "Cerapeel (registered trademark)" BLK (manufactured by Toray Film Processing Co., Ltd.). In the manner of producing a phosphor sheet, the coating property of the resin liquid for sheet production and the peelability of the substrate were confirmed. At the time of coating, shrinkage of the resin liquid for producing a phosphor sheet occurs, and pinholes are generated in a large amount, and the thickness of the phosphor sheet obtained by heating and hardening is not uniform. When the laminated body is transferred to the glass substrate, when the base film is peeled off, the phosphor sheet is always in close contact with the glass substrate without being peeled off or damaged, and the base film can be easily peeled off.

In the same manner, the phosphor sheet is attached to the LED element, and the luminescent color is measured by lighting. As a result, the variation in the correlated color temperature is also very large as compared with the first to fourth embodiments. Large, white LEDs do not achieve sufficient uniformity.

(Comparative Example 6)

The fluorenone fine particles 1 were added in an amount as shown in Table 1, and the amount of each component was adjusted so that the content of the phosphor particles in the phosphor sheet was kept at 60.0% by mass, and Comparative Example 5 was used. In the same manner, a phosphor sheet was produced, and the coatability of the resin liquid for sheet production and the peelability of the substrate were confirmed. At the time of coating, shrinkage of the resin liquid for producing a phosphor sheet is caused, and the thickness of the phosphor sheet obtained by heating and hardening is not uniform. After the laminated body is transferred to the glass substrate, when the base film is peeled off, the phosphor sheet is always in close contact with the glass substrate without being peeled off or damaged, so that it can be easily The base film is peeled off.

The phosphor sheet is attached to the LED element in the same manner, and the luminescent color is measured by lighting. As a result, the variation in the correlated color temperature is larger than that of the first to fourth embodiments, and the white LED is larger. Unable to achieve sufficient uniformity.

Claims (10)

A laminate comprising: a substrate containing polyphenylene sulfide; and a phosphor sheet comprising at least an anthrone resin and a phosphor laminated on the substrate. The laminate according to claim 1, wherein the fluorenone resin is hydrogenated by hydrazine of a compound having at least an alkenyl group bonded to a ruthenium atom and a compound having a hydrogen atom bonded to a ruthenium atom. The addition-hardening type fluorenone resin is formed. The laminate according to claim 1 or 2, wherein the phosphor sheet further contains an anthrone fine particle. The laminate according to claim 3, wherein the fluorenone microparticles are an fluorenone resin obtained by condensing an organic decane. The laminate according to the third aspect of the invention, wherein the amount of the fluorenone fine particles is 1% by mass or more and 20% by mass or less based on the total amount of the fluorenone resin and the fluorenone fine particles. The laminate according to the first or second aspect of the invention, wherein the content of the phosphor is 53% by mass or more with respect to the phosphor sheet. The laminate according to the first or second aspect of the invention, wherein the thickness of the phosphor sheet is 10 μm or more and 200 μm or less. The laminate according to claim 1 or 2, wherein a deviation of a film thickness of the phosphor sheet is within ±5%. Such as the layered body described in claim 1 or 2, The above-described phosphor sheet can be used as a wavelength conversion sheet of a light-emitting diode element. A method of manufacturing a light-emitting diode with a wavelength conversion layer, comprising: a step of bonding a laminate according to any one of claims 1 to 9 to an LED element; And a step of peeling the substrate from the laminate.