JP2014079905A - Method for manufacturing wavelength conversion member and method for manufacturing light-emitting device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide novel means capable of solving, with a simple measure, a problem of variation caused when manufacturing a wavelength conversion member, the problem of variation conventionally having necessitated adjustment of an entire lot.SOLUTION: A molded body having been molded is irradiated with light of a certain excitation wavelength to measure chromaticity of light irradiated from the molded body. A feedback of a result of the measurement is given to a molding process to adjust the thickness of the molded body.

Description

  The present invention relates to a method for manufacturing a wavelength conversion member that can convert excitation light into light having a wavelength different from that of the excitation light and emit the light.

Light-emitting devices using semiconductor light-emitting elements (hereinafter, also simply referred to as LED light-emitting devices) have increased presence as energy-saving light-emitting devices. Further, the development of LED light emitting devices that emit white light has progressed, and LED light emitting devices including a blue LED chip and a wavelength conversion member that is a phosphor-containing resin molded body are well known.
The wavelength conversion member including the phosphor is manufactured by, for example, molding a phosphor resin composition in which the phosphor is dispersed in the resin, but the phosphor in the phosphor resin composition is manufactured under certain conditions. Variations in the concentration and thickness and amount of the wavelength conversion layer affect the hue of the light emitting device.

With respect to such a variation problem, Patent Document 1 measures the chromaticity of the manufactured light emitting device, and irradiates the phosphor layer with laser light having a predetermined wavelength when the measurement result is out of a predetermined range. It has been proposed to adjust the chromaticity by deactivating part of the phosphor.
Patent Document 2 discloses that the chromaticity is controlled by partially removing the wavelength conversion material layer by ablation and reducing the amount of the wavelength conversion material.
Patent Document 3 discloses that the variation in hue is eliminated by operating the light emitting device, measuring the color of light emitted from the device, and depositing and / or removing the phosphor material according to the result. Has been.

JP 2011-165827 A JP 2007-324608 A JP 2010-541284 A

Although the solution is proposed as described above for the problem of variation, measures are taken for the wavelength conversion member and the light emitting device after molding. The above method is very time consuming, inefficient and inferior in economic efficiency.
In particular, when a wavelength conversion member is manufactured by melt-molding a pellet (phosphor resin composition) in which a phosphor is melt-kneaded with a resin, there are variations in emission characteristics depending on the lot of the raw material phosphor, If the phosphor concentration varies from lot to lot, it is necessary to adjust all the lots, and a simple method has been demanded.
It is an object of the present invention to provide a new means that can solve the above-mentioned variation problem by a simple method.

  The inventors of the present invention have repeatedly studied to solve the above problems, and measure the chromaticity of light emitted from the molded body by irradiating the molded body with light of a specific excitation wavelength. The present invention was completed by finding that the variation can be suppressed in-line by feeding back the result to the molding process and adjusting the thickness of the molded body.

This invention includes the manufacturing method of the wavelength conversion member as described below.
(1) A method for producing a wavelength conversion member comprising a step of molding a phosphor resin composition containing a phosphor by injection molding, wherein light having a specific excitation wavelength is applied to the molded body molded in the step. Including the step of measuring the chromaticity of the light emitted from the molded body by irradiation,
A method for producing a wavelength conversion member, wherein the thickness of a molded body to be molded can be adjusted by feeding back the measured chromaticity to the molding step.
(2) In the molding step, one or two or more selected from the group consisting of the filling amount of the resin composition into the molding step, the resin composition temperature, the injection pressure in injection molding, the holding pressure, and the holding pressure switching position. The manufacturing method of the wavelength conversion member as described in (1) which adjusts the thickness of the molded object shape | molded by adjustment of this.
(3) In the measurement step, when the chromaticity is shifted to the lower left on the xy chromaticity coordinates, the thickness of the molded body is increased, and when the chromaticity is shifted to the upper right on the xy chromaticity coordinates, the molded body is increased. The method for producing a wavelength conversion member according to (2), wherein the thickness of the molded body to be molded is adjusted so as to reduce the thickness of the wavelength conversion member.
(4) The method for manufacturing a wavelength conversion member according to any one of (1) to (3), wherein the phosphor composition includes a thermoplastic resin.
(5) The method for producing a wavelength conversion member according to any one of (1) to (4), wherein the phosphor resin composition includes a polycarbonate resin.
(6) The said phosphor resin composition is a manufacturing method of the wavelength conversion member as described in (4) or (5) formed by melt-mixing phosphor and resin.
(7) According to any one of (1) to (6), the film thickness of the molded body is changed by 0.5% or more from the film thickness of the molded body before feedback by feedback to the molding process. The manufacturing method of the wavelength conversion member of description.
(8) The manufacturing method of the wavelength conversion member in any one of (1) to (7) which contains only 1 type of fluorescent substance.
(9) The method for producing a wavelength conversion member according to (8), wherein the phosphor is a yellow phosphor.
(10) The method for producing a wavelength conversion member according to any one of (1) to (7), comprising two or more phosphors.
(11) The method for producing a wavelength conversion member according to (10), wherein the phosphor includes a yellow phosphor and a red phosphor, or a green phosphor and a red phosphor.
(12) In the measurement step, the wavelength conversion according to any one of (1) to (11), wherein a color temperature of light emitted from the molded body when irradiated with specific excitation light is 2500 K or more and 6500 K or less. Manufacturing method of member.
(13) The method for manufacturing a wavelength conversion member according to any one of (1) to (12), wherein the specific excitation light is blue light.

Moreover, this invention includes the manufacturing method of the light-emitting device as described below.
(14) A method for manufacturing a light emitting device including a wavelength conversion member, comprising a step of molding a phosphor resin composition containing a phosphor by injection molding,
Including the step of measuring the chromaticity of light emitted from the molded body by irradiating light of a specific excitation wavelength to the molded body molded in the step,
A method of manufacturing a light emitting device, wherein the thickness of a molded body to be molded can be adjusted by feeding back the measured chromaticity to the molding step.

According to the manufacturing method of the present invention, the chromaticity shift of the wavelength conversion member can be fed back in-line, so that the yield is improved.
Even if the phosphor concentration is slightly increased or decreased when creating the melt-kneaded pellets, if there is no feedback, there will be a difference in the light emission characteristics between the kneading lots. Improves uniformity.
In addition, according to the manufacturing method of the present invention, the difference in the light emission characteristics due to the difference in the raw material lots such as the particle diameter and the light emission characteristics of the raw material phosphor can be reduced, and the quality uniformity is improved.

It is a figure which shows the result of Experimental example 1-3. It is a figure which shows the result of Experimental example 4-6. It is a schematic diagram which shows one structural example of a semiconductor light-emitting device. It is a schematic diagram which shows one structural example of a semiconductor light-emitting device.

<1. Molding process>
An embodiment of the present invention includes a step of molding a phosphor resin composition containing a phosphor by injection molding.
The molding process according to this embodiment is not particularly limited as long as it is by injection molding, and may be manufactured according to a conventional method.

<1-1. Resin>
The resin used in the present embodiment is not particularly limited as long as it is a resin that can be used for injection molding, and a thermoplastic resin, a thermosetting resin, a photocurable resin, and the like can be used. A thermoplastic resin is preferably used. Examples of thermoplastic resins include polyethylene resins such as low, high density polyethylene, linear low density polyethylene, polypropylene resins, poly-3-methylbutene-1 resins, poly-4-methylpentene-1 resins, norbornene, etc. Polyolefin resins such as alicyclic polyolefin resins, including ethylene-vinyl acetate copolymers, copolymers of ethylene and methyl-, ethyl-, propyl-, and butyl-acrylates or methacrylates, ethylene-acrylic acid copolymer Ionomer resin such as coalescence; polystyrene resin, ABS resin, AS resin, AAS resin, AES resin, MBS resin and other styrene resins, polymethyl methacrylate, polymethacrylate and other acrylic resins; polyamide resin; polyacetal resin; polycarbonate Resin; Polyethylene Polyester resins such as phthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polylactic acid resin; modified polyphenylene ether resin; polyurethane resin; polyphenylene sulfide resin; polyarylate resin; polyether ether ketone resin; Resins; Fluorine-containing resins such as polytetrafluoroethylene resin and polyvinylidene fluoride resin are listed, and one or a blend of two or more of these is listed.
Of these, polycarbonate resin is most preferably used because it is excellent in transparency, heat resistance, mechanical properties, and flame retardancy. Hereinafter, the polycarbonate resin will be described in detail.

The polycarbonate resin used in this embodiment is a polymer having a basic structure having a carbonic acid bond represented by the following general chemical formula (1).

In the chemical formula (1), X ¹ is generally a hydrocarbon, but for imparting various properties, X ¹ into which a hetero atom or a hetero bond is introduced may be used.

  The polycarbonate resin can be classified into an aromatic polycarbonate resin in which carbon directly bonded to a carbonic acid bond is aromatic carbon and an aliphatic polycarbonate resin in which aliphatic carbon is aliphatic carbon, either of which can be used. Of these, aromatic polycarbonate resins are preferred from the viewpoints of heat resistance, mechanical properties, electrical characteristics, and the like.

  Although there is no restriction | limiting in the specific kind of polycarbonate resin, For example, the polycarbonate polymer formed by making a dihydroxy compound and a carbonate precursor react is mentioned. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Further, a method of reacting carbon dioxide with a cyclic ether using a carbonate precursor may be used. The polycarbonate polymer may be linear or branched. Further, the polycarbonate polymer may be a homopolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units. At this time, the copolymer can be selected from various copolymerization forms such as a random copolymer and a block copolymer. In general, such a polycarbonate polymer is a thermoplastic resin.

Examples of aromatic dihydroxy compounds among monomers used as raw materials for aromatic polycarbonate resins include dihydroxy compounds such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (ie, resorcinol), 1,4-dihydroxybenzene, and the like. Benzenes; dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl, 4,4′-dihydroxybiphenyl; 2,2′-dihydroxy-1,1′-binaphthyl, 1,2-dihydroxy Dihydroxynaphthalenes such as naphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene; 2 , 2'-di Droxydiphenyl ether, 3,3′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 1,4-bis (3-hydroxyphenoxy) benzene, 1, Dihydroxydiaryl ethers such as 3-bis (4-hydroxyphenoxy) benzene; 2,2-bis (4-hydroxyphenyl) propane (ie, bisphenol A), 1,1-bis (4-hydroxyphenyl) propane, 2 , 2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-methoxy-4-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (3-methoxy-4 -Hydroxyphenyl) propane, 1,1-bis (3-tert-butyl) 4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2- (4- Hydroxyphenyl) -2- (3-cyclohexyl-4-hydroxyphenyl) propane, α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene, 1,3-bis [2- (4-hydroxy Phenyl) -2-propyl] benzene, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) cyclohexylmethane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) (4-propenylphenyl) ) Methane, bis (4-hydroxyphenyl) diphenylmethane, bis (4- Loxyphenyl) naphthylmethane, 1-bis (4-hydroxyphenyl) ethane, 2-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -1-naphthylethane, 1-bis (4-hydroxyphenyl) butane, 2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 1,1 -Bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) hexane, 1-bis (4-hydroxyphenyl) octane, 2-bis (4-hydroxyphenyl) octane, 1-bis (4 -Hydroxyphenyl) hexane, 2-bis (4-hydroxyphenyl) hexane, 4,4-bis (4-hydro) Shifeniru) heptane, 2,2-bis (
Bis (hydroxyaryl) alkanes such as 4-hydroxyphenyl) nonane, 10-bis (4-hydroxyphenyl) decane, 1-bis (4-hydroxyphenyl) dodecane; 1-bis (4-hydroxyphenyl) cyclopentane; 1-bis (4-hydroxyphenyl) cyclohexane, 4-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane, 1-bis (4-hydroxyphenyl) -3,4-dimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1, 1-bis (4-hydroxy-3,5-dimethylphenyl) -3,3 -Trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane, 1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane, etc. Bis (hydroxyaryl) cycloalkanes; cardostructure-containing bisphenols such as 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene; 4,4 ′ -Dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3 ' Dihydroxy diaryl sulfides such as dimethyl diphenyl sulfide; dihydroxy diaryl sulfoxides such as 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide; 4,4′-dihydroxydiphenyl sulfone; Examples include dihydroxydiaryl sulfones such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone.

  Among these, bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane (ie, from the viewpoint of impact resistance and heat resistance). Bisphenol A) is preferred.

  In addition, 1 type may be used for an aromatic dihydroxy compound and it may use 2 or more types together by arbitrary combinations and a ratio.

Examples of the monomer that is a raw material for the aliphatic polycarbonate resin include ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, 2,2-dimethylpropane-1, 3-diol, 2-methyl-2-propylpropane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, decane-1,10-diol Alkanediols such as cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, 1,4-cyclohexanedimethanol, 4- (2-hydroxyethyl) cyclohexanol, Cycloalkanediols such as 2,2,4,4-tetramethyl-cyclobutane-1,3-diol; 2,2′-oxy Glycols such as sidiethanol (ie, ethylene glycol), diethylene glycol, triethylene glycol, propylene glycol, spiroglycol; 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 1 , 4-benzenediethanol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 2,3-bis (hydroxymethyl) naphthalene, 1,6-bis (hydroxy Ethoxy) naphthalene, 4,4′-biphenyldimethanol, 4,4′-biphenyldiethanol, 1,4-bis (2-hydroxyethoxy) biphenyl, bisphenol A bis (2-hydroxyethyl) ether, bisphenol S bis (2 -Hydroxyethyl) Aralkyl diols such as ether; 1,2-epoxyethane (ie, ethylene oxide), 1,2-epoxypropane (ie, propylene oxide), 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,4 -Cyclic ethers such as epoxycyclohexane, 1-methyl-1,2-epoxycyclohexane, 2,3-epoxynorbornane, 1,3-epoxypropane and the like may be used, and these may be used alone or in combination of two or more May be used in any combination and ratio.

  Among the monomers used as the raw material for the aromatic polycarbonate resin, examples of the carbonate precursor include carbonyl halide and carbonate ester. In addition, 1 type may be used for a carbonate precursor and it may use 2 or more types together by arbitrary combinations and a ratio.

  Specific examples of the carbonyl halide include phosgene, haloformates such as a bischloroformate of a dihydroxy compound, and a monochloroformate of a dihydroxy compound.

  Specific examples of the carbonate ester include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonate bodies of dihydroxy compounds, monocarbonate bodies of dihydroxy compounds, and cyclic carbonates. And carbonate bodies of dihydroxy compounds such as

  The method for producing the polycarbonate resin is not particularly limited, and any method can be adopted. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Hereinafter, the interfacial polymerization method and the melt transesterification method, which are particularly suitable among these methods, will be specifically described.

(Interfacial polymerization method)
In the interfacial polymerization method, a dihydroxy compound and a carbonate precursor (preferably phosgene) are reacted in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, usually at a pH of 9 or higher. Polycarbonate resin is obtained by interfacial polymerization in the presence. In the reaction system, a molecular weight adjusting agent (terminal terminator) may be present as necessary, or an antioxidant may be present to prevent the oxidation of the dihydroxy compound.

  The dihydroxy compound and the carbonate precursor are as described above. Of the carbonate precursors, phosgene is preferably used, and a method using phosgene is particularly called a phosgene method.

  Examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene. . In addition, 1 type may be used for an organic solvent and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the alkali compound contained in the alkaline aqueous solution include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate, among which sodium hydroxide and water Potassium oxide is preferred. In addition, 1 type may be used for an alkali compound and it may use 2 or more types together by arbitrary combinations and a ratio.

Although there is no restriction | limiting in the density | concentration of the alkali compound in aqueous alkali solution, Usually, in order to control pH in the aqueous alkali solution of reaction to 10-12, it is used at 5 to 10 weight%. For example, when phosgene is blown, the molar ratio of the bisphenol compound and the alkali compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. Among these, it is preferable that the ratio is 1: 2.0 or more, usually 1: 3.2 or less, and more preferably 1: 2.5 or less.

  Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic rings such as N, N′-dimethylcyclohexylamine and N, N′-diethylcyclohexylamine. Tertiary amines of formula; aromatic tertiary amines such as N, N′-dimethylaniline and N, N′-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride and triethylbenzylammonium chloride; Examples include pyridine, guanine, guanidine salts, and the like. In addition, 1 type may be used for a polymerization catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the molecular weight modifier include aromatic phenols having a monovalent phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol, mercaptans, and phthalimides, among which aromatic phenols are preferred. Specific examples of such aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. Substituted phenols: Vinyl group-containing phenols such as isopropanyl phenol, epoxy group-containing phenols, carboxyl group-containing phenols such as o-oxine benzoic acid, 2-methyl-6-hydroxyphenylacetic acid, and the like. In addition, a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The usage-amount of a molecular weight modifier is 0.5 mol or more normally with respect to 100 mol of dihydroxy compounds, Preferably it is 1 mol or more, and is 50 mol or less normally, Preferably it is 30 mol or less. By making the usage-amount of a molecular weight modifier into this range, the thermal stability and hydrolysis resistance of a polycarbonate resin composition can be improved.

  In the reaction, the order of mixing the reaction substrate, reaction medium, catalyst, additive and the like is arbitrary as long as a desired polycarbonate resin is obtained, and an appropriate order may be arbitrarily set. For example, when phosgene is used as the carbonate precursor, the molecular weight regulator can be mixed at any time as long as it is between the reaction (phosgenation) of the dihydroxy compound and phosgene and the start of the polymerization reaction. In addition, reaction temperature is 0-40 degreeC normally, and reaction time is normally several minutes (for example, 10 minutes)-several hours (for example, 6 hours).

(Melted ester exchange method)
In the melt transesterification method, for example, a transesterification reaction between a carbonic acid diester and a dihydroxy compound is performed.

  The dihydroxy compound is as described above. On the other hand, examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diphenyl carbonate; substituted diphenyl carbonate such as ditolyl carbonate, and the like. Of these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable. In addition, carbonic acid diester may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

The ratio of the dihydroxy compound and the carbonic acid diester is arbitrary as long as the desired polycarbonate resin can be obtained, but it is preferable to use an equimolar amount or more of the carbonic acid diester with respect to 1 mol of the dihydroxy compound. Is more preferable. The upper limit is usually 1.30 mol or less. By setting it as such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.

  In the polycarbonate resin, the amount of terminal hydroxyl groups tends to have a great influence on thermal stability, hydrolysis stability, color tone and the like. For this reason, you may adjust the amount of terminal hydroxyl groups as needed by a well-known arbitrary method. In the transesterification reaction, a polycarbonate resin in which the terminal hydroxyl group amount is adjusted can be usually obtained by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound, the degree of vacuum during the transesterification reaction, and the like. In addition, the molecular weight of the polycarbonate resin usually obtained can also be adjusted by this operation.

  When adjusting the amount of terminal hydroxyl groups by adjusting the mixing ratio of the carbonic acid diester and the dihydroxy compound, the mixing ratio is as described above. Further, as a more aggressive adjustment method, there may be mentioned a method in which a terminal terminator is mixed separately during the reaction. Examples of the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, carbonic acid diesters, and the like. In addition, 1 type may be used for a terminal terminator and it may use 2 or more types together by arbitrary combinations and a ratio.

  When producing a polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among them, it is preferable to use, for example, an alkali metal compound and / or an alkaline earth metal compound. In addition, auxiliary compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. In addition, 1 type may be used for a transesterification catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  In the melt transesterification method, the reaction temperature is usually 100 to 320 ° C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, a melt polycondensation reaction may be performed under the above-mentioned conditions while removing a by-product such as an aromatic hydroxy compound.

  The melt polycondensation reaction can be performed by either a batch method or a continuous method. When performing by a batch type, the order which mixes a reaction substrate, a reaction medium, a catalyst, an additive, etc. is arbitrary as long as a desired aromatic polycarbonate resin is obtained, What is necessary is just to set an appropriate order arbitrarily. However, considering the stability of the polycarbonate resin and the polycarbonate resin composition, the melt polycondensation reaction is preferably carried out continuously.

  In the melt transesterification method, a catalyst deactivator may be used as necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. In addition, 1 type may be used for a catalyst deactivator and it may use 2 or more types together by arbitrary combinations and a ratio.

  The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Furthermore, it is 1 ppm or more normally with respect to aromatic polycarbonate resin, and is 100 ppm or less normally, Preferably it is 20 ppm or less.

The molecular weight of the polycarbonate resin is arbitrary and may be appropriately selected and determined. The viscosity average molecular weight [Mv] converted from the solution viscosity is usually 10,000 or more, preferably 16,000 or more, more preferably 18, 000 or more, and usually 40,000 or less, preferably 30,000 or less. By setting the viscosity average molecular weight to be equal to or higher than the lower limit of the above range, the mechanical strength of the polycarbonate resin composition of the present invention can be further improved, which is more preferable when used for applications requiring high mechanical strength. On the other hand, by setting the viscosity average molecular weight to be equal to or lower than the upper limit of the above range, the polycarbonate resin composition of the present invention can be suppressed and improved in fluidity, and the molding processability can be improved and the molding process can be easily performed. Two or more types of polycarbonate resins having different viscosity average molecular weights may be mixed and used, and in this case, a polycarbonate resin having a viscosity average molecular weight outside the above-mentioned preferred range may be mixed.

The viscosity average molecular weight [Mv] is obtained by using methylene chloride as a solvent and obtaining an intrinsic viscosity [η] (unit: dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer. , Η = 1.23 × 10 ⁻⁴ Mv ^0.83 . The intrinsic viscosity [η] is a value calculated from the following formula (1) by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g / dl).

  The terminal hydroxyl group concentration of the polycarbonate resin is arbitrary and may be appropriately selected and determined, but is usually 1,000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less. Thereby, the residence heat stability and color tone of the polycarbonate resin composition of the present invention can be further improved. Moreover, the minimum is 10 ppm or more normally, Preferably it is 30 ppm or more, More preferably, it is 40 ppm or more. Thereby, the fall of molecular weight can be suppressed and the mechanical characteristic of the polycarbonate resin composition of this invention can be improved more. The unit of the terminal hydroxyl group concentration is the weight of the terminal hydroxyl group expressed in ppm relative to the weight of the polycarbonate resin. The measurement method is colorimetric determination (method described in Macromol. Chem. 88 215 (1965)) by the titanium tetrachloride / acetic acid method.

  A polycarbonate resin may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  The polycarbonate resin is a polycarbonate resin alone (the polycarbonate resin alone is not limited to an embodiment containing only one type of polycarbonate resin, and is used in a sense including an embodiment containing a plurality of types of polycarbonate resins having different monomer compositions and molecular weights, for example. .), Or an alloy (mixture) of a polycarbonate resin and another thermoplastic resin may be used in combination. Further, for example, for the purpose of further improving flame retardancy and impact resistance, a polycarbonate resin is copolymerized with an oligomer or polymer having a siloxane structure; for the purpose of further improving thermal oxidation stability and flame retardancy A monomer, oligomer or polymer having a copolymer; a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; Copolymers with oligomers or polymers having an olefin-based structure; for the purpose of improving chemical resistance, they may be configured as copolymers mainly composed of polycarbonate resins, such as copolymers with polyester resin oligomers or polymers. . When used in combination with other thermoplastic resins, the proportion of the polycarbonate resin in the resin component is preferably 50% by weight or more, more preferably 60% by weight, and further preferably 70% by weight or more. preferable.

Further, in order to improve the appearance of the molded product and improve the fluidity, the polycarbonate resin may contain a polycarbonate oligomer. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1,500 or more, preferably 2,000 or more,
Usually, it is 9,500 or less, preferably 9,000 or less. Furthermore, the polycarbonate ligomer contained is preferably 30% by weight or less of the polycarbonate resin (including the polycarbonate oligomer).

  Further, the polycarbonate resin may be not only a virgin raw material but also a polycarbonate resin regenerated from a used product (so-called material-recycled polycarbonate resin). Examples of the used products include: optical recording media such as optical disks; light guide plates; vehicle window glass, vehicle headlamp lenses, windshields and other vehicle transparent members; water bottles and other containers; eyeglass lenses; Examples include architectural members such as glass windows and corrugated sheets. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.

  However, the regenerated polycarbonate resin is preferably 80% by weight or less, more preferably 50% by weight or less, among the polycarbonate resins contained in the polycarbonate resin composition of the present invention. Recycled polycarbonate resin is likely to have undergone deterioration such as heat deterioration and aging deterioration, so when such polycarbonate resin is used more than the above range, hue and mechanical properties can be reduced. It is because there is sex.

As the characteristics of the resin used in this embodiment, in the case of a crystalline thermoplastic resin, the melting point is usually 80 ° C. or higher, and preferably 120 ° C. or higher. On the other hand, it is usually 350 ° C. or lower and preferably 300 ° C. or lower. In the case of an amorphous thermoplastic resin, the glass transition point is usually 80 ° C. or higher, and preferably 120 ° C. or higher. On the other hand, it is usually 350 ° C. or lower and preferably 300 ° C. or lower. By being in this range, injection molding is preferably performed.
In the case of a thermoplastic resin, the elastic modulus is preferably 600 MPa or more at room temperature, more preferably 700 MPa or more, and still more preferably 800 MPa or more. By being in this range, even when used for a lighting fixture or the like, a situation in which the rigidity is insufficient due to a temperature rise due to lighting is suppressed.

<1-2. Phosphor>
The wavelength conversion member according to this embodiment includes a phosphor. The type of phosphor contained is appropriately selected depending on the type of light emitted from the light emitting device and the wavelength of the light of the semiconductor light emitting element that serves as excitation light. For example, in a white light emitting device that emits white light, a blue semiconductor light emitting element that emits light in a blue region is used as an excitation source, and a yellow phosphor is included in the wavelength conversion member to emit white light. Can do. Moreover, it is also a preferable aspect to add a red fluorescent substance in addition to a yellow fluorescent substance, and it is also a preferable aspect to include a green fluorescent substance and a red fluorescent substance. Other phosphors may be added as appropriate.
When a violet semiconductor light emitting element that emits light in the purple region is used as an excitation source, white light can be emitted by including a blue phosphor, a green phosphor, and a red phosphor. Other phosphors may be added as appropriate.
The phosphor is preferably an inorganic phosphor. Examples of yellow, red (orange), green, blue, and phosphor include the following as typical phosphors.

<1-2-1. Yellow phosphor>
The emission peak wavelength of the yellow phosphor is usually 530 nm or more, preferably 540 nm or more, more preferably 550 nm or more, and usually 620 nm or less, preferably 600 nm or less, more preferably 580 nm or less. The full width at half maximum of the emission peak of the yellow phosphor is usually in the range of 80 nm to 130 nm. The external quantum efficiency is usually 60% or more, preferably 70% or more, and the weight median diameter is usually 0.1 μm or more, preferably 1.
It is 0 μm or more, more preferably 5.0 μm or more, and is usually 40 μm or less, preferably 30 μm or less, and more preferably 20 μm or less.

Examples of such yellow phosphors include various oxide-based, nitride-based, oxynitride-based, sulfide-based, and oxysulfide-based phosphors. In particular, RE ₃ M ₅ O ₁₂ : Ce (where RE represents at least one element selected from the group consisting of Y, Tb, Gd, Lu, and Sm, and M represents Al, Ga, and Sc. And Ma ₃ Mb ₂ Mc ₃ O ₁₂ : Ce (where Ma is a divalent metal element, Mb is a trivalent metal element, and Mc is tetravalent). A garnet phosphor having a garnet structure represented by AE ₂ MdO ₄ : Eu (where AE is selected from the group consisting of Ba, Sr, Ca, Mg, and Zn). Represents at least one element, and Md represents Si and / or Ge.) Orthosilicate phosphors represented by the above, etc., and part of oxygen of the constituent elements of these phosphors is replaced with nitrogen Oxynitride phosphor, AE lSiN _3: Ce (., where, AE is, Ba, Sr, Ca, represents at least one element selected from the group consisting of Mg and Zn) nitride phosphor having a CaAlSiN ₃ structure, such as with Ce Examples include activated phosphors.
Among these, garnet-based phosphors are preferably used, and among them, Y ₃ Al ₅ O ₁₂ : Ce (sometimes described as “YAG” in the present specification) is particularly preferably used.

In addition, as yellow phosphors, sulfide-based fluorescence such as CaGa ₂ S ₄ : Eu, (Ca, Sr) Ga ₂ S ₄ : Eu, (Ca, Sr) (Ga, Al) ₂ S ₄ : Eu, etc. _{body, Ca x (Si, Al)} 12 (O, N) 16: fluorescent material activated with Eu of oxynitride-based fluorescent material or the like having a SiAlON structure such as _{Eu, (M 1-a-} B Eu a Mn _{B) 2 (BO 3) 1} -P (PO 4) P X ( where, M represents Ca, Sr, and at least one element selected from the group consisting of Ba, X is F, Cl, and Represents one or more elements selected from the group consisting of Br. A, B, and P are 0.001 ≦ A ≦ 0.3, 0 ≦ B ≦ 0.3, and 0 ≦ P ≦ 0.2, respectively. Eu-activated or Eu / Mn co-activated halogenated borate phosphor, alkaline earth metal element It is also possible to use a Ce-activated nitride-based phosphor having a La ₃ Si ₆ N ₁₁ structure and the like, which may contain bismuth. Note that a part of the Ce-activated nitride phosphor described above may be partially substituted with Ca or O.

<1-2-2. Red phosphor> The emission peak wavelength of the red phosphor is usually in the wavelength range of 565 nm or more, preferably 575 nm or more, more preferably 580 nm or more, and usually 780 nm or less, preferably 700 nm or less, more preferably 680 nm or less. Is preferred.

The full width at half maximum of the emission peak of the red phosphor is usually in the range of 1 nm to 120 nm. The external quantum efficiency is usually 60% or more, preferably 70% or more, and the weight median diameter is usually 0.1 μm or more, preferably 1.0 μm or more, more preferably 5.0 μm or more, usually 40 μm. Hereinafter, it is preferably 30 μm or less, more preferably 20 μm or less.
As such a red phosphor, for example, CaAlSiN ₃ : Eu described in JP-A-2006-008721 (also referred to as “CASN” in this specification), JP-A-2008-7751, for example. (Sr, Ca) AlSiN ₃ : Eu described in the publication No., and Ca _1−x Al _1−x Si _{1 + x} N _3−x O _x : Eu and the like described in JP 2007-231245 A Activated oxides, nitrides, oxynitride phosphors, and the like, and Japanese Patent Application Laid-Open No. 2008-38081 (Sr, Ba, Ca) ₃ SiO ₅ : Eu (hereinafter, abbreviated as “SBS phosphor”). ) Can also be used.

In addition, as red phosphors, Eu-activated alkaline earth silicon nitride phosphors such as (Mg, Ca, Sr, Ba) ₂ Si ₅ N ₈ : Eu, (La, Y) ₂ O ₂ S: Eu Eu-activated oxysulfide phosphor such as (Y, La, Gd, Lu) ₂ O ₂ S: Eu, etc. Eu-activated rare earth oxychalcogenide-based phosphor, Y (V, P) O ₄ : Eu, Y Eu-activated oxide phosphor such as ₂ O ₃ : Eu, (Ba, Mg) ₂ SiO ₄ : Eu, Mn, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, Mn, etc. Activated silicate phosphor, LiW ₂ O ₈ : Eu, LiW ₂ O ₈ : Eu, Sm, Eu ₂ W ₂ O ₉ , Eu ₂ W ₂ O ₉ : Nb, Eu ₂ W ₂ O ₉ : Em with Eu, etc. Activated tungstate phosphor, Eu-activated sulfide such as (Ca, Sr) S: Eu Light body, YAlO _3: Eu-activated aluminate phosphor such as _{Eu, Ca 2 Y 8 (SiO} 4) 6 O 2: Eu, LiY 9 (SiO 4) 6 O 2: Eu -activated silicate such as Eu Phosphor, (Y, Gd) ₃ Al ₅ O ₁₂ : Ce, (Tb, Gd) ₃ Al ₅ O ₁₂ : Ce-activated aluminate phosphor such as Ce, (Mg, Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, (Mg, Ca, Sr, Ba) Si (N, O) ₂ : Eu, (Mg, Ca, Sr, Ba) AlSi (N, O) ₃ : Eu such as Eu Activated oxide, nitride or oxynitride phosphor, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, Mn activated halophosphate phosphor such as Eu, Mn, Ba _{3 MgSi 2 O 8: Eu, Mn} , (Ba, Sr, Ca, Mg) 3 (Zn, Mg) S ₂ O _8: Eu, Eu such as Mn, Mn-activated silicate _{phosphor, 3.5MgO · 0.5MgF 2 · GeO 2} : Mn activated germanate salt phosphors such as Mn, Eu-activated α sialon and the like Eu-activated oxynitride phosphor, (Gd, Y, Lu, La) ₂ O ₃ : Eu, Bi-activated oxide phosphor such as Eu, Bi, (Gd, Y, Lu, La) ₂ O ₂ S : Eu, Bi-activated oxysulfide phosphor such as Eu, Bi, (Gd, Y, Lu, La) VO ₄ : Eu, Bi-activated vanadate phosphor such as Eu, Bi, SrY ₂ S ₄ : Eu, Ce activated sulfide phosphors such as Eu and Ce, Ca activated sulfide phosphors such as CaLa ₂ S ₄ : Ce, (Ba, Sr, Ca) MgP ₂ O ₇ : Eu, Mn, (Sr, Ca, Ba, Mg, Zn) ₂ P ₂ O ₇ : Eu, Mn activated phosphor phosphor such as Eu, Mn, Y, Lu) ₂ WO ₆ : Eu, Mo activated tungstate phosphor such as Eu, Mo, (Ba, Sr, Ca) _x Si _y N _z : Eu, Ce (where x, y, z are Represents an integer of 1 or more. Eu, Ce-activated nitride phosphors such as (Ca, Sr, Ba, Mg) ₁₀ (PO ₄ ) ₆ (F, Cl, Br, OH): Eu, Mn-activated halophosphoric acid such as Eu, Mn Salt phosphors, ((Y, Lu, Gd, Tb) _1-xy Sc _x Ce _y ) ₂ (Ca, Mg) _1-r (Mg, Zn) _{2 + r} Si _z-q Ge _q O _{12 + δ and} other Ce An activated silicate phosphor or the like can also be used.

In addition, in order to improve the color rendering properties of the emitted light from the semiconductor light emitting device or to increase the light emission efficiency of the light emitting device, a red phosphor having a half-value width of the red emission spectrum of 20 nm or less (hereinafter referred to as “narrow”) as the red phosphor. May be used alone or in combination with other red phosphors, particularly red phosphors with a red emission spectrum having a half-value width of 50 nm or more. . As such a red phosphor, A _{2 + x} M _y Mn _z F _n (A is Na and / or K; M is Si and Al; −1 ≦ x ≦ 1 and 0.9 ≦ y + z ≦ 1.1 and 0) KSF, KSNAF, and solid solution of KSF and KSNAF represented by .001 ≦ z ≦ 0.4 and 5 ≦ n ≦ 7), (kx) MgO.xAF ₂ .GeO ₂ : yMn ⁴⁺ , K is a real number of 2.8-5, x is a real number of 0.1-0.7, y is a real number of 0.005-0.015, A is calcium (Ca), strontium ( Sr), barium (Ba), zinc (Zn), or a mixture thereof), which is represented by the chemical formula of 3.5MgO.0.5MgF ₂ .GeO ₂ : Mn and other deep red (600 nm to 670 nm) germanate phosphor, (La _{1-x-y, Eu x} , Ln y) 2 O 2 S (x and y represent the number of each satisfy 0.02 ≦ x ≦ 0.50 and 0 ≦ y ≦ 0.50, Ln is Y, A LOS phosphor represented by a chemical formula of at least one trivalent rare earth element of Gd, Lu, Sc, Sm, and Er.

Further, SrAlSi ₄ N ₇ described in International Publication WO 2008-096300 and Sr ₂ Al ₂ Si ₉ O ₂ N ₁₄ : Eu described in US Pat. No. 7,524,437 may be used.
Among these, as the red phosphor, CASN phosphor, SCASN phosphor, CASON phosphor, and SBS phosphor are preferable.
Any one of the red phosphors exemplified above may be used, or two or more may be used in any combination and ratio.

<1-2-3. Green phosphor> The emission peak wavelength of the green phosphor is usually larger than 500 nm, preferably 510 nm or more, more preferably 515 nm or more, and usually 550 nm or less, especially 540 nm or less, and further 535 nm or less. It is preferable. If this emission peak wavelength is too short, it tends to be bluish, while if it is too long, it tends to be yellowish, and there is a possibility that the characteristics as green light will deteriorate.

The full width at half maximum of the emission peak of the green phosphor is usually in the range of 1 nm to 80 nm. The external quantum efficiency is usually 60% or more, preferably 70% or more, and the weight median diameter is usually 0.1 μm or more, preferably 1.0 μm or more, more preferably 5.0 mμ or more, usually 40 μm. Hereinafter, it is preferably 30 μm or less, more preferably 20 μm or less.
As such a green phosphor, for example, (Ba, Ca, Sr, Mg) ₂ SiO ₄ : Eu (hereinafter referred to as “BSS phosphor”) may be described in International Publication WO2007-091687. And Eu-activated alkaline earth silicate phosphors.

In addition, as the green phosphor, for example, Si _6-z Al _z N ₈ -z O _z : Eu (provided that 0 <z ≦ 4.2, which is described in Japanese Patent No. 3911545). Eu-activated oxynitride phosphor such as “β-SiAlON phosphor”), or M ₃ Si ₆ O ₁₂ N ₂ : Eu described in International Publication WO 2007-088966. (However, M represents an alkaline earth metal element. Hereinafter, it may be abbreviated as “BSON phosphor”.) Eu-activated oxynitride phosphor, and Japanese Patent Application Laid-Open No. 2008-274254. It is also possible to use a BaMgAl ₁₀ O ₁₇ : Eu, Mn activated aluminate phosphor (hereinafter sometimes abbreviated as “GBAM phosphor”).

Other green phosphors include Eu-activated alkaline earth silicon oxynitride phosphors such as (Mg, Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu, Sr ₄ Al ₁₄ O ₂₅ : Eu, Eu-activated aluminate phosphors such as (Ba, Sr, Ca) Al ₂ O ₄ : Eu, (Sr, Ba) Al ₂ Si ₂ O ₈ : Eu, (Ba, Mg) ₂ SiO ₄ : Eu, ( Ba, Sr, Ca) ₂ (Mg, Zn) Si ₂ O ₇ : Eu, (Ba, Ca, Sr, Mg) ₉ (Sc, Y, Lu, Gd) ₂ (Si, Ge) ₆ O ₂₄ : Eu, etc. Eu-activated silicate _{phosphors, Y 2 SiO 5: Ce,} Ce and Tb such, Tb-activated silicate _{phosphor, Sr 2 P 2 O 7 -Sr} 2 B 2 O 5: Eu -activated borate such as Eu phosphate _{phosphor, Sr 2 Si 3 O 8 -2SrCl} 2: such as Eu u-activated halo silicate _phosphor, Zn 2 _SiO 4: Mn-activated silicate phosphors such as _{Mn, CeMgAl 11 O 19: Tb} , Y 3 Al 5 O 12: Tb -activated aluminate phosphors such as Tb , Ca ₂ Y ₈ (SiO ₄ ) ₆ O ₂ : Tb, La ₃ Ga ₅ SiO ₁₄ : Tb-activated silicate phosphors such as Tb, (Sr, Ba, Ca) Ga ₂ S ₄ : Eu, Tb, Sm Eu, Tb, Sm activated thiogallate phosphor such as Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Y, Ga, Tb, La, Sm, Pr, Lu) ₃ (Al, Ga) ₅ O ₁₂ : Ce-activated aluminate phosphor such as Ce, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, Ca ₃ (Sc, Mg, Na, Li) ₂ Si ₃ O ₁₂ : Ce-activated silicate fluorescence such as Ce body, CaSc ₂ O _4: Ce activated oxide such as Ce Phosphor, Eu Tsukekatsusan nitride phosphor such as Eu-activated β-sialon, SrAl ₂ O _4: Eu-activated aluminate phosphor such as _{Eu, (La, Gd, Y} ) 2 O 2 S: Tb , etc. Tb-activated oxysulfide phosphors, CePO4, Ceb-activated phosphate phosphors such as LaPO ₄ : Ce, Tb, sulfide phosphors such as ZnS: Cu, Al, ZnS: Cu, Au, Al, _{Y, Ga, Lu, Sc,} La) BO 3: Ce, Tb, Na 2 Gd 2 B 2 O 7: Ce, Tb, (Ba, Sr) 2 (Ca, Mg, Zn) B 2 O 6: K, Ce, Tb
Ce, Tb activated borate phosphor such as Ca ₈ Mg (SiO ₄ ) ₄ Cl ₂ : Eu, Mn activated halosilicate phosphor such as Eu, Mn, (Sr, Ca, Ba) (Al, Ga , In) ₂ S ₄ : Eu-activated thioaluminate phosphors and thiogallate phosphors such as Eu, (Ca, Sr) ₈ (Mg, Zn) (SiO ₄ ) ₄ Cl ₂ : Eu, Mn, etc. An activated halosilicate phosphor, Eu activated oxynitride phosphor such as M ₃ Si ₆ O ₉ N ₄ : Eu, or the like can also be used.

Also, Sr ₅ Al ₅ Si ₂₁ O ₂ N ₃₅ : Eu described in International Publication WO2009-072043 and Sr ₃ Si ₁₃ Al ₃ N ₂₁ O ₂ described in International Publication WO2007-105631 are disclosed. : Eu can also be used.
Among these, as the green phosphor, BSS phosphor, β-SiAlON phosphor, and BSON phosphor are preferable.
Any one of the green phosphors exemplified above may be used, or two or more may be used in any combination and ratio.

  In addition, in order to enhance the color rendering property of the emitted light from the semiconductor light emitting device or to increase the light emission efficiency of the light emitting device, a green phosphor having a half width of the green emission spectrum of 20 nm or less (hereinafter referred to as “narrow”) as the green phosphor. May be referred to as "band green phosphors") alone.

<1-2-4. Blue phosphor>
The emission peak wavelength of the blue phosphor is usually 420 nm or more, preferably 430 nm or more, more preferably 440 nm or more, usually less than 500 nm, preferably 490 nm or less, more preferably 480 nm or less, still more preferably 470 nm or less, particularly preferably. The wavelength range is 460 or less.

The full width at half maximum of the emission peak of the blue phosphor is usually in the range of 10 nm to 100 nm. The external quantum efficiency is usually 60% or more, preferably 70% or more, and the weight median diameter is usually 0.1 μm or more, preferably 1.0 μm or more, more preferably 5.0 μm or more, usually 40 μm. Hereinafter, it is preferably 30 μm or less, more preferably 20 μm or less.
As such a blue phosphor, for example, a europium activated calcium halophosphate phosphor represented by (Ca, Sr, Ba) ₅ (PO ₄ ) ₃ Cl: Eu, (Ca, Sr, Ba) ₂ B ₅ O Europium activated alkaline earth chloroborate phosphor represented by ₉ Cl: Eu, (Sr, Ca, Ba) Al ₂ O ₄ : Eu or (Sr, Ca, Ba) ₄ Al ₁₄ O ₂₅ : Eu And europium activated alkaline earth aluminate phosphors.

In addition, as the blue phosphor, Sn-activated phosphate phosphors such as Sr ₂ P ₂ O ₇ : Sn, Sr ₄ Al ₁₄ O ₂₅ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, BaAl ₈ O ₁₃ : Eu-activated aluminate phosphors such as Eu, Ce-activated thiogallate phosphors such as SrGa ₂ S ₄ : Ce, CaGa ₂ S ₄ : Ce, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, Tb, Sm activated aluminate phosphor such as Eu, Tb, Sm, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, Mn activated aluminate phosphor such as Eu, Mn (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, (Ba, Sr, Ca) ₅ (PO ₄ ) ₃ (Cl, F, Br, OH): Eu, Mn, Sb, etc. Eu, b, Sm-activated halophosphate _{phosphor, BaAl 2 Si 2 O 8:} Eu, (Sr, Ba) 3 MgSi 2 O 8: Eu -activated silicate phosphors such as _{Eu, Sr 2 P 2 O 7} : Eu Eu-activated phosphate phosphors such as ZnS: Ag, ZnS: Ag, Al and other sulfide phosphors, Ce-activated silicate phosphors such as Y ₂ SiO ₅ : Ce, and tungstates such as CaWO ₄ Phosphor, (Ba, Sr, Ca) BPO ₅ : Eu, Mn, (Sr, Ca) ₁₀ (PO ₄ ) ₆ · nB ₂ O ₃ : Eu, 2SrO · 0.84P ₂ O ₅ · 0.16B ₂ O ₃ : Eu, Mn activated borate phosphate phosphor such as Eu, Sr
It is also possible to use Eu-activated halosilicate phosphors such as ₂ Si ₃ O ₈ .2SrCl ₂ : Eu.
Among these, (Sr, Ca, Ba) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu ²⁺ and BaMgAl ₁₀ O ₁₇ : Eu can be preferably used. _{Further, (Sr, Ca, Ba)} 10 (PO 4) 6 Cl 2: Among the phosphors represented by ^{_{Eu 2+, Sr a Ba b Eu}} x (PO 4) c Cl d (c, d and x are 2 0.7 ≦ c ≦ 3.3, 0.9 ≦ d ≦ 1.1, 0.3 ≦ x ≦ 1.2, and x is preferably 0.3 ≦ x ≦ 1.0 Furthermore, a and b satisfy the condition of a + b = 5-x and 0.05 ≦ b / (a + b) ≦ 0.6, and b / (a + b) is preferably 0.1 ≦ b / The phosphor represented by (a + b) ≦ 0.6 can be preferably used.

  In addition, in order to enhance the color rendering properties of the emitted light from the semiconductor light emitting device or to increase the light emission efficiency of the light emitting device, a blue phosphor having a half-value width of blue emission spectrum of 20 nm or less (hereinafter referred to as “narrow”) as the blue phosphor. May be referred to as "band blue phosphor") alone.

In this embodiment, the phosphor content in the wavelength conversion member is preferably 0.5% by weight or more, and more preferably 1% by weight or more. On the other hand, it is preferably 30% by weight or less, and more preferably 20% by weight or less.
The phosphor is mixed with the resin and kneaded to form the wavelength conversion member according to this embodiment. Moreover, it becomes the wavelength conversion member which concerns on this embodiment also by shape | molding, after melt | dissolving resin, adding a phosphor, kneading | mixing.

<1-3. Other>
It is preferable that the wavelength conversion member in this embodiment contains a diffusing agent. By containing the diffusing agent, it is possible to impart the light diffusibility of the wavelength conversion member.
Examples of the diffusing agent include inorganic light diffusing agents, organic light diffusing agents, and bubbles.

  As the inorganic light diffusing agent, for example, an inorganic light diffusing agent containing an element such as silicon, aluminum, titanium, zirconium, calcium, magnesium, zinc and barium can be used, and silicon, aluminum, It is preferable to use an inorganic light diffusing agent containing at least one element of the group consisting of titanium and zirconium. As the organic light diffusing agent material, it is possible to use acrylic, styrene, polyamide, or an organic light diffusing agent containing silicon or fluorine as an element, and among them, an acrylic light diffusing agent or silicon as an element. It is preferable to use an organic light diffusing agent containing

Specific examples of inorganic light diffusing agents include silicon dioxide (silica), white carbon, fused silica, talc, magnesium oxide, zinc oxide, titanium oxide, aluminum oxide, zirconium oxide, boron oxide, boron nitride, aluminum nitride, and nitride. Silicon, calcium carbonate, barium carbonate, magnesium carbonate, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, barium sulfate, calcium silicate, magnesium silicate, aluminum silicate, sodium silicate aluminide, zinc silicate, zinc sulfide, Examples of the material include glass particles, glass fibers, glass flakes, mica, wollastonite, zeolite, sepiolite, bentonite, montmorillonite, hydrotalcite, kaolin, and potassium titanate.
These inorganic diffusing agents may be treated with various surface treatment agents such as silane coupling agents, titanate coupling agents, methyl hydrogen polysiloxanes, fatty acid-containing hydrocarbon compounds, and the surface is inactive. It may be coated with an inorganic compound.

Examples of the organic light diffusing agent include materials such as styrene (co) polymers, acrylic (co) polymers, siloxane (co) polymers, and polyamide (co) polymers. Some or all of these organic diffusing agent molecules may or may not be crosslinked. Here, “(co) polymer” means both “polymer” and “copolymer”.

  The diffusing agent preferably contains at least one selected from the group consisting of silica, glass, calcium carbonate, mica, crosslinked acrylic (co) polymer particles, and siloxane (co) polymer particles. Further, the average particle diameter is preferably 1 μm or more, and preferably 30 μm or less. The average particle size is a particle size measured with an integrated weight percentage, a particle size distribution meter or the like.

When a diffusing agent is used in the present embodiment, it is usually contained in the wavelength conversion member by 0.1% by weight or more, preferably 0.3% by weight or more. Further, it is usually contained in an amount of 40% by weight or less, preferably 30% by weight or less.
The diffusing agent is usually contained in an amount of 0.1% by weight or more, preferably 0.3% by weight or more with respect to the resin composition before molding the wavelength conversion member. Further, it is usually contained in an amount of 40% by weight or less, preferably 30% by weight or less.

  As the other additive, an effective amount of an additive that can be normally used for the resin can be used in the wavelength conversion member according to this embodiment. Specifically, other thermoplastic resins, crystal nucleating agents, antioxidants, anti-blocking agents, ultraviolet absorbers, light stabilizers, plasticizers, heat stabilizers, colorants, flame retardants, mold release agents, antistatic agents Agent, antifogging agent, surface wetting improver, incineration aid, lubricant, flame retardant, crosslinking agent, dispersion aid and various surfactants, slip agent, hydrolysis inhibitor, neutralizing agent, reinforcing material, heat conduction material Etc. These may be used alone or in combination of two or more.

Specific examples of the antioxidant include 2,6-di-tert-butyl-4-hydroxytoluene, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pentaerythritol tetrakis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene- 2,4,6-triyl) tri-p-cresol, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris [(4-tert-butyl -3-hydroxy-2,6-xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris (3,5-di) -Tert-Buchi Ru-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, calcium diethylbis [[3,5-bis (1,1-dimethylethyl)- 4-hydroxyphenyl] methyl] phosphonate, bis (2,2′-dihydroxy-3,3′-di-tert-butyl-5,5′-dimethylphenyl) ethane, N, N′-hexane-1,6- Diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide) and other hindered phenol antioxidants, tridecyl phosphite, diphenyldecyl phosphite, tetrakis (2,4-di-tert -Butylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonite, bis [2,4-bis (1,1-dimethylethyl) -6- Phosphorous antioxidants such as [tilphenyl] ethyl ester phosphorous acid, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, 3-hydroxy-5,7-di-tert-butyl-furan- Examples include lactone-based antioxidants such as reaction products of 2-one and xylene, sulfur-based antioxidants such as dilauryl thiodipropionate, distearyl thiodipropionate, etc. These antioxidants are 1 You may use a seed | species independently and may use 2 or more types together by arbitrary combinations and a ratio.
Although the usage-amount of antioxidant is arbitrary unless the effect of this invention is impaired remarkably, it is normally 100 weight ppm or more and 50000 weight ppm or less with respect to resin. If the lower limit of this range is not reached, the effect of the antioxidant may be reduced, and if the upper limit is exceeded, the antioxidant may bleed out or cause coloring.

  Specific examples of the crystal nucleating agent include inorganic nucleating agents such as talc, kaolin, montmorillonite, synthetic mica, clay, zeolite, silica, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, calcium sulfide, boron nitride. , Calcium carbonate, barium sulfate, aluminum oxide, neodymium oxide, and metal salts of phenylphosphonate. In addition, these inorganic nucleating agents may be modified with an organic substance in order to enhance dispersibility in the composition.

  On the other hand, organic nucleating agents include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate, calcium oxalate, lauric acid. Sodium phosphate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, barium stearate, Sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, zinc salicylate, aluminum Organic carboxylic acid metal salts such as mudibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, sodium cyclohexanecarboxylate; organic sulfonates such as sodium p-toluenesulfonate, sodium sulfoisophthalate; stearamide, Carboxylic acid amides such as ethylene bislauric acid amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide, trimesic acid tris (t-butylamide); low density polyethylene, high density polyethylene, polypropylene, polyisopropylene, polybutene, poly Polymers such as -4-methylpentene, polyvinylcycloalkane, polyvinyltrialkylsilane, and high melting point polylactic acid; ethylene-acrylic acid or methacrylic acid copoly Sodium salt or potassium salt of a polymer having a carboxyl group such as sodium salt of styrene-maleic anhydride copolymer (so-called ionomer); benzylidene sorbitol and its derivatives, sodium-2,2'-methylenebis (4 Phosphorus compound metal salts such as 6-di-t-butylphenyl) phosphate; and 2,2-methylbis (4,6-di-t-butylphenyl) sodium; polyethylene wax.

  The average particle diameter of the nucleating agent is arbitrary as long as the effects of the present invention are not significantly impaired. Usually, it is 50 μm or less, preferably 10 μm or less. A preferable blending amount of the nucleating agent is usually 0.01 parts by mass or more and 5 parts by mass or less based on 100 parts by mass of the resin.

Examples of the light stabilizer include decanoic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, bis (1,2,2 , 6,6-pentamethyl-4-piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate , 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl) -4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine -2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] Examples include hindered amine stabilizers.
A light stabilizer may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
Furthermore, the usage-amount of a light stabilizer is 0.1 to 5 mass parts normally with respect to 100 mass parts of resin.

  Examples of the ultraviolet absorber include organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, and triazine compounds in addition to inorganic ultraviolet absorbers such as cerium oxide and zinc oxide. Among these, benzotriazole compounds, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2,4-Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2 ′-(1,4-phenylene) bis [4H-3,1-benzoxazine -4-one], [(4-methoxyphenyl) -methylene] -propanedioic acid-dimethyl ester is preferred.

Specific examples of the benzotriazole compound include condensates of methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol. Specific examples of other benzotriazole compounds include 2-bis (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-di-tert-butyl-2′-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy- 3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′-methylene-bi [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] [methyl-3- [3-tert-butyl-5- (2H-benzotriazole) -2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol] condensate.
A ultraviolet absorber may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
Moreover, the usage-amount of a ultraviolet absorber is 100 ppm or more and 5 mass% or less normally.

Examples of the flame retardant include halogen-based, phosphorus-based, organic acid metal salt-based, silicone-based, antimony compounds, nitrogen compounds and inorganic compounds, and examples of the flame retardant aid include fluorine resin flame retardant aid. A flame retardant and a flame retardant aid can be used in combination, or a plurality of flame retardants can be used in combination. Among these, phosphorus flame retardants, organic acid metal salt flame retardants, and fluororesin flame retardant aids are preferred.
Examples of the halogen-based flame retardant include brominated polycarbonate, brominated epoxy resin, brominated phenoxy resin, brominated polyphenylene ether resin, brominated polystyrene resin, brominated bisphenol A, and pentabromobenzyl polyacrylate.
Examples of phosphorus flame retardants include aromatic phosphate esters, polyphosphoric acid, ammonium polyphosphate, red phosphorus, and phosphazene compounds.
Examples of the antimony compound include antimony trioxide, antimony pentoxide, sodium antimonate, and the like.
As the organic acid metal salt flame retardant, an organic sulfonic acid metal salt is preferable, and a fluorine-containing organic sulfonic acid metal salt is particularly preferable. Specific examples thereof include potassium perfluorobutane sulfonate.
Examples of the nitrogen compound include melamine, cyanuric acid, and melamine cyanurate.
Examples of inorganic compounds include aluminum hydroxide, magnesium hydroxide, and boron compounds.
As the fluorine-based flame retardant aid, a fluoroolefin resin is preferable, and a tetrafluoroethylene resin having a fibril structure can be exemplified. The fluorine-based flame retardant aid may be in a powder form, a dispersion form, a powder form in which a fluororesin is coated with another resin, or any form.

  The blending ratio of these flame retardants and flame retardant aids may be blended in an amount necessary to achieve a desired flame retardant level, but is usually 0.01 to 30 parts by weight with respect to 100 parts by weight of the resin. is there. Within the above range, one or more flame retardants and flame retardant aids can be used. If the amount is less than this range, it is difficult to improve the flame retardancy. If the amount is more than this range, the thermal stability and mechanical properties tend to decrease, which is not preferable.

<1-4. Injection molding>
The wavelength conversion member according to this embodiment is formed by injection molding. A known method may be used as the injection molding method. For example, in order to produce a composition containing a resin and a phosphor, preferably a diffusing agent and other additives added as necessary, a uniaxial or A twin screw extruder can be used as the kneader. These materials may be supplied all at once from one place or sequentially. Moreover, you may mix and knead | mix beforehand 2 or more types of components chosen from each component. In particular, the phosphor is preferably supplied after mixing with other powder components. In addition, the extruder may be provided with a vent port that can volatilize volatile components. After the kneading, the pellet-shaped composition is supplied to an injection molding machine and molded by injection molding.

In the injection molding, the resin composition is melted by heating, and the molten resin composition is molded by injection into a mold. It is also possible to supply two or more types of pellets having different composition blends by dry blending at an arbitrary ratio and melt-mixing and molding in an injection molding machine. In the case of an amorphous resin, the melting temperature is preferably a temperature above the glass transition point, and in the case of a crystalline resin, the temperature is preferably a melting point or higher, for example, 150 ° C. or higher, preferably 170 ° C. It is above ℃. When the molding temperature is too high, the molded body may be colored. Therefore, the molding is preferably performed at a temperature of 170 ° C. or higher and 320 ° C. or lower.
In the injection molding, it is preferable to use an injection molding apparatus with a hot runner because the loss of the sprue runner can be reduced.

  The molded body may have any shape as long as it can be a light emitting surface in the white LED light emitting device. Generally, the thickness is 0.3 mm to 5 mm. Further, the molded article of the present invention may have a single layer structure or a multilayer laminated structure of two or more layers. Further, the surface may be a mirror surface or may have a fine structure such as a texture, and the outer surface can be hard-coated or printed.

<2. Chromaticity measurement process>
The chromaticity measurement step according to this embodiment is a step of measuring the chromaticity of the molded article that has been molded. The chromaticity of the molded body is calculated based on, for example, the CIE xy 1931 chromaticity diagram by irradiating the molded body with light having a specific excitation wavelength and radiating light from the molded body. Specifically, the measurement of chromaticity is, for example, a light emitting device capable of obtaining white light by irradiating blue light of an LED chip having a peak wavelength of 455 nm, and an emission spectrum from the light emitting device, which is 20 inch manufactured by Sphere Optics. By observing with an integrating sphere and a spectroscope USB2000 + manufactured by Ocean Optics, and calculating xy chromaticity coordinates on the CIE 1931 chromaticity diagram based on JIS Z8724: 1997 (title: color measurement method—light source color—) Can be obtained.

In the chromaticity measurement step, the chromaticity of the molded article is measured. By measuring the chromaticity of the molded body, the chromaticity information of the molded body can be fed back to the molding of the molded body. For example, a threshold value of chromaticity is determined in advance, whether it is within the range or out of the range, and when the molded product is inappropriate as a product, the information is fed back as described later. It becomes possible.
In the chromaticity measurement step, it is also preferable to measure the color temperature. In white LEDs, the color temperature is important, and it is preferable to also grasp the color temperature of the molded body. The color temperature is converted into uv chromaticity coordinates on the CIE 1960 UCS chromaticity diagram based on the result of xy chromaticity coordinates, and then converted into JIS Z8725: 1999 (title: distribution temperature of light source and color temperature / correlated color temperature). It can be calculated based on the measurement method. When the specific excitation light is in the blue region, the color temperature of the light emitted from the molded body when irradiated with the specific excitation light can be adjusted to be in the vicinity of the black body radiation locus from 2500K to 6500K. Is preferred.

  In the chromaticity measurement step, the light having a specific excitation wavelength with which the molded body is irradiated may have any wavelength, and is appropriately selected according to the application of the wavelength conversion member. When the wavelength conversion member is used as a wavelength conversion member of a white light-emitting device, it is preferable that the excitation light having a specific wavelength is light in the purple region or light in the blue region.

<3. Feedback>
The manufacturing method according to this embodiment is characterized in that the thickness of the molded body can be adjusted by feeding back the chromaticity measured in the chromaticity measurement step to the molding step.
The feedback method is not particularly limited, and may be adjusted based on the chromaticity measured in the measurement process so as to increase or decrease the thickness of the molded body molded in the molding process.
The thickness adjustment in the molding process may be arbitrarily adjusted according to various setting conditions during injection molding, and is not particularly limited. For example, the filling amount of the resin composition in the molding process, and the adjustment conditions in the molding machine are molding resin temperature, mold temperature, injection pressure (including holding pressure), injection speed, injection time (including holding time), mold For example, adjustment of increase / decrease in tightening force can be exemplified.

The thickness of the molded body can be adjusted by, for example, how the chromaticity of the molded body is shifted on the xy chromaticity coordinates. When the chromaticity of the molded body shifts to the lower left on the xy chromaticity coordinates, the molded body is adjusted to increase its thickness. On the other hand, when the chromaticity of the molded body shifts to the upper right on the xy chromaticity coordinates, the molded body is adjusted to be thin.
As an example, when the thickness of the molded body is adjusted by holding pressure, when the chromaticity of the molded body shifts to the lower left on the xy chromaticity coordinates, the pressure of the molded body is adjusted to increase. When the chromaticity is shifted to the upper right on the xy chromaticity coordinates, adjustment is performed so as to reduce the holding pressure in the molding process.

  The control method of such feedback control is not particularly limited, automatic control may be performed by a computer, the result of chromaticity measurement may be confirmed with the human eye, and the thickness of the molded body in the molding process may be adjusted.

The molded body (wavelength conversion member) in this embodiment has a thickness of usually 0.3 mm or more, preferably 0.5 mm or more, and usually 5 mm or less, preferably 3 mm or less.
By the feedback in this embodiment, it is preferable to adjust the thickness of the molded body by changing the film thickness of the molded body before the feedback by 0.5% or more, more preferably by changing 1% or more. preferable.
The thickness error in the injection molding of a normal molded body is at most about 0.5% within the same production lot. Therefore, when the thickness difference between different production lots of the molded product (wavelength conversion member) is generally 0.5% or more, it is assumed that the thickness is intentionally controlled for some purpose. Is done.

<4. Light emitting device, lighting device>
The wavelength conversion member in the embodiment of the present invention is provided in the light emitting device together with the semiconductor light emitting element.
A light emitting device using the wavelength conversion member in this embodiment will be described. The light emitting device includes at least a blue semiconductor light emitting element and a wavelength conversion member according to this embodiment. The blue semiconductor light-emitting element and the wavelength conversion member according to this embodiment may be in close contact with each other, may have a space between them, or may have a light transmission member such as a light guide plate. A structure having a space between them is preferable. Hereinafter, the configuration will be described with reference to FIGS.

FIG. 3 is a schematic view of a light emitting device including the wavelength conversion member according to this embodiment.
The light emitting device 10 includes at least a blue semiconductor light emitting element 1 and a wavelength conversion member 3 as its constituent members. The molded body according to the embodiment of the present invention is used as a wavelength conversion member in a light emitting device. The blue semiconductor light emitting element 1 emits excitation light for exciting the phosphor contained in the wavelength conversion member 3.
The blue semiconductor light emitting element 1 usually emits excitation light having a peak wavelength of 425 nm to 475 nm, and preferably emits excitation light having a peak wavelength of 430 nm to 470 nm. The number of blue semiconductor light emitting elements 1 can be appropriately set depending on the intensity of excitation light required by the apparatus.
Instead of the blue semiconductor light emitting element 1, a purple semiconductor light emitting element can also be used. The violet semiconductor light emitting device usually emits excitation light having a peak wavelength of 390 nm to 425 nm, and preferably emits excitation light having a peak wavelength of 395 to 415 nm.

The blue semiconductor light emitting element 1 is mounted on the chip mounting surface 2 a of the wiring board 2. A wiring pattern (not shown) for supplying electrodes to these blue semiconductor light emitting elements 1 is formed on the wiring substrate 2 to constitute an electric circuit. In FIG. 3, the wavelength conversion member 3 is displayed on the wiring board 2, but the present invention is not limited to this, and the wiring board 2 and the wavelength conversion member 3 may be arranged via other members.
For example, in FIG. 4, the wiring substrate 2 and the wavelength conversion member 3 are arranged via the frame body 4. The frame body 4 may have a tapered shape in order to give light directivity. The frame 4 may be a reflective material.

  The wiring board 2 is excellent in electrical insulation, has good heat dissipation, and preferably has a high reflectance, but on the surface where the blue semiconductor light emitting element 1 is not present on the chip mounting surface of the wiring board 2, Alternatively, a reflective plate having a high reflectance can be provided on at least a part of the inner surface of another member that connects the wiring substrate 2 and the wavelength conversion member 3. The reflectance of such a wiring board or reflector is preferably 80% or more. As such a wiring board, alumina ceramic, resin, glass epoxy, composite resin containing filler in resin, or the like can be used. Further, as the reflection plate placed on the chip mounting surface 2a of the wiring board 2, a resin containing a white pigment such as alumina powder, silica powder, magnesium oxide, titanium oxide, zirconium oxide, zinc oxide, zinc sulfide is used. it can. Preferred resins include silicone resin, polycarbonate resin, polybutylene terephthalate resin, polyphenylene sulfide resin, fluorine-based resin and the like.

The wavelength conversion member 3 converts the wavelength of a part of incident light emitted from the blue semiconductor light emitting element 1 and emits outgoing light having a wavelength different from that of the incident light. The wavelength conversion member 3 contains a crystalline thermoplastic resin and a phosphor. The type of phosphor (not shown) is not particularly limited, and if the light emitting device is a white light emitting device, the type of phosphor is appropriately adjusted to emit white light according to the type of excitation light of the semiconductor light emitting element. do it.
When the semiconductor light emitting device is a blue semiconductor light emitting device, for example, a yellow phosphor, a yellow phosphor and a red phosphor (or an orange phosphor), a green phosphor and a red phosphor (or an orange phosphor) are used. ) Can be used as a light emitting device that emits white light.
When the semiconductor light emitting element is a purple semiconductor light emitting element, for example, a blue light emitting material, a green light emitting material, and a red light emitting material can be used to obtain a light emitting device that emits white light.

  The wavelength conversion member 3 preferably contains a small amount of a diffusing agent together with the phosphor. Examples of the diffusing agent include inorganic light diffusing agents, organic light diffusing agents, and bubbles. The diffusing agent preferably contains one or more selected from the group consisting of silica, glass, calcium carbonate, mica, crosslinked acrylic (co) polymer particles, and siloxane (co) polymer particles.

  The wavelength conversion member 3 has a distance from the blue semiconductor light emitting element 1. There may be a gap between the wavelength conversion member 3 and the blue semiconductor light emitting element 1 or may be filled with a filler. Thus, by the aspect which has distance between the wavelength conversion member 3 and the blue semiconductor light-emitting device 1, deterioration of the phosphor contained in the wavelength conversion member 3 and the wavelength conversion member by the heat which the blue semiconductor light-emitting device 1 emits is suppressed. can do. The distance between the blue semiconductor light emitting element 1 and the wavelength conversion member 3 is preferably 10 μm or more, more preferably 100 μm or more, particularly preferably 1.0 mm or more, on the other hand, 1.0 m or less, more preferably 500 mm or less, 100 mm or less is particularly preferable.

The light emitting device is preferably a light emitting device that emits white light. In the light emitting device that emits white light, the light emitted from the light emitting device has a deviation duv from the light-colored black body radiation locus of −0.0200 to 0.0200, and the color temperature is 2500 K or more and 6500 K or less. It is preferable that
Thus, the light-emitting device which radiate | emits white light is suitably provided in an illuminating device.

  Hereinafter, the present invention will be described in more detail with reference to actual examples.

<Production Examples 1-2>
Each material was weighed at a weight ratio shown in Table 1, and melt-kneaded at a set temperature of 260 to 270 ° C. and a screw rotation speed of 170 rpm using a 40 mmφ single screw extruder to obtain pellets of phosphor-containing polycarbonate resin composition, respectively. .

<Experimental example 1>
The phosphor-containing polycarbonate resin composition obtained in Production Example 1 was dry blended with the polycarbonate resin Iupilon S3000 at a weight ratio of 1: 1 to make the total charged concentration of the phosphor 4.00 wt%. Using an injection molding machine with a clamping force of 18t, this was 61.5mmφ × 2mm
A mold having a thick cavity was injection-molded at a mold set temperature of 80 ° C. and an injection set temperature of 280 ° C. The obtained wavelength conversion member, which is a molded product, was irradiated with excitation light having a wavelength of 455 nm using a light emitting device of the type shown in FIG. 4, and the chromaticity of light emitted from the light emitting device was measured. At this time, the chromaticity ranges were 0.455 ≦ x ≦ 0.465 and 0.409 ≦ y ≦ 0.417 as acceptable ranges.
When a polycarbonate composition having a phosphor concentration of 4.035 wt% was molded under pressure-holding conditions of 70 MPa for injection molding, 5 samples were molded and all 5 samples passed.

<Experimental example 2>
As an example in which the concentration of the phosphor during production falls, the phosphor-containing polycarbonate resin composition obtained in Production Example 1 is dry blended with the polycarbonate resin Iupilon S3000 at a weight ratio of 99: 101 to total the concentration of the phosphor charged. When a polycarbonate composition having a 3.995 wt% was molded under the same pressure holding conditions of 70 MPa, it was molded at 5 points and failed at 3 points.
<Experimental example 3>
When a polycarbonate composition having the same charge concentration of 3.995 wt% was molded by raising the holding pressure condition to 90 MPa, 5 samples were molded and all 5 samples passed.
These results are shown in FIG. In the sample molding of Experimental Example 1 which is a standard product, the pressure holding condition is increased even when the density decreases during molding and the chromaticity of the molded product shifts to the lower left in the xy chromaticity coordinates (Experimental Example 2). Thus, the chromaticity deviation can be eliminated (Experimental Example 3).
From these experimental results, the thickness of the molded body to be molded is measured by measuring the chromaticity of the light emitted from the molded body after the formation process and feeding back the measurement results to the molding conditions (holding pressure in this experimental example). The production of a non-standard molded body can be suppressed.

<Experimental example 4>
The phosphor-containing polycarbonate resin composition obtained in Production Example 2 was dry blended with the polycarbonate resin Iupilon S3000 at a weight ratio of 95: 105 to give a total phosphor concentration of 3.933 wt%, and injection molding was performed as in Experimental Example 1. Then, the chromaticity was measured. At this time, the chromaticity ranges were 0.435 ≦ x ≦ 0.450 and 0.390 ≦ y ≦ 0.401 as acceptable ranges.
When a polycarbonate composition having a total charged concentration of 3.933 wt% of this phosphor was molded under a pressure holding condition of 70 MPa, 5 samples were molded and all 5 samples passed.

<Experimental example 5>
As an example in which the concentration of the phosphor during production increased, the phosphor-containing polycarbonate resin composition obtained in Production Example 2 was dry blended with the polycarbonate resin Iupilon S3000 at a weight ratio of 97: 103 to obtain a total concentration of 4.016 wt. %, When the polycarbonate composition was molded under the same holding pressure condition of 70 MPa, it was molded at 5 points, and 2 points were rejected.
<Experimental example 6>
When a polycarbonate composition having the same charge concentration of 4.016 wt% was molded under reduced pressure holding conditions to 50 MPa, 5 samples were molded and all 5 samples passed.
These results are shown in FIG. In the sample molding of Experimental Example 4 which is a standard product, the pressure holding condition is lowered even when the density increases during molding and the chromaticity of the molded product shifts to the upper right in the xy chromaticity coordinates (Experimental Example 5). Thus, the chromaticity deviation can be eliminated (Experimental Example 6).
From these experimental results, the thickness of the molded body to be molded is measured by measuring the chromaticity of the light emitted from the molded body after the formation process and feeding back the measurement results to the molding conditions (holding pressure in this experimental example). The production of a non-standard molded body can be suppressed.

DESCRIPTION OF SYMBOLS 10 Light-emitting device 1 Semiconductor light-emitting element 2 Wiring board 2a Chip mounting surface 3 Wavelength conversion member 4 Frame

Claims (14)

A method for producing a wavelength conversion member comprising a molding step of molding a phosphor resin composition containing a phosphor by injection molding,
Including a measurement step of measuring the chromaticity of light emitted from the molded body by irradiating light of a specific excitation wavelength to the molded body molded in the molding step,
A method for producing a wavelength conversion member, wherein the thickness of a molded body to be molded can be adjusted by feeding back the measured chromaticity to the molding step.   In the molding step, one or more adjustments selected from the group consisting of the filling amount of the resin composition into the molding step, the resin composition temperature, the injection pressure in injection molding, the holding pressure, and the holding pressure switching position. The method for producing a wavelength conversion member according to claim 1, wherein the thickness of the molded body to be molded is adjusted.   In the measurement step, when the chromaticity is shifted to the lower left on the xy chromaticity coordinates, the thickness of the molded body is increased. When the chromaticity is shifted to the upper right on the xy chromaticity coordinates, the thickness of the molded body is increased. The manufacturing method of the wavelength conversion member of Claim 2 which adjusts the thickness of the molded object shape | molded so that it may become thin.   The said phosphor composition is a manufacturing method of the wavelength conversion member of any one of Claim 1 to 3 containing a thermoplastic resin.   The said fluorescent substance resin composition is a manufacturing method of the wavelength conversion member of any one of Claim 1 to 4 containing polycarbonate resin.   The said fluorescent substance resin composition is a manufacturing method of the wavelength conversion member of Claim 4 or 5 formed by melt-mixing fluorescent substance and resin.   The wavelength according to any one of claims 1 to 6, wherein the film thickness of the molded body is changed by 0.5% or more from the film thickness of the molded body before feedback by feedback to the molding process. Manufacturing method of conversion member.   The manufacturing method of the wavelength conversion member of any one of Claim 1 to 7 containing only 1 type of fluorescent substance.   The method for producing a wavelength conversion member according to claim 8, wherein the phosphor is a yellow phosphor.   The manufacturing method of the wavelength conversion member of any one of Claim 1 to 7 containing 2 or more types of fluorescent substance.   The method for producing a wavelength conversion member according to claim 10, wherein the phosphor includes a yellow phosphor and a red phosphor, or a green phosphor and a red phosphor.   The said conversion process WHEREIN: The color temperature of the light radiated | emitted from a molded object when irradiated with specific excitation light is 2500K or more and 6500K or less, The manufacture of the wavelength conversion member of any one of Claim 1 to 11 Method.   The method for manufacturing a wavelength conversion member according to any one of claims 1 to 12, wherein the specific excitation light is blue light. A method for producing a light emitting device including a wavelength conversion member, comprising a molding step of molding a phosphor resin composition containing a phosphor by injection molding,
Including a measurement step of measuring the chromaticity of light emitted from the molded body by irradiating light of a specific excitation wavelength to the molded body molded in the molding step,
A method of manufacturing a light emitting device, wherein the thickness of a molded body to be molded can be adjusted by feeding back the measured chromaticity to the molding step.

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