WO2010074038A1 - Module électroluminescent et son procédé de fabrication - Google Patents

Module électroluminescent et son procédé de fabrication Download PDF

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Publication number
WO2010074038A1
WO2010074038A1 PCT/JP2009/071258 JP2009071258W WO2010074038A1 WO 2010074038 A1 WO2010074038 A1 WO 2010074038A1 JP 2009071258 W JP2009071258 W JP 2009071258W WO 2010074038 A1 WO2010074038 A1 WO 2010074038A1
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emitting element
light emitting
amorphous
light
intermediate layer
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PCT/JP2009/071258
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English (en)
Japanese (ja)
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杉山　徳英
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旭硝子株式会社
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Priority to JP2010544058A priority Critical patent/JPWO2010074038A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/56—Materials, e.g. epoxy or silicone resin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/85—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a wire connector
    • H01L2224/85909—Post-treatment of the connector or wire bonding area
    • H01L2224/8592—Applying permanent coating, e.g. protective coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/54—Encapsulations having a particular shape

Definitions

  • the present invention relates to a light emitting element module and a manufacturing method thereof.
  • light-emitting elements such as white LEDs (Light Emitting Diodes) have been developed as next-generation energy-saving high-efficiency illumination light sources. These light emitting elements are sealed with a light-transmitting sealing resin such as a silicone resin in order to protect the elements and the wiring portions.
  • a light-transmitting sealing resin such as a silicone resin
  • silicone has high gas permeability, and water vapor is a cause of deterioration of LED elements and phosphors.
  • Ag with high light reflectivity is used as the electrode material, but the sulfur compound floating in the air permeates the silicone sealing part and blackens the Ag electrode, resulting in a decrease in reflectivity. Thus, there is a problem that the light extraction efficiency is lowered.
  • Patent Documents 1 and 2 propose translucent sealing of an LED with a film formed by a coating liquid composed of an amorphous fluorine-containing polymer and a fluorine-containing solvent.
  • Patent Document 2 discloses translucent sealing of an LED using a curable composition containing a curable amorphous fluorine-containing polymer.
  • Patent Document 1 it is difficult to obtain a thickness necessary for LED sealing.
  • amorphous fluoropolymers such as Patent Documents 1 and 2 are generally not particularly excellent in adhesiveness with the light emitting element module member, and may be peeled off from the light emitting element module member in some cases. There is a risk that. Therefore, using various silane coupling agents generally used to improve adhesion to inorganic materials such as metals and ceramics and plastics, adhesion between amorphous fluoropolymers and light emitting device module members It was considered to improve.
  • a protective film using a curable amorphous fluorine-containing polymer it is excellent in initial adhesiveness and heat resistance to a light-emitting element and an electric wiring passing through the light-emitting element, and can be used continuously at high temperatures. It is an object of the present invention to provide a light emitting element module having a stable protective film and capable of reducing deterioration of the light emitting element and electric wiring, and a manufacturing method thereof.
  • a light emitting element module including a light emitting element and an electric wiring for energizing the light emitting element, the light emitting element and the electric wiring being covered with a protective film, wherein the protective film is in contact with the light emitting element A layer and a coating layer formed on the intermediate layer, the intermediate layer containing an amorphous aromatic resin (A) having an aromatic ring in the main chain, and the coating layer having an aromatic ring
  • a light-emitting element module comprising an amorphous fluorine-containing resin (B) obtained by curing a non-curable amorphous fluorine-containing polymer (b).
  • the amorphous aromatic resin (A) is a polyethersulfone resin.
  • the amorphous aromatic resin (A) has a thermal expansion coefficient of 20 to 100 ppm / ° C.
  • a method for producing a light emitting device module comprising a light emitting device and an electric wiring for energizing the light emitting device, wherein the light emitting device and the electric wiring are covered with a protective film, wherein the crosslinkable functional group (x)
  • An aromatic fluorine-containing resin having an aromatic ring in the main chain after applying a coating solution prepared by dissolving the prepolymer (a) having a solvent in a solvent to the light emitting element and the electric wiring, and then curing the prepolymer (a) An intermediate layer forming step of forming an intermediate layer containing (A1), and a curable amorphous fluorine-containing polymer (b) having no aromatic ring applied on the intermediate layer, the curable amorphous A coating layer forming step of curing the fluorinated polymer (b) with heat or light to form a coating layer containing the amorphous fluorine-containing resin (B); Manufacturing method of light emitting element module having [10] A method for manufacturing a light emit
  • a coating layer forming step of forming a coating layer Manufacturing method of light emitting element module having [11] The method for producing a light-emitting element module according to [9] or [10], wherein the curable amorphous fluoropolymer (b) includes a polymerizable compound (b1) having a polymerizable double bond. .
  • the light-emitting element module of the present invention is excellent in initial adhesion and heat resistance to a light-emitting element and an electric wiring passing through the light-emitting element as a protective film using a curable amorphous fluoropolymer, and continuously at a high temperature. Even in use, it has a stable protective film. Therefore, deterioration of the light emitting element and the electric wiring can be reduced by the protective film even in continuous use at a high temperature.
  • a protective film using a curable amorphous fluorine-containing polymer it is excellent in initial adhesiveness and heat resistance to a light emitting element and an electric wiring passing through the light emitting element, and has a high temperature.
  • a light-emitting element module having a stable protective film even in continuous use and capable of reducing deterioration of the light-emitting element and electric wiring can be obtained.
  • the light-emitting element module of the present invention is a light-emitting element module that includes a light-emitting element and electric wiring for energizing the light-emitting element, and the light-emitting element and the electric wiring are covered with a protective film.
  • the protective film has an intermediate layer in contact with the light emitting element, and a coating layer formed on the intermediate layer, the intermediate layer containing an amorphous aromatic resin (A),
  • the coating layer includes an amorphous fluorine-containing resin (B).
  • the light emitting element module of this invention is comprised by the module member 10 and the protective film 20, as shown in FIG. [Module members]
  • the module member 10 includes a substrate 11, electrodes 12 a and 12 b provided on the substrate 11, an optical element 13 provided on the electrodes 12 a and 12 b, and a bonding wire that connects the electrodes 12 a and 12 b and the optical element 13. 14 and a reflector 15 that reflects the light emitted from the optical element 13.
  • a recess 16 is formed by the substrate 11 and the reflector 15 provided at the end of the substrate 11.
  • a desired circuit is formed by the electrodes 12 a and 12 b on the substrate 11, and the light emitting element 13 is installed on the electrode 12 a.
  • the light emitting element 13 is connected to and connected to the electrodes 12a and 12b by the bonding wire 14, and the light emitting element 13 can be energized by connecting the electrodes 12a and 12b to an external power source (not shown). ing.
  • the electrodes 12 a and 12 b and the bonding wire 14 constitute an electrical wiring for energizing the light emitting element 13.
  • a substrate usually used for an optical element module can be used.
  • a resin or ceramic substrate, or a metal substrate provided with an insulating layer between the electrodes 12 a and 12 b can be used.
  • the shape and thickness of the substrate 11 are not particularly limited and can be appropriately selected depending on the application.
  • electrodes 12a and 12b electrodes usually used in an optical element module can be used, and examples thereof include an Ag electrode, an Au electrode, and an Al electrode.
  • the optical element 13 a known light emitting element can be used, and examples thereof include a blue LED, an ultraviolet LED, and a laser diode (LD).
  • the reflector 15 only needs to reflect visible light having a wavelength of 400 to 700 nm emitted from the optical element 13 with high efficiency, and examples thereof include those made of resin and ceramic.
  • the electrodes 12 a and 12 b and the light emitting element 13 are covered with the light-transmitting protective film 20 including the intermediate layer 21 and the covering layer 22 in the recess 16.
  • the bonding wire 14 is buried in the protective film 20.
  • the protective film 20 includes an intermediate layer 21 formed on the light emitting element 13 and the electrodes 12 a and 12 b and a coating layer 22 formed on the intermediate layer 21.
  • the protective film 20 plays a role of protecting the optical element 13 and the electrodes 12a and 12b.
  • the bonding wire only needs to cover at least a part of the connection portion with the electrode by the intermediate layer, and the entire bonding wire is not necessarily covered by the intermediate layer.
  • the intermediate layer 21 plays a role of improving the initial adhesiveness between the light emitting element 13 and the electrodes 12 a and 12 b and the protective film 20 and the heat resistance of the protective film 20.
  • the amorphous aromatic resin (A) used for forming the intermediate layer 21 is an amorphous resin having an aromatic ring in the main chain.
  • the amorphous aromatic resin (A) is a resin that does not undergo a curing reaction by itself after the intermediate layer 21 is formed. That is, when a non-curable resin is used to form the intermediate layer 21, it means the resin itself, and when a curable polymer is used, it means that the curing reaction is terminated.
  • the intermediate layer 21 having a high Tg and a low coefficient of thermal expansion is obtained, and the heat generation of the light emitting element 13 reaches a high temperature of 150 ° C. or higher.
  • the intermediate layer 21 is not deformed or thermally decomposed, the adhesiveness is hardly lowered, and the reliability of the light emitting element module is ensured.
  • the amorphous aromatic resin (A) for example, polyimide resin, polyamide resin, polyamideimide resin, polysulfone resin, polyethersulfone resin, polyetherketone resin, polyarylene resin, polyarylene ether resin, aromatic series-containing A fluororesin etc. are mentioned. Of these, polyethersulfone resins, polyarylene resins, polyarylene ether resins, and aromatic fluorine-containing resins are preferable. In terms of transparency, polyethersulfone resin is more preferable. In view of light resistance and transparency, an aromatic fluorine-containing resin is more preferable. In addition, the amorphous aromatic resin (A) preferably has a heteroatom in a portion to which an aromatic ring is bonded because the adhesion between the intermediate layer 21 and the coating layer 22 is improved.
  • the aromatic fluorine-containing resin is an amorphous fluorine-containing resin having an aromatic ring in the main chain.
  • the aromatic fluorine-containing resin include fluorine-containing polyarylenes and fluorine-containing polyarylene ethers described in JP-T-5-502257, JP-A-10-247646, WO 03/8483, and the like.
  • aromatic fluorine-containing resins described in JP-A-2005-105115 Of these, an aromatic fluorine-containing resin (A1) obtained by curing a prepolymer (a) having a crosslinkable functional group (x) described in JP-A-2005-105115 is preferable.
  • aromatic fluorine-containing resin (A1) examples include a compound (a1-1) having a crosslinkable functional group (x) and a phenolic hydroxyl group (hereinafter referred to as “compound (a1-1)”) and / or.
  • Compound (a1-2) having a crosslinkable functional group (x) and a fluorine atom-substituted aromatic ring (hereinafter referred to as “compound (a1-2)”), a fluorine-containing aromatic compound (a2) described later, and phenol A resin (cured) obtained by curing a prepolymer (a) obtained by subjecting a compound (a3) having 3 or more functional hydroxyl groups (hereinafter referred to as “compound (a3)”) to a condensation reaction in the presence of a deHF agent.
  • the aromatic fluororesin (A1) thus obtained has a crosslinkable functional group (x) and an ether bond.
  • the crosslinkable functional group (x) in the compound (a1-1) and the compound (a1-2) does not substantially react during the production of the prepolymer (a) (during the condensation reaction) and gives external energy.
  • Reactive functional groups that react with each other to cause cross-linking or chain extension between prepolymers.
  • the external energy heat, light, an electron beam, or a combination thereof is preferable from the viewpoint of excellent applicability in the mounting process of the optical element 13.
  • crosslinkable functional group (x) examples include vinyl group, allyl group, methacryloyl (oxy) group, acryloyl (oxy) group, vinyloxy group, trifluorovinyl group, trifluorovinyloxy group, ethynyl group, 1- Examples include oxocyclopenta-2,5-dien-3-yl group, cyano group, alkoxysilyl group, diarylhydroxymethyl group, hydroxyfluorenyl group and the like.
  • a vinyl group, a methacryloyl (oxy) group, an acryloyl (oxy) group, a trifluorovinyloxy group, and an ethynyl group are preferable because of excellent reactivity when external energy is applied and high crosslink density can be obtained. From the point which is excellent in the heat resistance of the protective film 20 obtained, an ethynyl group and a vinyl group are more preferable.
  • the crosslinkable functional group (x) When heat is used as external energy for curing the prepolymer, the crosslinkable functional group (x) preferably has a reaction temperature of 40 to 500 ° C., more preferably 60 to 400 ° C., and 70 to 350 ° C. It is particularly preferred that When the reaction temperature of the crosslinkable functional group (x) is 40 ° C. or higher, it is easy to ensure storage stability. Moreover, if the reaction temperature of a crosslinkable functional group (x) is 500 degrees C or less, it will be easy to suppress that thermal decomposition of prepolymer itself generate
  • the content of the crosslinkable functional group (x) in the aromatic fluorine-containing resin (A1) is such that the amount of the crosslinkable functional group (x) per 1 g of the aromatic fluorine-containing resin (A1) is 0.1 to 4 mmol. It is preferable that it is 0.2 to 3 mmol.
  • the content of the crosslinkable functional group (x) is 0.1 mmol or more, it is easy to obtain the protective film 20 having excellent heat resistance and low gas permeability.
  • the said content of a crosslinkable functional group (x) is 4 mmol or less, it will be easy to reduce the brittleness of the intermediate
  • a compound having one phenolic hydroxyl group and a compound having two phenolic hydroxyl groups are preferable.
  • the compound having one phenolic hydroxyl group include phenols having a reactive double bond (crosslinkable functional group (x)) such as 4-hydroxystyrene; 3-ethynylphenol, 4-phenylethynylphenol, 4 And ethynylphenols such as-(4-fluorophenyl) ethynylphenol.
  • Examples of the compound having two phenolic hydroxyl groups include 2,2′-bis (phenylethynyl) -5,5′-dihydroxybiphenyl and 2,2′-bis (phenylethynyl) -4,4′-dihydroxybiphenyl.
  • Bis (phenylethynyl) dihydroxybiphenyls such as 4,4′-dihydroxytolane, 3,3′-dihydroxytolane, and the like.
  • These compounds (a1-1) may be used alone or in combination of two or more.
  • a compound having a crosslinkable functional group (x) and a perfluoroaromatic ring such as perfluorophenyl or perfluorobiphenyl is preferable.
  • Fluorine-containing aryls having a reactive double bond Fluorine-containing aryls having a cyano group such as pentafluorobenzonitrile; Fluorine-containing arylacetylene having a reactive triple bond such as pentafluorophenylacetylene and nonafluorobiphenylacetylene Fluorine-containing diaries such as phenylethynylpentafluorobenzene, phenylethynylnonafluorobiphenyl, decafluorotolane, etc. Acetylenes, and the like.
  • the cross-linking reaction proceeds at a relatively low temperature, and the resulting aromatic fluorine-containing resin (A1) (cured product) is more excellent in heat resistance, so that a double bond (crosslinkable functional group (x)) is obtained.
  • fluorine-containing arylacetylenes having a triple bond are preferred.
  • These compounds (a1-2) may be used alone or in combination of two or more.
  • the fluorine-containing aromatic compound (a2) is a compound represented by the following formula (1).
  • n represents an integer of 0 to 3
  • a and b each independently represents an integer of 0 to 3
  • Rf 1 and Rf 2 each independently represents a fluorine-containing alkyl group having 8 or less carbon atoms
  • F in the ring represents that all the hydrogen atoms of the aromatic ring are substituted with fluorine atoms.
  • the carbon number of Rf 1 and Rf 2 in the fluorinated aromatic compound (a2) is 8 or less, and preferably 3 or less.
  • Rf 1 and Rf 2 are preferably perfluoroalkyl groups from the viewpoint of heat resistance.
  • Specific examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group.
  • a and b are each independently preferably 0 to 2, particularly preferably 0.
  • n is an integer of 0 to 3, and preferably an integer of 1 to 3.
  • N 3, perfluoro (1,3,5-triphenylbenzene) and perfluoro (1,2,4-triphenylbenzene) are preferable.
  • perfluorotoluene, perfluoro (1,3,5-triphenylbenzene), perfluoro (1,2,4-triphenylbenzene), and perfluorobiphenyl are more preferable.
  • a particularly preferred fluorine-containing aromatic compound (a2) is perfluorobiphenyl because it has excellent heat resistance and low gas permeability, and a highly flexible intermediate layer 21 can be easily obtained.
  • fluorine-containing aromatic compounds (a2) may be used alone or in combination of two or more.
  • the compound (a3) is a compound having 3 or more phenolic hydroxyl groups.
  • the number of phenolic hydroxyl groups in the compound (a3) is 3 or more, practically 3-6, and particularly preferably 3-4.
  • polyfunctional phenols are preferable.
  • trihydroxybenzene, trihydroxybiphenyl, trihydroxynaphthalene, 1,1,1-tris (4-hydroxyphenyl) ethane, tris (4-hydroxyphenyl) benzene, tetrahydroxybenzene, tetrahydroxybiphenyl, tetrahydroxybinaphthyl Examples include tetrahydroxy spiroindanes.
  • the compound (a3) a compound having three phenolic hydroxyl groups is more preferable because the flexibility of the intermediate layer 21 is higher.
  • trihydroxybenzene, 1,1,1-tris (4-hydroxy Phenyl) ethane is particularly preferred.
  • the number average molecular weight of the prepolymer (a) is preferably 1 ⁇ 10 3 to 5 ⁇ 10 5 .
  • the number average molecular weight of the prepolymer (a) is 1 ⁇ 10 3 or more, the heat resistance, mechanical properties, and solvent resistance of the intermediate layer 21 formed of the aromatic fluorine-containing resin (A1) become better. .
  • the number average molecular weight of the prepolymer (a) is 5 ⁇ 10 5 or less, the coating properties of the prepolymer (a) will be better.
  • the prepolymer (a) before curing of the aromatic fluorine-containing resin (A1) can be produced by the method described in JP-A-2005-105115. For example, the following methods (i) to (iii) Is mentioned.
  • IIi A method in which a fluorine-containing aromatic compound (a2), a compound (a3), and a compound (a1-2) are subjected to a condensation reaction in the presence of a deHF agent.
  • (Iii) A method in which a fluorine-containing aromatic compound (a2), a compound (a3), a compound (a1-1), and a compound (a1-2) are subjected to a condensation reaction in the presence of a deHF agent.
  • the condensation reaction may be performed in one step or in multiple steps. Moreover, after reacting a specific compound preferentially among reaction raw materials, you may make it react with another compound continuously.
  • the condensation reaction is performed in multiple stages, the intermediate product obtained in the middle may be once separated from the reaction system and purified, and then used for the subsequent condensation reaction.
  • the reaction raw materials may be charged all at once, may be charged continuously, or may be charged intermittently.
  • a basic compound is preferable, and an alkali metal carbonate, hydrogen carbonate or hydroxide is particularly preferable.
  • an alkali metal carbonate, hydrogen carbonate or hydroxide is particularly preferable.
  • sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide and the like can be mentioned.
  • the aromatic fluorine-containing resin (A1) has a branched molecular structure and is a cured product that is crosslinked at a high density, and therefore has a high Tg. Therefore, the intermediate layer 21 having lower gas permeability can be formed. Further, the intermediate layer 21 formed using the aromatic fluorine-containing resin (A1) has stronger adhesiveness, is excellent in heat resistance and mechanical characteristics, and is protected from the optical element 13 due to temperature change. The effect which prevents 20 peeling is excellent.
  • the polyethersulfone resin is a polymer having a repeating unit represented by the following formula (2).
  • Ar and Ar ′ are each independently a paraphenylene group or a 4,4′-biphenylene group.
  • the molecular weight of the polyethersulfone resin is not particularly limited, but is preferably 0.3 to 1.0 dL / g within the range represented by the intrinsic viscosity.
  • the amorphous aromatic resin (A) in the present invention preferably has a glass transition temperature (Tg) of 150 ° C. or higher, more preferably 200 ° C. or higher. If Tg is 150 ° C. or higher, the temperature around the light emitting element 13 such as the protective film 20 is heated to 150 ° C. or higher due to the heat generated by the LED element (light emitting element 13), such as in the case of a white LED for illumination. However, since the intermediate layer 21 is difficult to flow, the dimensional change of the intermediate layer 21 is small, and thermal deformation hardly occurs. Therefore, it is easy to suppress peeling of the protective film 20 when the temperature is lowered.
  • Tg glass transition temperature
  • a preferable Tg amorphous aromatic resin (A) can be obtained, for example, by appropriately selecting from commercially available products.
  • amorphous aromatic resins (A) having a Tg of 150 ° C. or higher examples include aromatic fluorine-containing resins, polyimide resins, polyamide resins, polyamideimide resins, polysulfone resins, polyethersulfone resins, and polyethers. Examples thereof include ketone resins, polyarylene resins, polyarylene ether resins, and the like.
  • the aromatic fluorine-containing resin (A1) When the aromatic fluorine-containing resin (A1) is used as the amorphous aromatic resin (A), its Tg is measured according to JIS K7121: 1987 using a differential scanning calorimeter (DSC), and the midpoint glass transition It can obtain
  • the thermal expansion coefficient of the amorphous aromatic resin (A) is preferably 20 to 100 ppm / ° C., and more preferably 50 to 100 ppm / ° C.
  • the lower the coefficient of thermal expansion of the resin the smaller the degree of expansion and contraction due to temperature even if the temperature changes. For this reason, it is considered that the lower the thermal expansion coefficient, the easier it is to maintain the adhesiveness with the optical element 13, the electrodes 12a and 12b, the ceramics of the substrate 11, and the like, and the peeling is less likely to occur. Therefore, the thermal expansion coefficient of the amorphous aromatic resin (A) is preferably 100 ppm / ° C. or less.
  • the thermal expansion coefficient of the amorphous aromatic resin (A) is 100 ppm / ° C. or less, the light emitting element 13 of the light emitting element module 1, electrical wiring (electrodes 12 a and 12 b, wire bonding 14), substrate 11 (ceramics), etc. Excellent adhesion.
  • the thermal expansion coefficient of the amorphous fluorine-containing resin (B) is large (100 to 200 ppm / ° C.)
  • the thermal expansion coefficient of the amorphous aromatic resin (A) is too small, the intermediate layer 21 is changed due to temperature change. There is a risk of peeling at the interface between the coating layer 22 and the coating layer 22.
  • the thermal expansion coefficient of the amorphous aromatic resin (A) is preferably 20 ppm / ° C. or higher. If the thermal expansion coefficient of the amorphous aromatic resin (A) is 20 ppm / ° C. or more, the difference from the thermal expansion coefficient of the amorphous fluorine-containing resin (B) used for the coating layer 22 can be reduced. Therefore, in the protective film 20, peeling hardly occurs at the interface between the intermediate layer 21 and the coating layer 22.
  • amorphous aromatic resins (A) having a thermal expansion coefficient of 20 to 100 ppm / ° C. include, for example, polyamide imide resins (Toyobo Viromax HR-15ET, etc.), polyether sulfone resins (Sumitomo Chemical Co., Ltd.) Sumika Excel 5003P, etc.), polyimide resin (Semicofine SP-483, etc. manufactured by Toray Industries), and polysulfone resin (Udel P3500, manufactured by Solvay Advanced Polymer).
  • the intermediate layer 21 can be formed of the amorphous aromatic resin (A) described above.
  • the intermediate layer 21 in the present invention is preferably formed of only the amorphous aromatic resin (A).
  • the amorphous aromatic resin (A) can be used for the intermediate layer 21 as long as the heat resistance, gas permeability, and adhesion to the light emitting element and the coating layer are not excessively deteriorated.
  • other resins may be contained.
  • Examples of other substances that can be contained in the intermediate layer 21 include cured products of thermosetting resins such as epoxy resins, alkyd resins, phenol resins, diallyl phthalate resins, and dehydration condensates derived from alkoxysilanes. .
  • the content of the other polymer in the intermediate layer 21 (100% by mass) is preferably 30% by mass or less, and preferably 10% by mass or less. Is more preferable. That is, the intermediate layer preferably contains more than 70% by mass of amorphous aromatic resin (A) having an aromatic ring in the main chain, more preferably more than 90% by mass.
  • the thickness of the intermediate layer 21 is preferably 0.1 to 100 ⁇ m, and more preferably 1 to 10 ⁇ m. If the thickness of the intermediate layer 21 is less than 0.1 ⁇ m, it may be difficult to maintain gas permeability low. When the thickness of the intermediate layer 21 exceeds 100 ⁇ m, depending on the type of the amorphous aromatic resin (A), light of a short wavelength is absorbed, which may cause a decrease in light extraction efficiency from the light emitting element 13. is there. Further, when the thickness is within this range, it is easy to maintain the gas permeability low while enhancing the adhesion between the light emitting element 13 and the protective film 20.
  • the light transmittance of visible light with a wavelength of 400 to 700 nm of the intermediate layer 21 is preferably 90% or more, and more preferably 95% or more under the condition that the thickness is 5 to 10 ⁇ m. If the light transmittance is 90% or more, adverse effects on the light extraction efficiency from the light emitting element 13 can be suppressed, and thus the light emitting element module 1 having high light emission luminance can be easily obtained.
  • the gas permeability of the intermediate layer 21 at a temperature of 0 to 200 ° C. is preferably low from the viewpoint of easily suppressing discoloration of an Ag electrode or the like, and is 1/10 to 1/1000 with respect to the gas permeability of polydimethylsiloxane.
  • the ratio is preferably 1/100 to 1/1000.
  • the gas permeability of the intermediate layer 21 can be adjusted by the film thickness of the amorphous aromatic resin (A).
  • the amorphous fluorine-containing resin (B) is a resin (cured product) obtained by curing an amorphous and curable curable amorphous fluorine-containing polymer (b) having no aromatic ring. . Since the amorphous fluorine-containing resin (B) forming the coating layer 22 does not have an aromatic ring, the aromatic ring is cleaved by the light from the optical element 13 to deteriorate the coating layer 22, thereby protecting the protective film. It is possible to prevent the performance from deteriorating.
  • the curable amorphous fluorine-containing polymer (b) a known polymer used for protecting optical elements can be used as long as it is an amorphous and curable fluorine-containing polymer.
  • a fluorinated polymer having a curable reactive group such as a carboxy group, a cyano group or a double bond at the terminal, or a curable perfluoropolyalkylene ether described in JP-A-8-67819.
  • the curable amorphous fluorine-containing polymer (b) may be used alone or in combination of two or more.
  • the curable amorphous fluorine-containing polymer (b) can be easily cured by light or heat to form the coating layer 22, so that a polymerizable double bond (carbon) such as the curable perfluoropolymer is used.
  • a polymerizable compound (b1) having a —carbon double bond) is preferred.
  • Specific examples of the polymerizable compound (b1) include, for example, a tetrafluoroethylene (TFE) / perfluoro (1,4-butanediol divinyl ether) copolymer and a TFE / perfluoro (1,2-ethylene glycol divinyl ether) copolymer.
  • the amorphous aromatic resin (A) forming the intermediate layer 12 has a hetero atom in the bonded portion of the aromatic ring of the main chain, the terminal or side in the amorphous fluorine-containing resin (B)
  • a functional group such as a carboxylic acid group, an ester group, an amide group, a hydroxyl group, a cyano group, or a thiol group
  • the adhesion between the intermediate layer and the coating layer can be improved. This is because the amorphous aromatic resin (A) has polarity due to the influence of heteroatoms and interacts with the functional group of the amorphous fluorine-containing resin (B).
  • a method for introducing the functional group into the amorphous fluorine-containing resin (B) for example, in the case of an amide group, —COOH or —COF existing as a terminal group of the amorphous fluorine-containing resin (B) is 1
  • a method of converting to an alkylamide by reacting with a secondary amine or secondary amine can be mentioned.
  • a cyano group there may be mentioned a method in which —COOH or —COF existing as a terminal group is reacted with ammonia to form —CONH 2 and then converted into a cyano group by a dehydration reaction.
  • an amino group can be obtained by reducing the cyano group.
  • -COOH or -COF can be converted to a hydroxyl group by methylation and then reduction.
  • the Tg of the amorphous fluorine-containing resin (B) is preferably ⁇ 50 ° C. to 100 ° C., and more preferably ⁇ 20 ° C. to 50 ° C.
  • Tg is ⁇ 50 ° C. or higher, the effect of stickiness on the surface of the coating layer 22 is small. Further, since it is easy to keep gas permeability low, it becomes easy to suppress discoloration of Ag electrodes used for electric wiring.
  • the Tg of the amorphous aromatic resin (A) is 100 ° C. or lower, the flexibility is maintained, so that peeling occurs due to the generation of stress at the interface between the intermediate layer 21 and the coating layer 22 due to temperature change. It becomes easy to suppress.
  • the Tg of the amorphous fluorine-containing resin (B) can be adjusted by the amount of the curable reactive group (polymerizable double bond) in the curable amorphous fluorine-containing polymer (b).
  • the thermal expansion coefficient of the amorphous fluorine-containing resin (B) can be adjusted by selecting the resin.
  • the coating layer 22 can be formed of the amorphous fluorine-containing resin (B) described above.
  • the coating layer 22 in the present invention is preferably formed only from the amorphous fluorine-containing resin (B).
  • the coating layer 22 may contain other resins in addition to the amorphous fluorine-containing resin (B) as long as the gas permeability of the coating layer 22 is not excessively deteriorated.
  • Examples of other substances that can be contained in the coating layer 22 include perfluoropolyether that has the effect of increasing the flexibility by lowering the Tg. Moreover, the inorganic type or organic type fluorescent substance which show
  • the thickness of the coating layer 22 is preferably 100 ⁇ m or more.
  • the thickness of the covering layer 22 is 100 ⁇ m or more, it is easy to suppress deterioration of the light emitting element 13 and the electric wiring, and the light resistance is excellent.
  • the light transmittance of the coating layer 22 with respect to visible light having a wavelength of 400 to 700 nm is preferably 90% or more, and more preferably 95% or more under the condition that the thickness is 0.1 to 2 mm. If the light transmittance is 90% or more, adverse effects on the light extraction efficiency from the light emitting element 13 can be suppressed, and thus the light emitting element module 1 having high light emission luminance can be easily obtained.
  • the gas permeability at 25 ° C. of the covering layer 22 is preferably 10 ⁇ 15 to 10 ⁇ 13 mol ⁇ m / m 2 ⁇ s ⁇ Pa in the case of oxygen and water vapor, and is preferably 10 ⁇ 15 to 10 ⁇ 14 mol ⁇ m. More preferably, it is / m 2 ⁇ s ⁇ Pa. If the gas permeability is 10 ⁇ 13 mol ⁇ m / m 2 ⁇ s ⁇ Pa or less, water vapor and sulfur compounds in the air are blocked to prevent deterioration of the LED element (light emitting element 13) and the electrodes 12a and 12b. Is easy.
  • the curable amorphous fluoropolymer (b) can be easily obtained.
  • the gas permeability of the coating layer 22 can be adjusted by the Tg of the amorphous fluororesin (B), the crosslinking density, and the like.
  • the protective film using the amorphous fluorine-containing resin (B) is excellent in initial adhesiveness and gas permeability with the light emitting element. Moreover, since it is excellent also in heat resistance, even if it uses continuously at high temperature, peeling of a protective film can be suppressed and it can be used stably.
  • the amorphous fluorine-containing resin (B) is not usually excellent in adhesion to various substrates.
  • the optical element 13 and the protective film 20 are formed by forming the intermediate layer 21 from the amorphous aromatic resin (A) having a polarity intermediate between the module member 10 such as the optical element 13 and the covering layer 22. Improves the adhesion.
  • the amorphous aromatic resin (A) having a Tg of 150 ° C. or higher is used for forming the intermediate layer 21, it is possible to further suppress softening of the intermediate layer 21 when the optical element module is heated to a high temperature. It is easy to keep the gas permeability of the protective film 20 low, and the protective film 20 can be made thinner. Furthermore, by using the amorphous aromatic resin (A) having a smaller thermal expansion coefficient than the amorphous fluorine-containing resin (B) of the coating layer 22, the intermediate layer 21 is changed due to a temperature change caused by the use of the light emitting element module. It becomes easy to suppress expansion and contraction and to prevent the protective film 20 from peeling from the optical element 13.
  • the manufacturing method of the present invention is a method of manufacturing an optical element module that includes an optical element and an electric wiring for energizing the optical element, and the optical element and the electric wiring are covered with a protective film.
  • the manufacturing method (I) of the optical element module in which the protective film having the intermediate layer containing the aromatic fluorine-containing resin (A1) described above is formed and the amorphous aromatic resin (A) synthesized in advance are used.
  • a method (II) for producing an optical element module in which a protective film having an intermediate layer is formed will be described.
  • Manufacturing method (I) has the following processes.
  • Intermediate layer forming step After applying a coating solution prepared by dissolving a prepolymer (a) having a crosslinkable functional group (x) in a solvent to the light emitting element and the electric wiring, the prepolymer (a) is cured, The process of forming the intermediate
  • Coating layer forming step After coating the curable amorphous fluorinated polymer (b) having no aromatic ring on the intermediate layer, the curable amorphous fluorinated polymer (b) is subjected to heat or light. A step of forming a coating layer containing the amorphous fluorine-containing resin (B) by curing by the method.
  • the method of manufacturing the module member 10 is not particularly limited, and the module member 10 may be manufactured by mounting the electrodes 12a and 12b, the optical element 13, the bonding wire 14, and the reflector 15 on the substrate 11 by a known method. Moreover, you may use the commercially available module member in which they were mounted.
  • the prepolymer (a) is dissolved in a solvent to prepare a coating solution. Thereafter, the coating liquid is applied to the light emitting element 13 and the electrodes 12 a and 12 b in the recess 16 to form the intermediate layer 21.
  • the intermediate layer 21 By forming the intermediate layer 21 by applying the coating liquid, the intermediate layer 21 can be easily formed. Therefore, it is preferable to use a combination in which the prepolymer (a) is soluble in the solvent.
  • Examples of the solvent for the coating liquid include aromatic hydrocarbons, aprotic polar solvents, ketones, esters, ethers, and halogenated hydrocarbons.
  • aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, cumene, mesitylene, tetralin, methylnaphthalene, o-chlorophenol, nitrobenzene, anisole and the like.
  • Examples of the aprotic polar solvents include N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, ⁇ -butyrolactone, dimethyl sulfoxide, 1-methyl-2-pyrrolidone, sulfolane and the like.
  • Examples of ketones include cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methyl amyl ketone, and the like.
  • ethers include tetrahydrofuran, pyran, dioxane, dimethoxyethane, diethoxyethane, diphenyl ether, anisole, phenetole, diglyme, triglyme and the like.
  • esters examples include ethyl lactate, methyl benzoate, ethyl benzoate, butyl benzoate, benzyl benzoate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono Examples include propyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate.
  • halogenated hydrocarbons include carbon tetrachloride, chloroform, methylene chloride, dichloroethane, tetrachloroethylene, chlorobenzene, dichlorobenzene, and the like.
  • a method for applying the coating liquid known methods can be used, for example, spin coating, spray coating, dip coating, die coating, roll coating, flexo coating, gravure coating, bar coating, Examples include a curtain coating method, a screen coating method, an ink jet method, and a flow coating method.
  • the intermediate layer containing the aromatic fluorine-containing resin (A1) is cured by curing the prepolymer (a) by light, heat, electron beam, or the like, or a combination thereof. 21 is formed.
  • the curing temperature may be any temperature that allows the prepolymer (a) to be cured, and is preferably 100 to 200 ° C, more preferably 150 to 200 ° C. Is more preferable.
  • the curing temperature of the prepolymer (a) is 100 ° C. or higher, the formation efficiency of the intermediate layer 21 is improved.
  • the curing temperature of prepolymer (a) is 200 degrees C or less, it will be easy to suppress that the obtained intermediate
  • the coating liquid to be applied may contain a photo radical generator, photo acid generator, sensitizer, or the like suitable for light of a specific wavelength. preferable.
  • light having a wavelength of 150 to 400 nm can be used.
  • a metal halide lamp, 254, 313, and 365 nm can be a high pressure or low pressure mercury lamp.
  • a KrF excimer laser can be used for 248 nm, an ArF excimer laser for 193 nm, and an F 2 laser for 157 nm. Curing can be performed, for example, by irradiation for 1 minute to 10 hours in an irradiation intensity range of 0.1 to 500 mW / cm 2 .
  • the curable amorphous fluorine-containing polymer (b) is applied onto the intermediate layer 21, and then the curable amorphous fluorine-containing polymer (b) is cured by heat or light to be coated.
  • Layer 22 is formed.
  • the coating layer 22 can be easily formed.
  • the coating method of the curable amorphous fluoropolymer (b) in the coating layer forming step is not particularly limited, but the thickness of the coating layer 22 is preferably larger than the thickness of the intermediate layer 21, It is not a coating method using a coating solution dissolved in a solvent as in the intermediate layer forming step, but is heated at a temperature lower than the curing temperature to flow the curable amorphous fluoropolymer (b) and apply it. It is preferable to use the method to do.
  • the curing temperature when the curable amorphous fluoropolymer (b) is cured by heat may be any temperature that can cure the curable amorphous fluoropolymer (b) to be used. Depending on the temperature, it is preferably 100 to 200 ° C, more preferably 150 to 200 ° C. If the curing temperature is 100 ° C. or higher, the curing reaction can be performed in a shorter time to improve productivity. Moreover, if the curing temperature is 200 ° C. or less, the coating layer 22 having excellent dimensional stability is easily obtained.
  • the curing reaction may be performed in multiple stages so that the temperature increases stepwise. When the curing reaction is performed in multiple stages, the curing temperature may be set so that at least the maximum temperature is within the above range.
  • a curing agent such as a fluorine-containing organic peroxide may be used.
  • fluorine-containing organic oxide examples include (C 6 F 5 C (CO) O) 2 and ((CF 3 ) 3 O) 2 .
  • the curable amorphous fluorinated polymer (b) may be cured by light (ultraviolet rays) having a wavelength of 150 to 400 nm.
  • the curing reaction proceeds even at room temperature, and the coating layer 22 having a higher hardness than that obtained by thermosetting can be obtained.
  • the wavelength of the ultraviolet light is preferably 150 to 400 nm, more preferably 193 to 365 nm, and particularly preferably 248 to 365 nm.
  • a cured product when irradiating 254 nm short wavelength ultraviolet rays, it is not necessary to use a photoinitiator, and a cured product can be prepared by adjusting the irradiation time according to the ultraviolet irradiation intensity. Curing can be performed, for example, by irradiation for 1 minute to 10 hours in an irradiation intensity range of 0.1 to 500 mW / cm 2 .
  • a photoinitiator when used, it can be cured by irradiating ultraviolet rays of 300 to 400 nm.
  • the photoinitiator include various types of ketone-based compounds such as acetophenone-based, benzoin ether-based, benzyl ketal-based, benzophenone, and benzyl.
  • it is a fluorine-containing photoinitiator in which a part of hydrogen is substituted with fluorine or a fluoroalkyl group because of compatibility with the polymerizable compound (b1).
  • the amount of photoinitiator used is preferably 0.01 to 10% by mass, more preferably 0.1 to 1% by mass. If the usage-amount of a photoinitiator exists in the said range, it will become easy to obtain the transparent coating layer 22 with little coloring, without reducing a cure rate.
  • the optical element module 1 is obtained by forming the protective film 20 having the intermediate layer 21 and the covering layer 22 by the intermediate layer forming process and the covering layer forming process as described above.
  • Manufacturing method (II) has the following processes.
  • Intermediate layer forming step A step of forming an intermediate layer by applying a coating solution obtained by dissolving the amorphous aromatic resin (A) in a solvent to the light emitting element and the electric wiring.
  • Coating layer forming step After applying the curable amorphous fluoropolymer (b) on the intermediate layer, the curable amorphous fluoropolymer (b) is cured by heat or light to be amorphous.
  • the method of manufacturing the module member 10 is not particularly limited, and the module member 10 may be manufactured by mounting the electrodes 12a and 12b, the optical element 13, the bonding wire 14, and the reflector 15 on the substrate 11 by a known method. Moreover, you may use the commercially available module member in which they were mounted.
  • the amorphous aromatic resin (A) is dissolved in a solvent to prepare a coating solution. Thereafter, the coating liquid is applied to the light emitting element 13 in the recess 16 to form the intermediate layer 21.
  • the intermediate layer 21 By forming the intermediate layer 21 by applying the coating liquid and drying, the intermediate layer 21 can be easily formed.
  • the amorphous aromatic resin (A) and the solvent a combination in which the amorphous aromatic resin (A) is soluble in the solvent is preferably used.
  • Examples of the solvent are the same as those mentioned in the production method (I).
  • a polyethersulfone resin is used as the amorphous aromatic resin (A)
  • N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane are used as the solvent.
  • ⁇ -butyrolactone, o-chlorophenol, anisole, nitrobenzene, methylene chloride, dichloroethane and the like can be used.
  • a coating layer formation process can perform the same process as manufacturing method (I), and its preferable aspect is also the same.
  • middle layer containing both the amorphous aromatic resin (A) synthesize
  • the intermediate layer 21 can be formed by curing the aromatic fluorine-containing resin (A1).
  • the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited by the following description.
  • “parts” in this example means parts by mass.
  • “Measuring method] In this example, the thickness of the intermediate layer and the coating layer, the molecular weight of the prepolymer (a), the glass transition temperature (Tg) of the aromatic fluorine-containing resin (A1), and the coefficient of thermal expansion were measured by the following methods. went. (Thickness of intermediate layer and coating layer) The thickness of the intermediate layer and the coating layer on the silver-plated copper plate shown in the following examples was calculated by measuring a step with the substrate using a surface roughness meter.
  • Glass transition temperature (Tg) The glass transition temperature of the aromatic fluororesin (A1) was measured using a differential scanning calorimeter (DSC) according to JIS K7121: 1987. The midpoint glass transition temperature was defined as the glass transition temperature (Tg).
  • Tg Glass transition temperature
  • the Tg of the amorphous aromatic resin (A) other than the aromatic fluorine-containing resin (A1) is Tg described in the product.
  • the thermal expansion coefficient was measured by raising the temperature from 100 ° C. to 200 ° C. at a rate of 10 ° C./min using a TMA device (manufactured by Seiko Denshi, TMA120C).
  • the molecular weight of the aromatic fluorine-containing resin (A1) was measured as a number average molecular weight in terms of polystyrene by gel permeation chromatography (GPC method). Tetrahydrofuran was used as the carrier solvent.
  • the molecular weight of the curable amorphous fluorine-containing polymer (b) was measured as a number average molecular weight in terms of polymethyl methacrylate using Asahi Clin AK225 as a carrier solvent.
  • Example 1 (Intermediate layer forming process) Polyethersulfone (trade name: Sumika Excel PES5003P, manufactured by Sumitomo Chemical Co., Ltd., Tg: 226 ° C., coefficient of thermal expansion: 55 ppm / ° C.) (PES (polyether sulfone) concentration: 20 mass%) is dissolved in N, N-dimethylacetamide. Thus, a coating solution for forming the intermediate layer was prepared. The obtained coating solution is cast on a silver-plated copper plate, heated at 100 ° C. for 30 minutes in a nitrogen gas atmosphere, and further heated at 150 ° C. for 1 hour to form an intermediate layer (thickness of about 5 ⁇ m). Formed.
  • PES polyether sulfone
  • the intermediate layer thus obtained had a Tg of 226 ° C. and a thermal expansion coefficient of 55 ppm / ° C. (Coating layer forming process)
  • tetrafluoroethylene / perfluoro (1,4-butanediol divinyl ether) / perfluoro (propyl vinyl ether) copolymer (copolymerization composition: 70/12/18 (molar ratio), PMMA equivalent mass)
  • a high viscosity liquid polymerizable compound (b1-1) having an average molecular weight of 9600
  • Example 2 (Intermediate layer forming process) A 100 mL glass four-necked flask equipped with a Dimroth condenser, a thermocouple thermometer, and a mechanical stirrer was charged with pentafluorostyrene (1.0 g), 1,1,1-tris (4-hydroxyphenyl) ethane (2.4 g). ), Dimethylacetamide (hereinafter referred to as “DMAc”) (31.1 g). The flask was heated on an oil bath with stirring, and sodium carbonate (3.8 g) was quickly added when the liquid temperature reached 60 ° C. The mixture was heated at 60 ° C. for 24 hours while stirring was continued.
  • DMAc Dimethylacetamide
  • the obtained prepolymer (a-1) was dissolved in cyclohexanone so that the concentration of the prepolymer (a-1) was 30% by mass to obtain a coating solution.
  • the coating solution was filtered through a PTFE (polytetrafluoroethylene) filter (Omnipore membrane filter manufactured by Millipore) having a pore size of 0.5 ⁇ m.
  • a coating film was prepared by spin coating on a copper plate obtained by silver-plating the obtained coating solution. The spin conditions were 1000 rpm and 30 seconds. Next, the silver-plated copper plate on which the coating film is formed is heated by a hot plate at 100 ° C. for 90 seconds, further subjected to heat treatment at 200 ° C. for 90 seconds, and then heated at 200 ° C.
  • the polymerizable compound (b1-1) is applied onto the intermediate layer, heated at 100 ° C. to develop a film, cooled to room temperature, and then irradiated with ultraviolet light having a wavelength of 254 nm by a low-pressure mercury lamp.
  • the coating was further heated at 150 ° C. for 30 minutes to form a coating layer having a thickness of 300 ⁇ m to form a protective film.
  • the silver-plated copper plate having this protective film was kept in an oven at 200 ° C. for 3 weeks, peeling of the coating layer, and silver plating and discoloration of the coating layer were hardly observed.
  • the liquid polymerizable compound (b1-1) is applied, heated at 100 ° C. to develop into a film, cooled to room temperature, and then irradiated with ultraviolet light having a wavelength of 254 nm at 6 mW / cm 2 for 30 minutes. After being cured, the film was further heated at 150 ° C. for 30 minutes to form a cured film having a thickness of 300 ⁇ m.
  • the silver-plated copper plate on which this cured film was formed was kept in an oven at 200 ° C. for 1 week, almost no discoloration of the silver plating or discoloration of the cured film was observed.
  • the protective films of Examples 1 and 2 having the intermediate layer and the coating layer of the present invention were in a state after 3 weeks of holding in the oven for 1 week of Comparative Example 1 having no intermediate layer. Even compared with the later state, the adhesion between the module member and the protective film was maintained, and the protective effect of the silver-plated portion covered with the protective film 20 was high. Further, the protective films of Examples 1 and 2 have sufficient adhesion between the module member 10 and the protective film 20 as compared with Comparative Example 2 using a silane coupling agent after 3 weeks of holding in the oven. The protective effect of the silver-plated portion covered with the protective film 20 was high. From these results, the protective film in the present invention is not only excellent in initial adhesiveness with the module member, but also has high heat resistance, so that the protective film does not peel off even in continuous use at high temperature, and the protective performance is stable. I found out.
  • a light-emitting element module was formed by forming a protective film on the LED element, which is a light-emitting element, and sealing it.
  • a recess is formed by an alumina substrate (substrate 11) and an alumina reflector (reflector 15) as illustrated in FIG. 1, and an Ag electrode (circuit) is formed on the substrate (
  • a surface mount type LED module (module member 10) having electrodes 12a and 12b), on which an LED element (light emitting element 13) having an emission wavelength of 460 nm is mounted, and the Ag electrode and the LED element are connected and connected by a bonding wire 14.
  • Example 1 The coating liquid used in Example 1 (diluted to a PES concentration of 10% by mass) is dropped into the recess 16 and heated at 100 ° C. for 30 minutes in a nitrogen gas atmosphere, and further heated at 150 ° C. for 1 hour.
  • an intermediate layer 21 having a thickness of 4 ⁇ m was formed on the surfaces of the LED element (light emitting element 13) and the Ag electrode (electrodes 12a and 12b).
  • the polymerizable compound (b1-1) was heated to 100 ° C. and poured into the recess 16, and cured by irradiating UV light having a wavelength of 254 nm at 6 mW / cm 2 for 30 minutes with a low-pressure mercury lamp, and further at 150 ° C. Then, the coating layer 22 having a thickness of 1 mm was formed to produce the protective film 20, and an LED module 1A (light-emitting element module 1) was obtained. The obtained LED module 1A was continuously energized at 3.4 V and 350 mA.
  • the resin surface temperature of the cured polymerizable compound (b1-1) of the coating layer 22 was measured with a radiation thermometer and found to be 80 ° C. From this result, it is considered that the temperature in the vicinity of the LED element exceeds 100 ° C.
  • the protective film 20 and the Ag electrode were visually observed, no change was observed. Thereafter, energization was continued for 3 months, but no change such as discoloration of the protective film 20 or Ag electrode or peeling of the protective film 20 was observed.
  • Example 4 (Intermediate layer forming process) Using the same surface-mounted LED module as in Example 3 (module member 10 mounted with an LED element (light emitting element 13) having an emission wavelength of 460 nm), the prepolymer (a-1) obtained in Synthesis Example 1 was formed in the recess 16 By adding dropwise a coating solution dissolved in cyclohexanone so that the concentration becomes 10% by mass, heating at 100 ° C. for 30 minutes in a nitrogen gas atmosphere, and further heating to 200 ° C. and then heating for 2 hours. An intermediate layer 21 having a thickness of 4 ⁇ m was formed on the surfaces of the LED element (light emitting element 13) and the Ag electrodes (electrodes 12a and 12b).
  • the polymerizable compound (b1-1) is heated to 100 ° C. and poured into the recess 16, and cured by irradiating UV light having a wavelength of 254 nm at 6 mW / cm 2 for 30 minutes with a low-pressure mercury lamp, and coating with a thickness of 1 mm.
  • the protective film 20 was produced by forming the layer 22, and the LED module 1B (light emitting element module 1) was obtained. The obtained LED module 1B was continuously energized at 3.4 V and 350 mA. During this time, the resin surface temperature of the cured polymerizable compound (b-1) of the coating layer 22 was measured with a radiation thermometer and found to be 80 ° C.
  • the light-emitting element module of the present invention is used for white LEDs used as an energy-saving high-efficiency illumination light source and other various light-emitting elements.
  • the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2008-327533 filed on Dec. 24, 2008 are cited here as disclosure of the specification of the present invention. Incorporated.
  • 1 light emitting element module 11 substrate, 12a, 12b electrode, 13 light emitting element, 14 bonding wire, 15 reflector, 20 protective film, 21 intermediate layer, 22 covering layer.

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Abstract

L'invention porte sur un module électroluminescent qui porte un film protecteur comprenant un polymère fluoré amorphe réticulable, présentant une excellente adhérence à un élément électroluminescent, et présentant également une excellente résistance à la chaleur et une excellente perméabilité au gaz, et qui est stable même lorsqu'il est utilisé de façon continue à température élevée. L'invention porte également sur un procédé de fabrication du module électroluminescent. L'invention concerne de façon spécifique un module électroluminescent (1) qui comprend un élément électroluminescent (13) et un câblage électrique (des électrodes (12a et 12b) et un fil de connexion (14)) pour appliquer un courant à l'élément électroluminescent (13), l'élément électroluminescent (13) et le câblage électrique étant tous les deux recouverts d'un film protecteur (20). Le film protecteur (20) comprend une couche intermédiaire (21) qui est en contact avec l'élément électroluminescent (13) et une couche de revêtement (22) qui est formée sur la couche intermédiaire (21). La couche intermédiaire (21) comprend une résine aromatique amorphe (A), et la couche de revêtement (22) comprend une résine fluorée amorphe (B).
PCT/JP2009/071258 2008-12-24 2009-12-21 Module électroluminescent et son procédé de fabrication WO2010074038A1 (fr)

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WO2013183705A1 (fr) * 2012-06-06 2013-12-12 日立化成株式会社 Procédé de production de dispositif à semi-conducteur optique et dispositif à semi-conducteur optique
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JP2014130963A (ja) * 2012-12-28 2014-07-10 Nichia Chem Ind Ltd 発光装置
WO2014178288A1 (fr) * 2013-04-30 2014-11-06 創光科学株式会社 Dispositif émetteur de lumière ultraviolette
WO2015037608A1 (fr) * 2013-09-12 2015-03-19 創光科学株式会社 Dispositif émetteur de lumière ultraviolette
JP2015076585A (ja) * 2013-10-11 2015-04-20 住友電工プリントサーキット株式会社 Ｌｅｄモジュール及びｌｅｄ照明器具
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KR20190138103A (ko) * 2018-06-04 2019-12-12 주식회사 루멘스 Uv 엘이디 패키지
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