WO2013157618A1 - Composition de matériau d'encapsulation pour diode électroluminescente - Google Patents

Composition de matériau d'encapsulation pour diode électroluminescente Download PDF

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Publication number
WO2013157618A1
WO2013157618A1 PCT/JP2013/061558 JP2013061558W WO2013157618A1 WO 2013157618 A1 WO2013157618 A1 WO 2013157618A1 JP 2013061558 W JP2013061558 W JP 2013061558W WO 2013157618 A1 WO2013157618 A1 WO 2013157618A1
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Prior art keywords
group
component
carbon atoms
examples
silsesquioxane compound
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PCT/JP2013/061558
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English (en)
Japanese (ja)
Inventor
竹中　潤治
百田　潤二
雅和 大原
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株式会社トクヤマ
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Publication of WO2013157618A1 publication Critical patent/WO2013157618A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • 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
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder

Definitions

  • the present invention is a novel encapsulant composition for a light-emitting diode (hereinafter sometimes simply referred to as “LED”) containing a fluorescent material (fluorescent dye), which has good dispersibility of the phosphor.
  • LED light-emitting diode
  • the present invention relates to a novel sealant composition.
  • a fluorescent dye is mixed for the purpose of converting light from the light emitting element into light having a desired wavelength with high efficiency.
  • yttria / aluminum / garnet-based inorganic material (hereinafter sometimes simply referred to as “YAG-based inorganic material”) is used as the fluorescent dye.
  • YAG-based inorganic material Such fluorescent dyes usually have a specific gravity larger than that of the resin component contained in the sealant, and thus have a problem that they settle downward with time.
  • a method of using a translucent resin as a filler for a sealant has been proposed (see Japanese Patent Application Laid-Open No. 2009-117831).
  • the translucent resin since the translucent resin is well dispersed in the encapsulant, the fluorescent dye is present between the translucent resins, the chromaticity is stable, and the encapsulant itself White turbidity can be prevented.
  • the translucent resin used in the method is polymethyl methacrylate and is an organic polymer, the method has room for improvement in terms of heat resistance.
  • a method of blending silica as a filler in the sealant has been proposed, but since the aggregated particle diameter of silica is about 100 nm to several microns, the method scatters light, and the sealant There was a problem of clouding itself. Therefore, development of the sealing agent composition which can disperse
  • an object of the present invention is to provide an LED encapsulant composition that eliminates the above-mentioned drawbacks of the prior art, achieves more stable dispersibility of the fluorescent dye, and is excellent in transparency.
  • the present inventors have improved the dispersibility of the fluorescent dye by blending the silsesquioxane compound into the sealing agent containing the fluorescent dye. It discovered that the sealing compound composition for LED was obtained, and came to complete this invention. That is, the present invention A sealing composition for a light emitting diode, comprising (I) a silsesquioxane compound, (II) a fluorescent dye, and (III) a resin.
  • the average particle size of the (I) silsesquioxane compound is preferably 0.1 to 50 nm. According to the present invention, the use of (I) a silsesquioxane compound as a filler in a sealant composition for a light emitting diode is further provided.
  • the composition for sealing agents of this invention contains (I) silsesquioxane compound, (II) fluorescent dye, and (III) resin.
  • component (I) silsesquioxane compound used in the present invention will be described in detail.
  • component (I) Silsesquioxane Compound: Component (I)
  • the silsesquioxane compound means a siloxane-based compound having a main chain skeleton composed of Si—O bonds and having 1.5 oxygen atoms in the unit composition.
  • Examples of such silsesquioxane compounds include the following formula (1): The compound shown by these is preferable.
  • g R 1 s may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, A halogenated alkyl group having 1 to 6 carbon atoms, a phenyl group, a phenyl group substituted with a halogen, a phenyl group substituted with a halogenated alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a vinyl group, a trimethylsiloxy group, or An organic group having any one of an amino group, a cyano group, an epoxy group, an acrylic group, a methacryl group, a maleimide group, a vinyl group or a cyclohexenyl group; g represents the degree of polymerization.
  • Examples of the alkyl group having 1 to 10 carbon atoms in R 1 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, Examples include n-hexyl group, n-octyl group, isooctyl group, and n-decyl group.
  • Examples of the cycloalkyl group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclooctyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
  • Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, and n-hexoxy. Groups.
  • Examples of the halogenated alkyl group having 1 to 6 carbon atoms include trifluoromethyl group, pentafluoroethyl group, chloromethyl group, 2-chloroethyl group, and bromomethyl group.
  • Examples of the phenyl group substituted with halogen include a 4-chlorophenyl group and a 4-bromophenyl group.
  • Examples of the phenyl group substituted with a halogenated alkyl group having 1 to 6 carbon atoms include a 4-chloromethylphenyl group.
  • Examples of the organic group having any one of an amino group, a cyano group, an epoxy group, an acrylic group, a methacryl group, a maleimide group, a vinyl group, and a cyclohexenyl group include the following organic groups.
  • Examples of the organic group having an amino group include an aminopropyl group, an N-methylaminopropyl group, an aminoethylaminopropyl group, and an N-phenylaminopropyl group.
  • Examples of the organic group having a cyano group include a cyanopropyl group.
  • Examples of the organic group having an epoxy group include an epoxymethyl group, an epoxyethyl group, an epoxypropyl group, an epoxycyclohexylmethyl group, an epoxycyclohexylethyl group, a glycidylpropyl group, and a (glycidylethyl) dimethylsiloxy group.
  • Examples of the organic group having an acrylic group include acryloxymethyl group, acryloxypropyl group, and (3-acryloxypropyl) dimethylsiloxy group.
  • Examples of the organic group having a methacryl group include a methacryloxymethyl group, a methacryloxypropyl group, and a (3-methacryloxypropyl) dimethylsiloxy group.
  • Examples of the organic group having a maleimide group include an N-maleimidopropyl group.
  • Examples of the organic group having a vinyl group include an allyl group, a vinylpropyl group, a vinyloctyl group, a vinyldimethylsiloxy group, an allylpropyl group, and an allylpropyldimethylsiloxy group.
  • Examples of the organic group having a cyclohexenyl group include a (4-cyclohexenyl) ethyldimethylsiloxy group.
  • R 1 is an organic group having an acrylic group or a methacryl group or an organic group having an epoxy group
  • R 1 is an organic group having an acrylic group or a methacryl group or an organic group having an epoxy group
  • g represents the degree of polymerization. This g is preferably in the range of 5 to 100 from the viewpoint of improving the dispersibility of the fluorescent dye and the dispersibility of the fluorescent dye in the resin.
  • the silsesquioxane compound described above can take various structures such as ladder shape, cage shape, and random shape, and any of those structures can be used in the present invention without any limitation. It is also possible to use a mixture having the following structure.
  • the ladigo-like silsesquioxane compound is preferably the following formula (2): here, X 1 to X h may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 1 carbon atom.
  • halogenated alkyl group phenyl group, phenyl group substituted by halogen, phenyl group substituted by halogenated alkyl group having 1 to 6 carbon atoms, hydroxyl group, vinyl group, trimethylsiloxy group, or amino group
  • the end groups X a and X b are each independently a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms,
  • the end groups X c and X d are each independently a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms, h represents the degree of polymerization.
  • the preferable group is also the same.
  • Examples of the alkoxy group having 1 to 6 carbon atoms in the end groups X a X b , X c, and X d include the same groups as the alkoxy groups described for R 1 in the formula (1).
  • the preferable group is also the same.
  • h represents the degree of polymerization. h is preferably in the range of 5 to 100 from the viewpoint of improving the dispersibility of the fluorescent dye and the dispersibility of the fluorescent dye in the resin.
  • Y 1 to Y i may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 1 carbon atom.
  • halogenated alkyl group phenyl group, phenyl group substituted by halogen, phenyl group substituted by halogenated alkyl group having 1 to 6 carbon atoms, hydroxyl group, vinyl group, trimethylsiloxy group, or amino group
  • the compound shown by can be mentioned.
  • Y 1 to Y i substituted with an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, or a halogen Phenyl group substituted with a halogenated alkyl group having 1 to 6 carbon atoms, trimethylsiloxy group, or amino group, cyano group, epoxy group, acrylic group, methacryl group, maleimide group, vinyl group, or cyclo
  • the organic group having any one of the hexenyl groups include the same groups as those described for R 1 in the formula (1), and preferred groups are also the same.
  • i represents the degree of polymerization. This degree of polymerization is preferably an integer of 6 to 12.
  • a silsesquioxane compound that can be particularly preferably used is, for example, cage-shaped T8 (in the above formula (3), i is 8 and formed of 4 Si atoms and 4 0 atoms).
  • the above silsesquioxane compounds can be produced by known methods. A commercially available product may also be used.
  • AC-SQ TA-100 a mixture of polysiloxane compounds containing polyacryloxypropyl polyorganosiloxane (cage-like T8) (Toagosei Co., Ltd.) (Made by)
  • MAC-SQ TM-100 a mixture of polysiloxane compounds containing polymethacryloxypropyl polyorganosiloxane (cage-shaped T8) (manufactured by Toagosei Co., Ltd.)
  • Q-8 Octa [(3-methacryloxypropyl) dimethylsiloxy] silsesquioxane (manufactured by Toagosei Co., Ltd.)
  • Q-6 Octa [2- (vinyl) dimethylsiloxy] silsesquioxane (manufactured by Toagosei Co., Ltd.) and the like,
  • the component (I) is 0.5 to the specific gravity of the resin component from the viewpoint of dispersibility in the encapsulant resin (component (III) described below) and dispersion stability. Those having a specific gravity of 1.1 times are preferable. Further, the component (I) preferably has an average particle size of 0.1 to 50 nm, more preferably 0.1 to 20 nm, from the viewpoint of preventing sedimentation of the fluorescent dye (component (II)). The thickness is preferably 0.5 to 5 nm. In addition, when component (I) is a mixture, it is preferable that the average particle diameter of the mixture satisfies the said range.
  • the component (I) preferably has a weight average molecular weight of 500 to 20,000 from the viewpoint of preventing sedimentation of the fluorescent dye (component (II)).
  • the molecular weight is a value confirmed by GPC (gel permeation chromatography), and in the case of a mixture, it is the weight average molecular weight of the mixture.
  • the fluorescent dye (II) (hereinafter sometimes referred to as component (II)) is not particularly limited, and a fluorescent inorganic substance that is usually used can be used.
  • a YAG inorganic material doped with a rare earth element such as YAG: Nd ZnS: Mn, ZnS: Cu, ZnS: Ag, Cl, 3Ca 3 (PO 4 ) 2 .Ca (F, Cl) 2 :
  • fluorescent dyes such as Sb, Mn, BaMg 2 Al 16 O 27 : Eu 2+ , LaPO 4 : Ce 3+ , Th 3+ , Y 2 O 3 : Eu 3+ , Sr 2 P 2 O 7 : Eu 2+ .
  • thermoplastic resin and a thermosetting resin used for an LED sealing agent can be used without any limitation.
  • thermosetting silicone resins forming organopolysiloxane cured products (crosslinked products) such as silicone rubber and silicone gel
  • thermosetting resins such as urea resins, fluorine resins, polyester resins, Polycarbonate resin
  • the blending ratio of each component is not particularly limited, and may be appropriately determined according to the size of the LED chip, the shape of the package, and the like.
  • the component (I) is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, with respect to 100 parts by weight of the component (III). It is particularly preferable that
  • component (I) contains multiple types of silsesquioxane compounds, let the total amount of multiple types of silsesquioxane compounds be the compounding quantity of component (I).
  • the component (II) is preferably contained in an amount of 0.3 to 60 parts by weight, more preferably 0.5 to 30 parts by weight, and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the component (III). It is particularly preferable to do this.
  • the sealing agent composition of this invention can be manufactured by mixing the said component (I), component (II), and component (III) by a well-known means. Moreover, a publicly known compounding (addition) agent can also be mix
  • Example 1 As a silsesquioxane compound, the following formula (MS0805) 5 parts by mass of a mixture of silsesquioxane compounds containing T8 in the form of cage (MS0805 manufactured by Hybrid Plastics, average particle diameter of the mixture: 1.5 nm, weight average molecular weight of the mixture: 1322) represented by 3 parts by mass of YAG-based phosphor ZYP550H (manufactured by Beijing Ugoku Technological Development Co., Ltd.) was mixed with silicone resin (100 parts by mass) to produce a composition for sealant. Table 1 summarizes the type and composition of each component.
  • Example 3 is a silsesquioxane compound represented by the following formula (MS0830).
  • Example 4 is a silsesquioxane compound represented by the following formula (EP0409) 5 parts by mass of a mixture of silsesquioxane compounds containing cage-shaped T8 (Hybrid Plastics EP0409, average particle diameter of the mixture: 2.0 nm, weight average molecular weight of the mixture: 1336) shown in FIG.
  • Example 5 shows a silsesquioxane compound represented by the following formula (MA0735).
  • Example 1 5 parts by mass of a cage-like silsesquioxane compound mixture (MA0735 manufactured by Hybrid Plastics Co., Ltd., average particle diameter of the mixture: 2.0 nm, weight average molecular weight of the mixture: 1434) represented by the formula (1) was used. Comparative Examples 1 and 2 In Example 1, it carried out like Example 1 except not adding a silsesquioxane compound (Comparative Example 1 does not add a filler, and Comparative Example 2 adds a silica.). These types and formulations are summarized in Table 2. Moreover, LED was produced like the Example using the obtained sealing agent composition, evaluation similar to Example 1 was performed, and the result was put together in Table 3. FIG.
  • the present invention is an LED encapsulant composition
  • a silsesquioxane compound comprising (I) a silsesquioxane compound, (II) a fluorescent dye, and (III) a resin.
  • a resin By sealing the LED chip using this composition, it has excellent transparency and further excellent dispersibility and dispersion stability of the fluorescent dye, and even when used repeatedly for a long time, the emission color changes. It is possible to manufacture an LED having characteristics such as low durability and high durability. The LED can have a very long life.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Led Device Packages (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

L'invention concerne une composition de matériau d'encapsulation, pour des diodes électroluminescentes, qui comporte un dérivé de silsesquioxane, une substance fluorescente et une résine, et dans laquelle la substance fluorescente a été dispersée de manière satisfaisante. Lorsque cette composition est utilisée pour encapsuler une diode électroluminescente, l'irrégularité de la chromaticité de la diode électroluminescente peut être réduite.
PCT/JP2013/061558 2012-04-16 2013-04-12 Composition de matériau d'encapsulation pour diode électroluminescente WO2013157618A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012092778A JP2015120767A (ja) 2012-04-16 2012-04-16 発光ダイオード用封止剤組成物
JP2012-092778 2012-04-16

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WO2013157618A1 true WO2013157618A1 (fr) 2013-10-24

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006321832A (ja) * 2005-05-17 2006-11-30 Konishi Kagaku Ind Co Ltd 光半導体封止用樹脂組成物及びこれを用いた光半導体装置
JP2008159713A (ja) * 2006-12-21 2008-07-10 Momentive Performance Materials Japan Kk 発光装置

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006321832A (ja) * 2005-05-17 2006-11-30 Konishi Kagaku Ind Co Ltd 光半導体封止用樹脂組成物及びこれを用いた光半導体装置
JP2008159713A (ja) * 2006-12-21 2008-07-10 Momentive Performance Materials Japan Kk 発光装置

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