WO2013157618A1 - Encapsulant composition for light-emitting diode - Google Patents
Encapsulant composition for light-emitting diode Download PDFInfo
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- 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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- WIPO (PCT)
- Prior art keywords
- group
- component
- carbon atoms
- examples
- silsesquioxane compound
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 49
- 239000008393 encapsulating agent Substances 0.000 title claims abstract description 11
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims description 42
- 238000007789 sealing Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 33
- -1 trimethylsiloxy group Chemical group 0.000 description 29
- 239000007850 fluorescent dye Substances 0.000 description 22
- 125000000217 alkyl group Chemical group 0.000 description 18
- 125000000962 organic group Chemical group 0.000 description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 11
- 125000003545 alkoxy group Chemical group 0.000 description 10
- 239000000565 sealant Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 125000003700 epoxy group Chemical group 0.000 description 8
- 125000005641 methacryl group Chemical group 0.000 description 8
- 125000003277 amino group Chemical group 0.000 description 7
- 125000004093 cyano group Chemical group *C#N 0.000 description 7
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 6
- 125000000753 cycloalkyl group Chemical group 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- HITZGLBEZMKWBW-UHFFFAOYSA-N ac1n8rtr Chemical group C1CC2OC2CC1CC[Si](O1)(O2)O[Si](O3)(C4CCCC4)O[Si](O4)(C5CCCC5)O[Si]1(C1CCCC1)O[Si](O1)(C5CCCC5)O[Si]2(C2CCCC2)O[Si]3(C2CCCC2)O[Si]41C1CCCC1 HITZGLBEZMKWBW-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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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Abstract
Provided is an encapsulant composition for light-emitting diodes which comprises a silsesquioxane derivative, a fluorescent substance, and a resin and in which the fluorescent substance has been satisfactorily dispersed. When this composition is used to encapsulate a light-emitting diode, the unevenness in chromaticity of the light-emitting diode can be reduced.
Description
本発明は、蛍光物質（蛍光色素）を含む発光ダイオード（以下、単に「ＬＥＤ」とする場合もある）用の新規な封止剤組成物であって、該蛍光体の分散性を良好にした新規な封止剤組成物に関する。
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. The present invention relates to a novel sealant composition.
ＬＥＤチップを封止するための封止剤中には、発光素子からの光を高効率に所望の波長の光に変換することを目的として、蛍光色素が混入されている。この蛍光色素は、例えば、イットリア・アルミニウム・ガーネット系無機物質（以下、単に「ＹＡＧ系無機物質」とする場合もある）が使用されている。
このような蛍光色素は、通常、該封止剤に含まれる樹脂成分と比べて比重が大きいため、時間の経過と共に下方に沈降してしまうという問題がある。このような問題を解決するために、封止剤の充填体として透光性樹脂を使用する方法が提案されている（特開２００９−１１７８３１号公報参照）。この方法によれば、該透光性樹脂が封止剤中で良好に分散するため、この透光性樹脂間に蛍光色素が存在するようになり、色度が安定し、封止剤そのものの白濁を防止することができる。
しかしながら、該方法に使用されている透光性樹脂は、ポリメチルメタアクリレートであり、有機高分子であるため、該方法では、耐熱性という点で改善の余地があった。
一方、該封止剤にフィラーとしてシリカを配合する方法が提案されているが、シリカの凝集粒子径は１００ｎｍ~数ミクロン程度であるため、該方法では、光を散乱してしまい、封止剤そのものを白濁させるという問題があった。
そのため、封止剤の透明性を保持しつつ、蛍光色素を安定して分散させることができる封止剤組成物の開発が望まれている。 In the sealant for sealing the LED chip, 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. For example, yttria / aluminum / garnet-based inorganic material (hereinafter sometimes simply referred to as “YAG-based inorganic material”) is used as the fluorescent dye.
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. In order to solve such a problem, 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). According to this method, 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.
However, since 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.
On the other hand, 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 | distribute fluorescent dye stably, maintaining the transparency of sealing agent is desired.
このような蛍光色素は、通常、該封止剤に含まれる樹脂成分と比べて比重が大きいため、時間の経過と共に下方に沈降してしまうという問題がある。このような問題を解決するために、封止剤の充填体として透光性樹脂を使用する方法が提案されている（特開２００９−１１７８３１号公報参照）。この方法によれば、該透光性樹脂が封止剤中で良好に分散するため、この透光性樹脂間に蛍光色素が存在するようになり、色度が安定し、封止剤そのものの白濁を防止することができる。
しかしながら、該方法に使用されている透光性樹脂は、ポリメチルメタアクリレートであり、有機高分子であるため、該方法では、耐熱性という点で改善の余地があった。
一方、該封止剤にフィラーとしてシリカを配合する方法が提案されているが、シリカの凝集粒子径は１００ｎｍ~数ミクロン程度であるため、該方法では、光を散乱してしまい、封止剤そのものを白濁させるという問題があった。
そのため、封止剤の透明性を保持しつつ、蛍光色素を安定して分散させることができる封止剤組成物の開発が望まれている。 In the sealant for sealing the LED chip, 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. For example, yttria / aluminum / garnet-based inorganic material (hereinafter sometimes simply referred to as “YAG-based inorganic material”) is used as the fluorescent dye.
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. In order to solve such a problem, 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). According to this method, 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.
However, since 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.
On the other hand, 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 | distribute fluorescent dye stably, maintaining the transparency of sealing agent is desired.
したがって、本発明の目的は、上記の従来技術の欠点を解消し、蛍光色素のより安定した分散性を達成し、且つ透明性に優れたＬＥＤ用封止剤組成物を提供することにある。
本発明者らは、上記課題を解決するために鋭意検討を重ねた結果、蛍光色素を含有した封止剤中に、シルセスキオキサン化合物を配合することにより、蛍光色素の分散性が向上したＬＥＤ用封止剤組成物が得られることを見出し、本発明を完成するに至った。
すなわち、本発明は、
（Ｉ）シルセスキオキサン化合物、（ＩＩ）蛍光色素、及び（ＩＩＩ）樹脂を含むことを特徴とする発光ダイオード用封止剤組成物である。
前記組成物において、前記（Ｉ）シルセスキオキサン化合物の平均粒子径は０．１~５０ｎｍであることが好ましい。
本発明によれば、さらに（Ｉ）シルセスキオキサン化合物の発光ダイオード用封止剤組成物へのフィラーとしての使用も提供される。 Accordingly, 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.
As a result of intensive studies to solve the above problems, 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.
In the composition, 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.
本発明者らは、上記課題を解決するために鋭意検討を重ねた結果、蛍光色素を含有した封止剤中に、シルセスキオキサン化合物を配合することにより、蛍光色素の分散性が向上したＬＥＤ用封止剤組成物が得られることを見出し、本発明を完成するに至った。
すなわち、本発明は、
（Ｉ）シルセスキオキサン化合物、（ＩＩ）蛍光色素、及び（ＩＩＩ）樹脂を含むことを特徴とする発光ダイオード用封止剤組成物である。
前記組成物において、前記（Ｉ）シルセスキオキサン化合物の平均粒子径は０．１~５０ｎｍであることが好ましい。
本発明によれば、さらに（Ｉ）シルセスキオキサン化合物の発光ダイオード用封止剤組成物へのフィラーとしての使用も提供される。 Accordingly, 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.
As a result of intensive studies to solve the above problems, 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.
In the composition, 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.
本発明の封止剤用組成物は、（Ｉ）シルセスキオキサン化合物、（ＩＩ）蛍光色素、及び、（ＩＩＩ）樹脂を含むものである。まず、本発明に用いる、シルセスキオキサン化合物（以下、成分（Ｉ）とする場合もある）について詳細に説明する。
（（Ｉ）シルセスキオキサン化合物：成分（Ｉ））
本発明において、シルセスキオキサン化合物とは、主鎖骨格がＳｉ−Ｏ結合からなり、単位組成中に１．５個の酸素を有するシロキサン系化合物を意味する。かかるシルセスキオキサン化合物としては、下記式（１）
で示される化合物が好ましい。
式中、ｇ個のＲ１は、互いに同一もしくは異なっていてもよく、水素原子、炭素数１~１０のアルキル基、炭素数３~８のシクロアルキル基、炭素数１~６のアルコキシ基、炭素数１~６のハロゲン化アルキル基、フェニル基、ハロゲンで置換されたフェニル基、炭素数１~６のハロゲン化アルキル基で置換されたフェニル基、ヒドロキシル基、ビニル基、トリメチルシロキシ基、または
アミノ基、シアノ基、エポキシ基、アクリル基、メタクリル基、マレイミド基、ビニル基もしくはシクロヘキセニル基のいずれかを有する有機基
であり、
ｇは、重合度を表す。
Ｒ１における、炭素数１~１０のアルキル基としては、例えばメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−オクチル基、イソオクチル基、ｎ−デシル基が挙げられる。
炭素数３~８のシクロアルキル基としては、例えばシクロプロピル基、シクロブチル基、シクロオクチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基が挙げられる。
炭素数１~６のアルコキシ基としては、例えばメトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基、ｎ−ペントキシ基、ｎ−ヘキソキシ基が挙げられる。
炭素数１~６のハロゲン化アルキル基としては、例えばトリフルオロメチル基、ペンタフルオロエチル基、クロロメチル基、２−クロロエチル基、ブロモメチル基が挙げられる。
ハロゲンで置換されたフェニル基としては、例えば４−クロロフェニル基、４−ブロモフェニル基が挙げられる。
炭素数１~６のハロゲン化アルキル基で置換されたフェニル基としては、例えば４−クロロメチルフェニル基等が挙げられる。
アミノ基、シアノ基、エポキシ基、アクリル基、メタクリル基、マレイミド基、ビニル基あるいはシクロヘキセニル基のいずれかを有する有機基としては、例えば以下の有機基が挙げられる。
アミノ基を有する有機基としては、例えばアミノプロピル基、Ｎ−メチルアミノプロピル基、アミノエチルアミノプロピル基、Ｎ−フェニルアミノプロピル基が挙げられる。
シアノ基を有する有機基としては、例えばシアノプロピル基が挙げられる。
エポキシ基を有する有機基としては、例えばエポキシメチル基、エポキシエチル基、エポキシプロピル基、エポキシシクロヘキシルメチル基、エポキシシクロヘキシルエチル基、グリシジルプロピル基、（グリシジルエチル）ジメチルシロキシ基が挙げられる。
アクリル基を有する有機基としては、例えばアクリロキシメチル基、アクリロキシプロピル基、（３−アクリロキシプロピル）ジメチルシロキシ基が挙げられる。
メタクリル基を有する有機基としては、例えばメタクリロキシメチル基、メタクリロキシプロピル基、（３−メタクリロキシプロピル）ジメチルシロキシ基が挙げられる。
マレイミド基を有する有機基としては、例えばＮ−マレイミドプロピル基が挙げられる。
ビニル基を有する有機基としては、例えばアリル基、ビニルプロピル基、ビニルオクチル基、ビニルジメチルシロキシ基、アリルプロピル基、アリルプロピルジメチルシロキシ基が挙げられる。
シクロヘキセニル基を有する有機基としては、例えば（４−シクロヘキセニル）エチルジメチルシロキシ基が挙げられる。
以上のような基の中でも、Ｒ１が、アクリル基またはメタクリル基を有する有機基、エポキシ基を有する有機基である化合物は封止樹脂成分と一緒に硬化することができるため、優れた硬度を得やすい点で特に好ましい。
ｇは、重合度を示す。このｇは、蛍光色素の分散性向上効果および蛍光色素の樹脂中への分散性の観点から、５~１００の範囲が好適である。
上記のシルセスキオキサン化合物は、ハシゴ状、ケージ状、ランダムといった種々の構造を取ることができ、本発明においてはそのいずれの構造のものも何ら制限なく用いることができ、また、それらの複数の構造からなる混合物を使用することもできる。
これらの構造のうち、ハジゴ状シルセスキオキサン化合物としては、好ましくは下記式（２）
ここで、
Ｘ１~Ｘｈは、互いに同一もしくは異なっていてもよく、水素原子、炭素数１~１０のアルキル基、炭素数３~８のシクロアルキル基、炭素数１~６のアルコキシ基、炭素数１~６のハロゲン化アルキル基、フェニル基、ハロゲンで置換されたフェニル基、炭素数１~６のハロゲン化アルキル基で置換されたフェニル基、ヒドロキシル基、ビニル基、トリメチルシロキシ基、または
アミノ基、シアノ基、エポキシ基、アクリル基、メタクリル基、マレイミド基、ビニル基、あるいはシクロヘキセニル基のいずれかを有する有機基
であり、
末端基Ｘａ及びＸｂは、それぞれ独立に、ヒドロキシル基または炭素数１~６のアルコキシ基であり、
末端基Ｘｃ及びＸｄは、それぞれ独立に、水素原子または炭素原子１~６のアルコキシ基であり、
ｈは、重合度を表す。
で示される化合物が挙げられる。
上記Ｘ１~Ｘｈにおいて、炭素数１~１０のアルキル基、炭素数３~８のシクロアルキル基、炭素数１~６のアルコキシ基、炭素数１~６のハロゲン化アルキル基、ハロゲンで置換されたフェニル基、炭素数１~６のハロゲン化アルキル基で置換されたフェニル基、トリメチルシロキシ基、または
アミノ基、シアノ基、エポキシ基、アクリル基、メタクリル基、マレイミド基、ビニル基、あるいはシクロヘキセニル基のいずれかを有する有機基としては、前記式（１）のＲ１で説明した基と同様の基が挙げられる。好ましい基も同様である。
末端基ＸａＸｂ、Ｘｃ及びＸｄにおける炭素数１~６のアルコキシ基としても、前記式（１）のＲ１で説明したアルコキシ基と同様の基が挙げられる。好ましい基も同様である。
ｈは、重合度を示す。ｈは、蛍光色素の分散性の向上効果および蛍光色素の樹脂中への分散性の観点から、５~１００の範囲が好適である。
また、ケージ状のシルセスキオキサン化合物としては、好ましくは下記式（３）
ここで、
Ｙ１~Ｙｉは、互いに同一もしくは異なっていてもよく、水素原子、炭素数１~１０のアルキル基、炭素数３~８のシクロアルキル基、炭素数１~６のアルコキシ基、炭素数１~６のハロゲン化アルキル基、フェニル基、ハロゲンで置換されたフェニル基、炭素数１~６のハロゲン化アルキル基で置換されたフェニル基、ヒドロキシル基、ビニル基、トリメチルシロキシ基、または
アミノ基、シアノ基、エポキシ基、アクリル基、メタクリル基、マレイミド基、ビニル基、あるいはシクロヘキセニル基のいずれかを有する有機基
であり、
ｉは、重合度を表し、６~１２の整数である。
で示される化合物を挙げることができる。
上記Ｙ１~Ｙｉにおいて、炭素数１~１０のアルキル基、炭素数３~８のシクロアルキル基、炭素数１~６のアルコキシ基、炭素数１~６のハロゲン化アルキル基、ハロゲンで置換されたフェニル基、炭素数１~６のハロゲン化アルキル基で置換されたフェニル基、トリメチルシロキシ基、または
アミノ基、シアノ基、エポキシ基、アクリル基、メタクリル基、マレイミド基、ビニル基、あるいはシクロヘキセニル基のいずれかを有する有機基としては、前記式（１）のＲ１で説明した基と同様の基が挙げられる、好ましい基も同様である。
ｉは、重合度を示す。この重合度は、６~１２の整数であることが好ましい。
本発明において、特に好適に使用できるシルセスキオキサン化合物は例えば、ケージ状のＴ８（前記式（３）において、ｉが８であって、４個のＳｉ原子と４個の０原子で形成される８角形からなる面６面で構成される６面体構造のもの）、ケージ状のＴ１０（前記式（３）において、ｉが１０であって、５個のＳｉ原子と５個の０原子で形成される１０角形からなる面７面で構成される７面体構造のもの）、ケージ状のＴ１２（前記式（３）において、ｉが１２であって、６個のＳｉ原子と６個の０原子で形成される１２角形からなる面で構成される８面体構造のもの）
を好ましいものとして挙げることができる。
以上のシルセスキオキサン化合物は、公知の方法で製造することができる。また、市販のものであってもよい。市販のものとして、ケージ状のシルセスキオキサン化合物を含むものとしては、例えば
ＡＣ−ＳＱ ＴＡ−１００：ポリアクリロキシプロピルポリオルガノシロキサン（ケージ状のＴ８）を含むポリシロキサン化合物の混合物（東亞合成（株）製）、
ＭＡＣ−ＳＱ ＴＭ−１００：ポリメタクリロキシプロピルポリオルガノシロキサン（ケージ状のＴ８）を含むポリシロキサン化合物の混合物（東亜合成（株）製）、
Ｑ−８：オクタ［（３−メタクリロキシプロピル）ジメチルシロキシ］シルセスキオキサン（東亞合成（株）製）、
Ｑ−６：オクタ［２−（ビニル）ジメチルシロキシ］シルセスキオキサン（東亞合成（株）製）等、さらには、
ハイブリッドプラスチックス社製のＰＯＳＳシリーズが挙げられる。
本発明において、前記成分（Ｉ）は、封止剤樹脂（下記に説明する成分（ＩＩＩ））中への分散性と分散の安定性の観点から、樹脂成分の比重に対して０．５~１．１倍の比重を持つものが好ましい。
さらに、前記成分（Ｉ）は、蛍光色素（成分（ＩＩ））の沈降防止の観点から、その平均粒子径が０．１~５０ｎｍであることが好ましく、０．１~２０ｎｍであることがさらに好ましく、０．５~５ｎｍであることが特に好ましい。なお、成分（Ｉ）が混合物の場合は、その混合物の平均粒子径が前記範囲を満足することが好ましい。
また、前記成分（Ｉ）は、同じく蛍光色素（成分（ＩＩ））の沈降防止の観点から、重量平均分子量が５００~２０，０００であることが好ましい。なお、分子量はＧＰＣ（ゲルパーメーションクロマトグラフィー）により確認した値であり、混合物の場合は、その混合物の重量平均分子量である。
（ＩＩ）蛍光色素（成分（ＩＩ））
本発明において、（ＩＩ）蛍光色素（以下、成分（ＩＩ）とする場合もある）は特に制限されるものではなく、通常、使用されている蛍光無機物質を使用することができる。具体的には、例えばＹＡＧ：Ｎｄの如き希土類元素をドープしたＹＡＧ系無機物質ＺｎＳ：Ｍｎ、ＺｎＳ：Ｃｕ、ＺｎＳ：Ａｇ、Ｃｌ、３Ｃａ３（ＰＯ４）２・Ｃａ（Ｆ、Ｃｌ）２：Ｓｂ、Ｍｎ、ＢａＭｇ２Ａｌ１６Ｏ２７：Ｅｕ２＋、ＬａＰＯ４：Ｃｅ３＋、Ｔｈ３＋、Ｙ２Ｏ３：Ｅｕ３＋、Ｓｒ２Ｐ２Ｏ７：Ｅｕ２＋の如き蛍光色素を挙げることができる。
（ＩＩＩ）樹脂（成分（ＩＩＩ））
本発明において、（ＩＩＩ）樹脂（以下、成分（ＩＩＩ）とする場合もある）としては、ＬＥＤの封止剤に使用される熱可塑性樹脂および熱硬化性樹脂が何ら制限なく使用できる。具体的には、エポキシ樹脂、熱硬化性シリコーン樹脂（シリコーン ゴム、シリコーンゲル等のオルガノポリシロキサン硬化物（架橋物）を形成する）、ユリア樹脂の如き熱硬化性樹脂およびフッ素樹脂、ポリエステル樹脂、ポリカーボネート樹脂を用いることができる。中でも、成分（Ｉ）との関係から、シリコーン樹脂、ポリエステル樹脂を使用することが好ましい。
（各成分の配合割合 成分（Ｉ）、成分（ＩＩ）、成分（ＩＩＩ）の配合割合）
本発明において、各成分の配合割合は、特に制限されるものではなく、ＬＥＤチップの大きさ、パッケージの形状等に応じて適宜決定すればよい。
中でも、成分（ＩＩＩ）１００質量部に対して、成分（Ｉ）を０．１~２０質量部とすることが好ましく、０．５~１５質量部とするのがさらに好ましく、１~１０質量部とするのが特に好ましい。なお、成分（Ｉ）が複数種類のシルセスキオキサン化合物を含む場合には、複数種類のシルセスキオキサン化合物の合計量を成分（Ｉ）の配合量とする。
また、成分（ＩＩＩ）１００質量部に対して、成分（ＩＩ）を０．３~６０質量部含むことが好ましく、０．５~３０質量部とするのがさらに好ましく、１~１０質量部とするのが特に好ましい。
本発明の封止剤組成物は、前記成分（Ｉ）、成分（ＩＩ）、及び成分（ＩＩＩ）を公知の手段により混合することにより製造することができる。また、該封止剤組成物には、本発明の効果を損なわない範囲で公知の配合（添加）剤を配合（添加）することもできる。 The composition for sealing agents of this invention contains (I) silsesquioxane compound, (II) fluorescent dye, and (III) resin. First, the silsesquioxane compound (hereinafter sometimes referred to as component (I)) used in the present invention will be described in detail.
((I) Silsesquioxane Compound: Component (I))
In the present invention, 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.
In the formula, 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.
Among the above groups, compounds in which R 1 is an organic group having an acrylic group or a methacryl group or an organic group having an epoxy group can be cured together with the encapsulating resin component, and thus have excellent hardness. It is particularly preferable because it is easy to obtain.
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.
Of these structures, 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. ~ 6 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, An organic group having any of a cyano group, an epoxy group, an acrylic group, a methacryl group, a maleimide group, a vinyl group, or a cyclohexenyl 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 compound shown by these is mentioned.
In the above X 1 to X h , 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 Examples of the organic group having any one of hexenyl groups include the same groups as those described for R 1 in the formula (1). 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.
Moreover, as a cage-like silsesquioxane compound, Preferably following formula (3)
here,
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. ~ 6 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, An organic group having any of a cyano group, an epoxy group, an acrylic group, a methacryl group, a maleimide group, a vinyl group, or a cyclohexenyl group;
i represents the degree of polymerization and is an integer of 6 to 12.
The compound shown by can be mentioned.
In 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 Examples of 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.
In the present invention, 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). A hexahedral structure composed of six octagonal faces), cage-shaped T10 (in the above formula (3), i is 10, and 5 Si atoms and 5 0 atoms) 7-sided structure composed of 7 faces formed of a dodecagon, and cage-shaped T12 (in the above formula (3), i is 12, 6 Si atoms and 6 0s) (With octahedral structure composed of dodecagonal surfaces formed by atoms)
Can be mentioned as preferred.
The above silsesquioxane compounds can be produced by known methods. A commercially available product may also be used. As a commercially available product containing a cage-like silsesquioxane compound, for example, 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 POSS series manufactured by Hybrid Plastics can be mentioned.
In the present invention, 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.
(II) Fluorescent dye (component (II))
In the present invention, 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. Specifically, for example, 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 : Examples thereof include 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+ .
(III) Resin (component (III))
In the present invention, as the (III) resin (hereinafter sometimes referred to as component (III)), a thermoplastic resin and a thermosetting resin used for an LED sealing agent can be used without any limitation. Specifically, epoxy resins, 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 can be used. Especially, it is preferable to use a silicone resin and a polyester resin from a relationship with a component (I).
(Blend ratio of each component Component ratio of component (I), component (II), component (III))
In the present invention, 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.
Among them, 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 In addition, when 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 | blended (added) to this sealing agent composition in the range which does not impair the effect of this invention.
（（Ｉ）シルセスキオキサン化合物：成分（Ｉ））
本発明において、シルセスキオキサン化合物とは、主鎖骨格がＳｉ−Ｏ結合からなり、単位組成中に１．５個の酸素を有するシロキサン系化合物を意味する。かかるシルセスキオキサン化合物としては、下記式（１）
式中、ｇ個のＲ１は、互いに同一もしくは異なっていてもよく、水素原子、炭素数１~１０のアルキル基、炭素数３~８のシクロアルキル基、炭素数１~６のアルコキシ基、炭素数１~６のハロゲン化アルキル基、フェニル基、ハロゲンで置換されたフェニル基、炭素数１~６のハロゲン化アルキル基で置換されたフェニル基、ヒドロキシル基、ビニル基、トリメチルシロキシ基、または
アミノ基、シアノ基、エポキシ基、アクリル基、メタクリル基、マレイミド基、ビニル基もしくはシクロヘキセニル基のいずれかを有する有機基
であり、
ｇは、重合度を表す。
Ｒ１における、炭素数１~１０のアルキル基としては、例えばメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−オクチル基、イソオクチル基、ｎ−デシル基が挙げられる。
炭素数３~８のシクロアルキル基としては、例えばシクロプロピル基、シクロブチル基、シクロオクチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基が挙げられる。
炭素数１~６のアルコキシ基としては、例えばメトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基、ｎ−ペントキシ基、ｎ−ヘキソキシ基が挙げられる。
炭素数１~６のハロゲン化アルキル基としては、例えばトリフルオロメチル基、ペンタフルオロエチル基、クロロメチル基、２−クロロエチル基、ブロモメチル基が挙げられる。
ハロゲンで置換されたフェニル基としては、例えば４−クロロフェニル基、４−ブロモフェニル基が挙げられる。
炭素数１~６のハロゲン化アルキル基で置換されたフェニル基としては、例えば４−クロロメチルフェニル基等が挙げられる。
アミノ基、シアノ基、エポキシ基、アクリル基、メタクリル基、マレイミド基、ビニル基あるいはシクロヘキセニル基のいずれかを有する有機基としては、例えば以下の有機基が挙げられる。
アミノ基を有する有機基としては、例えばアミノプロピル基、Ｎ−メチルアミノプロピル基、アミノエチルアミノプロピル基、Ｎ−フェニルアミノプロピル基が挙げられる。
シアノ基を有する有機基としては、例えばシアノプロピル基が挙げられる。
エポキシ基を有する有機基としては、例えばエポキシメチル基、エポキシエチル基、エポキシプロピル基、エポキシシクロヘキシルメチル基、エポキシシクロヘキシルエチル基、グリシジルプロピル基、（グリシジルエチル）ジメチルシロキシ基が挙げられる。
アクリル基を有する有機基としては、例えばアクリロキシメチル基、アクリロキシプロピル基、（３−アクリロキシプロピル）ジメチルシロキシ基が挙げられる。
メタクリル基を有する有機基としては、例えばメタクリロキシメチル基、メタクリロキシプロピル基、（３−メタクリロキシプロピル）ジメチルシロキシ基が挙げられる。
マレイミド基を有する有機基としては、例えばＮ−マレイミドプロピル基が挙げられる。
ビニル基を有する有機基としては、例えばアリル基、ビニルプロピル基、ビニルオクチル基、ビニルジメチルシロキシ基、アリルプロピル基、アリルプロピルジメチルシロキシ基が挙げられる。
シクロヘキセニル基を有する有機基としては、例えば（４−シクロヘキセニル）エチルジメチルシロキシ基が挙げられる。
以上のような基の中でも、Ｒ１が、アクリル基またはメタクリル基を有する有機基、エポキシ基を有する有機基である化合物は封止樹脂成分と一緒に硬化することができるため、優れた硬度を得やすい点で特に好ましい。
ｇは、重合度を示す。このｇは、蛍光色素の分散性向上効果および蛍光色素の樹脂中への分散性の観点から、５~１００の範囲が好適である。
上記のシルセスキオキサン化合物は、ハシゴ状、ケージ状、ランダムといった種々の構造を取ることができ、本発明においてはそのいずれの構造のものも何ら制限なく用いることができ、また、それらの複数の構造からなる混合物を使用することもできる。
これらの構造のうち、ハジゴ状シルセスキオキサン化合物としては、好ましくは下記式（２）
Ｘ１~Ｘｈは、互いに同一もしくは異なっていてもよく、水素原子、炭素数１~１０のアルキル基、炭素数３~８のシクロアルキル基、炭素数１~６のアルコキシ基、炭素数１~６のハロゲン化アルキル基、フェニル基、ハロゲンで置換されたフェニル基、炭素数１~６のハロゲン化アルキル基で置換されたフェニル基、ヒドロキシル基、ビニル基、トリメチルシロキシ基、または
アミノ基、シアノ基、エポキシ基、アクリル基、メタクリル基、マレイミド基、ビニル基、あるいはシクロヘキセニル基のいずれかを有する有機基
であり、
末端基Ｘａ及びＸｂは、それぞれ独立に、ヒドロキシル基または炭素数１~６のアルコキシ基であり、
末端基Ｘｃ及びＸｄは、それぞれ独立に、水素原子または炭素原子１~６のアルコキシ基であり、
ｈは、重合度を表す。
で示される化合物が挙げられる。
上記Ｘ１~Ｘｈにおいて、炭素数１~１０のアルキル基、炭素数３~８のシクロアルキル基、炭素数１~６のアルコキシ基、炭素数１~６のハロゲン化アルキル基、ハロゲンで置換されたフェニル基、炭素数１~６のハロゲン化アルキル基で置換されたフェニル基、トリメチルシロキシ基、または
アミノ基、シアノ基、エポキシ基、アクリル基、メタクリル基、マレイミド基、ビニル基、あるいはシクロヘキセニル基のいずれかを有する有機基としては、前記式（１）のＲ１で説明した基と同様の基が挙げられる。好ましい基も同様である。
末端基ＸａＸｂ、Ｘｃ及びＸｄにおける炭素数１~６のアルコキシ基としても、前記式（１）のＲ１で説明したアルコキシ基と同様の基が挙げられる。好ましい基も同様である。
ｈは、重合度を示す。ｈは、蛍光色素の分散性の向上効果および蛍光色素の樹脂中への分散性の観点から、５~１００の範囲が好適である。
また、ケージ状のシルセスキオキサン化合物としては、好ましくは下記式（３）
Ｙ１~Ｙｉは、互いに同一もしくは異なっていてもよく、水素原子、炭素数１~１０のアルキル基、炭素数３~８のシクロアルキル基、炭素数１~６のアルコキシ基、炭素数１~６のハロゲン化アルキル基、フェニル基、ハロゲンで置換されたフェニル基、炭素数１~６のハロゲン化アルキル基で置換されたフェニル基、ヒドロキシル基、ビニル基、トリメチルシロキシ基、または
アミノ基、シアノ基、エポキシ基、アクリル基、メタクリル基、マレイミド基、ビニル基、あるいはシクロヘキセニル基のいずれかを有する有機基
であり、
ｉは、重合度を表し、６~１２の整数である。
で示される化合物を挙げることができる。
上記Ｙ１~Ｙｉにおいて、炭素数１~１０のアルキル基、炭素数３~８のシクロアルキル基、炭素数１~６のアルコキシ基、炭素数１~６のハロゲン化アルキル基、ハロゲンで置換されたフェニル基、炭素数１~６のハロゲン化アルキル基で置換されたフェニル基、トリメチルシロキシ基、または
アミノ基、シアノ基、エポキシ基、アクリル基、メタクリル基、マレイミド基、ビニル基、あるいはシクロヘキセニル基のいずれかを有する有機基としては、前記式（１）のＲ１で説明した基と同様の基が挙げられる、好ましい基も同様である。
ｉは、重合度を示す。この重合度は、６~１２の整数であることが好ましい。
本発明において、特に好適に使用できるシルセスキオキサン化合物は例えば、ケージ状のＴ８（前記式（３）において、ｉが８であって、４個のＳｉ原子と４個の０原子で形成される８角形からなる面６面で構成される６面体構造のもの）、ケージ状のＴ１０（前記式（３）において、ｉが１０であって、５個のＳｉ原子と５個の０原子で形成される１０角形からなる面７面で構成される７面体構造のもの）、ケージ状のＴ１２（前記式（３）において、ｉが１２であって、６個のＳｉ原子と６個の０原子で形成される１２角形からなる面で構成される８面体構造のもの）
を好ましいものとして挙げることができる。
以上のシルセスキオキサン化合物は、公知の方法で製造することができる。また、市販のものであってもよい。市販のものとして、ケージ状のシルセスキオキサン化合物を含むものとしては、例えば
ＡＣ−ＳＱ ＴＡ−１００：ポリアクリロキシプロピルポリオルガノシロキサン（ケージ状のＴ８）を含むポリシロキサン化合物の混合物（東亞合成（株）製）、
ＭＡＣ−ＳＱ ＴＭ−１００：ポリメタクリロキシプロピルポリオルガノシロキサン（ケージ状のＴ８）を含むポリシロキサン化合物の混合物（東亜合成（株）製）、
Ｑ−８：オクタ［（３−メタクリロキシプロピル）ジメチルシロキシ］シルセスキオキサン（東亞合成（株）製）、
Ｑ−６：オクタ［２−（ビニル）ジメチルシロキシ］シルセスキオキサン（東亞合成（株）製）等、さらには、
ハイブリッドプラスチックス社製のＰＯＳＳシリーズが挙げられる。
本発明において、前記成分（Ｉ）は、封止剤樹脂（下記に説明する成分（ＩＩＩ））中への分散性と分散の安定性の観点から、樹脂成分の比重に対して０．５~１．１倍の比重を持つものが好ましい。
さらに、前記成分（Ｉ）は、蛍光色素（成分（ＩＩ））の沈降防止の観点から、その平均粒子径が０．１~５０ｎｍであることが好ましく、０．１~２０ｎｍであることがさらに好ましく、０．５~５ｎｍであることが特に好ましい。なお、成分（Ｉ）が混合物の場合は、その混合物の平均粒子径が前記範囲を満足することが好ましい。
また、前記成分（Ｉ）は、同じく蛍光色素（成分（ＩＩ））の沈降防止の観点から、重量平均分子量が５００~２０，０００であることが好ましい。なお、分子量はＧＰＣ（ゲルパーメーションクロマトグラフィー）により確認した値であり、混合物の場合は、その混合物の重量平均分子量である。
（ＩＩ）蛍光色素（成分（ＩＩ））
本発明において、（ＩＩ）蛍光色素（以下、成分（ＩＩ）とする場合もある）は特に制限されるものではなく、通常、使用されている蛍光無機物質を使用することができる。具体的には、例えばＹＡＧ：Ｎｄの如き希土類元素をドープしたＹＡＧ系無機物質ＺｎＳ：Ｍｎ、ＺｎＳ：Ｃｕ、ＺｎＳ：Ａｇ、Ｃｌ、３Ｃａ３（ＰＯ４）２・Ｃａ（Ｆ、Ｃｌ）２：Ｓｂ、Ｍｎ、ＢａＭｇ２Ａｌ１６Ｏ２７：Ｅｕ２＋、ＬａＰＯ４：Ｃｅ３＋、Ｔｈ３＋、Ｙ２Ｏ３：Ｅｕ３＋、Ｓｒ２Ｐ２Ｏ７：Ｅｕ２＋の如き蛍光色素を挙げることができる。
（ＩＩＩ）樹脂（成分（ＩＩＩ））
本発明において、（ＩＩＩ）樹脂（以下、成分（ＩＩＩ）とする場合もある）としては、ＬＥＤの封止剤に使用される熱可塑性樹脂および熱硬化性樹脂が何ら制限なく使用できる。具体的には、エポキシ樹脂、熱硬化性シリコーン樹脂（シリコーン ゴム、シリコーンゲル等のオルガノポリシロキサン硬化物（架橋物）を形成する）、ユリア樹脂の如き熱硬化性樹脂およびフッ素樹脂、ポリエステル樹脂、ポリカーボネート樹脂を用いることができる。中でも、成分（Ｉ）との関係から、シリコーン樹脂、ポリエステル樹脂を使用することが好ましい。
（各成分の配合割合 成分（Ｉ）、成分（ＩＩ）、成分（ＩＩＩ）の配合割合）
本発明において、各成分の配合割合は、特に制限されるものではなく、ＬＥＤチップの大きさ、パッケージの形状等に応じて適宜決定すればよい。
中でも、成分（ＩＩＩ）１００質量部に対して、成分（Ｉ）を０．１~２０質量部とすることが好ましく、０．５~１５質量部とするのがさらに好ましく、１~１０質量部とするのが特に好ましい。なお、成分（Ｉ）が複数種類のシルセスキオキサン化合物を含む場合には、複数種類のシルセスキオキサン化合物の合計量を成分（Ｉ）の配合量とする。
また、成分（ＩＩＩ）１００質量部に対して、成分（ＩＩ）を０．３~６０質量部含むことが好ましく、０．５~３０質量部とするのがさらに好ましく、１~１０質量部とするのが特に好ましい。
本発明の封止剤組成物は、前記成分（Ｉ）、成分（ＩＩ）、及び成分（ＩＩＩ）を公知の手段により混合することにより製造することができる。また、該封止剤組成物には、本発明の効果を損なわない範囲で公知の配合（添加）剤を配合（添加）することもできる。 The composition for sealing agents of this invention contains (I) silsesquioxane compound, (II) fluorescent dye, and (III) resin. First, the silsesquioxane compound (hereinafter sometimes referred to as component (I)) used in the present invention will be described in detail.
((I) Silsesquioxane Compound: Component (I))
In the present invention, 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):
In the formula, 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.
Among the above groups, compounds in which R 1 is an organic group having an acrylic group or a methacryl group or an organic group having an epoxy group can be cured together with the encapsulating resin component, and thus have excellent hardness. It is particularly preferable because it is easy to obtain.
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.
Of these structures, the ladigo-like silsesquioxane compound is preferably the following formula (2):
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. ~ 6 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, An organic group having any of a cyano group, an epoxy group, an acrylic group, a methacryl group, a maleimide group, a vinyl group, or a cyclohexenyl 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 compound shown by these is mentioned.
In the above X 1 to X h , 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 Examples of the organic group having any one of hexenyl groups include the same groups as those described for R 1 in the formula (1). 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.
Moreover, as a cage-like silsesquioxane compound, Preferably following formula (3)
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. ~ 6 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, An organic group having any of a cyano group, an epoxy group, an acrylic group, a methacryl group, a maleimide group, a vinyl group, or a cyclohexenyl group;
i represents the degree of polymerization and is an integer of 6 to 12.
The compound shown by can be mentioned.
In 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 Examples of 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.
In the present invention, 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). A hexahedral structure composed of six octagonal faces), cage-shaped T10 (in the above formula (3), i is 10, and 5 Si atoms and 5 0 atoms) 7-sided structure composed of 7 faces formed of a dodecagon, and cage-shaped T12 (in the above formula (3), i is 12, 6 Si atoms and 6 0s) (With octahedral structure composed of dodecagonal surfaces formed by atoms)
Can be mentioned as preferred.
The above silsesquioxane compounds can be produced by known methods. A commercially available product may also be used. As a commercially available product containing a cage-like silsesquioxane compound, for example, 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 POSS series manufactured by Hybrid Plastics can be mentioned.
In the present invention, 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.
(II) Fluorescent dye (component (II))
In the present invention, 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. Specifically, for example, 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 : Examples thereof include 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+ .
(III) Resin (component (III))
In the present invention, as the (III) resin (hereinafter sometimes referred to as component (III)), a thermoplastic resin and a thermosetting resin used for an LED sealing agent can be used without any limitation. Specifically, epoxy resins, 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 can be used. Especially, it is preferable to use a silicone resin and a polyester resin from a relationship with a component (I).
(Blend ratio of each component Component ratio of component (I), component (II), component (III))
In the present invention, 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.
Among them, 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 In addition, when 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 | blended (added) to this sealing agent composition in the range which does not impair the effect of this invention.
次に、実施例及び比較例を用いて本発明を詳細に説明するが、本発明は本実施例に限定されるものではない。
実施例１
（Ｉ）シルセスキオキサン化合物として、下記式（ＭＳ０８０５）
で示されるケージ状のＴ８を含むシルセスキオキサン化合物の混合物（ハイブリッドプラスチックス社製ＭＳ０８０５、混合物の平均粒子径：１．５ｎｍ、混合物の重量平均分子量：１３２２）を５質量部、蛍光体としてＹＡＧ系蛍光体ＺＹＰ５５０Ｈ（北京宇極科技発展有限公司製）３質量部をシリコーン樹脂（１００質量部）に混合して封止剤用組成物を製造した。各成分の種類、配合を表１にまとめた。
得られた封止剤用組成物を硬化させ、蛍光体の分散状態と硬化物の白濁度を目視で評価した。結果を表３に示した。
実施例２~５
実施例１におけるシルセスキオキサン化合物の種類と質量比を代えた以外は、実施例１と同様の評価を行った。封止剤組成物の配合割合、及び各成分の種類を表１にまとめた。また、得られた封止剤組成物を使用して実施例１と同様の評価を行いその結果を表３にまとめた。
実施例２は、実施例１で使用したシルセスキオキサン化合物と同じものの配合量を１０質量部に変更したものである。
実施例３は、シルセスキオキサン化合物として、下記式（ＭＳ０８３０）
で示されるケージ状のＴ８を含むシルセスキオキサン化合物の混合物（ハイブリッドプラスチック社製ＭＳ０８３０、混合物の平均粒子径：１．０ｎｍ、混合物の重量平均分子量：５５０）を５質量部使用した。
実施例４は、シルセスキオキサン化合物として、下記式（ＥＰ０４０９）
で示されるケージ状のＴ８を含むシルセスキオキサン化合物の混合物（ハイブリッドプラスチック社製ＥＰ０４０９、混合物の平均粒子径：２．０ｎｍ、混合物の重量平均分子量：１３３６）を５質量部使用した。
実施例５は、シルセスキオキサン化合物として、下記式（ＭＡ０７３５）
で示されるケージ状のＴ８を含むシルセスキオキサン化合物の混合物（ハイブリッドプラスチック社製ＭＡ０７３５、混合物の平均粒子径：２．０ｎｍ、混合物の重量平均分子量：１４３４）を５質量部使用した。
比較例１、２
実施例１において、シルセスキオキサン化合物を添加しない以外は、実施例１と同様に行った（比較例１はフィラーの添加なし、比較例２はシリカを添加。）。これら種類、配合を表２にまとめた。また、得られた封止剤組成物を使用して実施例と同様にＬＥＤを作製し、実施例１と同様の評価を行いその結果を表３にまとめた。
表３から、実施例１~５の封止剤用組成物の場合、封止部分はきわめて透明度が高く、さらに蛍光体の沈降も見られず良好な分散状態で、均一な硬化物が得られた。また、比較例１、２では、シルセスキオキサン化合物を添加しなかった場合、蛍光体が沈降し２層に分離した。また粒径の大きなシリカを添加した場合、白濁を示した。従って本発明により、シルセスキオキサン化合物の混合により、高い透明度で且つ均一な硬化物が得られることが確認された。
Next, the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to the examples.
Example 1
(I) 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.
The obtained composition for sealants was cured, and the dispersion state of the phosphor and the white turbidity of the cured product were visually evaluated. The results are shown in Table 3.
Examples 2-5
Evaluation similar to Example 1 was performed except having changed the kind and mass ratio of the silsesquioxane compound in Example 1. FIG. The blending ratio of the sealant composition and the types of each component are summarized in Table 1. Moreover, the same evaluation as Example 1 was performed using the obtained sealing agent composition, and the result was put together in Table 3.
Example 2 changes the compounding quantity of the same thing as the silsesquioxane compound used in Example 1 to 10 mass parts.
Example 3 is a silsesquioxane compound represented by the following formula (MS0830).
5 parts by mass of a cage-like silsesquioxane compound mixture (MS0830, manufactured by Hybrid Plastics Co., Ltd., average particle diameter of the mixture: 1.0 nm, weight average molecular weight of the mixture: 550) represented by the formula (1) was used.
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).
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.
From Table 3, in the case of the compositions for encapsulants of Examples 1 to 5, the encapsulated portion is extremely transparent, and further, no sedimentation of the phosphor is observed, and a uniform cured product is obtained in a good dispersion state. It was. In Comparative Examples 1 and 2, when the silsesquioxane compound was not added, the phosphor settled and separated into two layers. When silica having a large particle size was added, white turbidity was exhibited. Therefore, according to the present invention, it was confirmed that a uniform cured product with high transparency can be obtained by mixing the silsesquioxane compound.
実施例１
（Ｉ）シルセスキオキサン化合物として、下記式（ＭＳ０８０５）
得られた封止剤用組成物を硬化させ、蛍光体の分散状態と硬化物の白濁度を目視で評価した。結果を表３に示した。
実施例２~５
実施例１におけるシルセスキオキサン化合物の種類と質量比を代えた以外は、実施例１と同様の評価を行った。封止剤組成物の配合割合、及び各成分の種類を表１にまとめた。また、得られた封止剤組成物を使用して実施例１と同様の評価を行いその結果を表３にまとめた。
実施例２は、実施例１で使用したシルセスキオキサン化合物と同じものの配合量を１０質量部に変更したものである。
実施例３は、シルセスキオキサン化合物として、下記式（ＭＳ０８３０）
実施例４は、シルセスキオキサン化合物として、下記式（ＥＰ０４０９）
実施例５は、シルセスキオキサン化合物として、下記式（ＭＡ０７３５）
実施例１において、シルセスキオキサン化合物を添加しない以外は、実施例１と同様に行った（比較例１はフィラーの添加なし、比較例２はシリカを添加。）。これら種類、配合を表２にまとめた。また、得られた封止剤組成物を使用して実施例と同様にＬＥＤを作製し、実施例１と同様の評価を行いその結果を表３にまとめた。
Next, the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to the examples.
Example 1
(I) As a silsesquioxane compound, the following formula (MS0805)
The obtained composition for sealants was cured, and the dispersion state of the phosphor and the white turbidity of the cured product were visually evaluated. The results are shown in Table 3.
Examples 2-5
Evaluation similar to Example 1 was performed except having changed the kind and mass ratio of the silsesquioxane compound in Example 1. FIG. The blending ratio of the sealant composition and the types of each component are summarized in Table 1. Moreover, the same evaluation as Example 1 was performed using the obtained sealing agent composition, and the result was put together in Table 3.
Example 2 changes the compounding quantity of the same thing as the silsesquioxane compound used in Example 1 to 10 mass parts.
Example 3 is a silsesquioxane compound represented by the following formula (MS0830).
Example 4 is a silsesquioxane compound represented by the following formula (EP0409)
Example 5 shows a silsesquioxane compound represented by the following formula (MA0735).
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.
本発明は、（Ｉ）シルセスキオキサン化合物、（ＩＩ）蛍光色素、及び（ＩＩＩ）樹脂を含むＬＥＤ用封止剤組成物である。この組成物を使用してＬＥＤチップを封止することにより、透明性に優れ、さらに優れた蛍光色素の分散性と分散安定性を有し、長期間繰り返し使用した場合でも、発光色の変化が少なく耐久性も高いといった特性を有するＬＥＤを製造することができる。そして、該ＬＥＤは、極めて高寿命化することができる。
The present invention is an LED encapsulant composition comprising (I) a silsesquioxane compound, (II) a fluorescent dye, and (III) 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.
Claims (3)
- （Ｉ）シルセスキオキサン化合物、（ＩＩ）蛍光色素、及び（ＩＩＩ）樹脂を含むことを特徴とする発光ダイオード用封止剤組成物。 (I) Silsesquioxane compound, (II) fluorescent pigment | dye, and (III) resin sealing agent composition characterized by including.
- 前記（Ｉ）シルセスキオキサン化合物の平均粒子径が０．１~５０ｎｍである請求項１に記載の発光ダイオード用封止剤組成物。 2. The encapsulant composition for light emitting diodes according to claim 1, wherein the (I) silsesquioxane compound has an average particle size of 0.1 to 50 nm.
- （Ｉ）シルセスキオキサン化合物の、発光ダイオード用封止剤組成物へのフィラーとしての使用。 (I) Use of a silsesquioxane compound as a filler for a light-emitting diode encapsulant composition.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2012092778A JP2015120767A (en) | 2012-04-16 | 2012-04-16 | Sealant composition for light-emitting diode |
| JP2012-092778 | 2012-04-16 |
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|---|---|---|---|---|
| JP2006321832A (en) * | 2005-05-17 | 2006-11-30 | Konishi Kagaku Ind Co Ltd | Resin composition for sealing optical semiconductor and optical semiconductor device using the same |
| JP2008159713A (en) * | 2006-12-21 | 2008-07-10 | Momentive Performance Materials Japan Kk | Light emitting device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006321832A (en) * | 2005-05-17 | 2006-11-30 | Konishi Kagaku Ind Co Ltd | Resin composition for sealing optical semiconductor and optical semiconductor device using the same |
| JP2008159713A (en) * | 2006-12-21 | 2008-07-10 | Momentive Performance Materials Japan Kk | Light emitting device |
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