JP6435594B2 - Silicone resin composition - Google Patents
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- JP6435594B2 JP6435594B2 JP2012279137A JP2012279137A JP6435594B2 JP 6435594 B2 JP6435594 B2 JP 6435594B2 JP 2012279137 A JP2012279137 A JP 2012279137A JP 2012279137 A JP2012279137 A JP 2012279137A JP 6435594 B2 JP6435594 B2 JP 6435594B2
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- 229920002050 silicone resin Polymers 0.000 title claims description 41
- 239000011342 resin composition Substances 0.000 title claims description 27
- 239000010954 inorganic particle Substances 0.000 claims description 53
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 23
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 11
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 229910052712 strontium Inorganic materials 0.000 description 9
- 229910052684 Cerium Inorganic materials 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- 238000001723 curing Methods 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- -1 cerium-activated yttrium Chemical class 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 229910052693 Europium Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 229920002379 silicone rubber Polymers 0.000 description 5
- 239000004945 silicone rubber Substances 0.000 description 5
- 229910052688 Gadolinium Inorganic materials 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 238000006459 hydrosilylation reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 229910052771 Terbium Inorganic materials 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- 229910003668 SrAl Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 102100032047 Alsin Human genes 0.000 description 1
- 101710187109 Alsin Proteins 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 229910017639 MgSi Inorganic materials 0.000 description 1
- 229920006269 PPS film Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 101000709029 Toxoplasma gondii Rhomboid-like protease 5 Proteins 0.000 description 1
- QVMHUALAQYRRBM-UHFFFAOYSA-N [P].[P] Chemical compound [P].[P] QVMHUALAQYRRBM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229940075613 gadolinium oxide Drugs 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical group 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- ZYMHKOVQDOFPHH-UHFFFAOYSA-N trimethoxy(oct-1-enyl)silane Chemical compound CCCCCCC=C[Si](OC)(OC)OC ZYMHKOVQDOFPHH-UHFFFAOYSA-N 0.000 description 1
- OWUTVCVPEOXXHD-UHFFFAOYSA-N trimethoxy(prop-1-enyl)silane Chemical compound CO[Si](OC)(OC)C=CC OWUTVCVPEOXXHD-UHFFFAOYSA-N 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- 150000003746 yttrium Chemical class 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、シリコーン樹脂組成物に関する。より詳しくは、発光ダイオードに用いられるシリコーン樹脂組成物に関する。 The present invention relates to a silicone resin composition. In more detail, it is related with the silicone resin composition used for a light emitting diode.
発光ダイオード（ＬＥＤ）は、その発光効率の目覚しい向上を背景とし、低い消費電力、高寿命、意匠性などを特長として液晶ディスプレイ（ＬＣＤ）のバックライト向けや、特殊照明分野で急激に市場を拡大している。さらに、更なる発光効率の向上により、前述のような環境低負荷を特長として、今後一般照明分野で巨大な市場を形成すると期待されている。 Light-emitting diodes (LEDs) are rapidly expanding in the field of liquid crystal display (LCD) backlights and special lighting fields with low power consumption, long service life, and design, etc. due to the remarkable improvement in luminous efficiency. doing. Furthermore, by further improving the luminous efficiency, it is expected to form a huge market in the general lighting field in the future, characterized by the low environmental load as described above.
ＬＥＤの発光スペクトルは、ＬＥＤチップを形成する半導体材料に依存するため、ＬＣＤバックライトや一般照明向けの白色光を得るために、ＬＥＤチップ上にそれぞれのチップにあう蛍光体を設置している。例えば、青色を発光するＬＥＤチップ上に黄色蛍光体を設置する方法、青色ＬＥＤチップ上に赤および緑の蛍光体を設置する方法、さらには紫外線を発するＬＥＤチップ上に赤、緑、青の蛍光体を設置する方法などがある。ＬＥＤチップの発光効率やコストの面から、青色ＬＥＤチップ上に黄色蛍光体を設置する方法、または赤および緑の蛍光体を設置する方法が、現在最も広く採用されている。 Since the emission spectrum of the LED depends on the semiconductor material forming the LED chip, in order to obtain white light for an LCD backlight or general illumination, a phosphor corresponding to each chip is installed on the LED chip. For example, a method of installing a yellow phosphor on a blue LED chip, a method of installing red and green phosphors on a blue LED chip, and a red, green and blue fluorescence on an LED chip emitting ultraviolet light. There are ways to install the body. From the viewpoint of luminous efficiency and cost of the LED chip, a method of installing a yellow phosphor on a blue LED chip or a method of installing red and green phosphors is currently most widely adopted.
ＬＥＤチップ上に蛍光体を設置する方法の一つとして、蛍光体粒子を分散した樹脂組成物をチップ上に膜形成し、その後、透明性が高く、耐熱性、耐光性の良好なシリコーン系の樹脂で封止する方法が行われている。しかしながら、この様な方法では、蛍光体の分散性をコントロールできず、蛍光体がＬＥＤチップから発生する光を吸収し発生する光について、取り出し性が不十分となり、ＬＥＤパッケージの輝度が低いといった課題があった。この課題を改善するため、例えば特許文献１、２には、屈折率の高い正方晶のジルコニア粒子を添加することが検討されている。また、特許文献３には、分散剤として平均粒径Ｄ５０の値が蛍光体の平均粒径Ｄ５０の１／１０以上である酸化ケイ素、酸化アルミニウム、エポキシ系樹脂、硫酸バリウム、炭酸カルシウム、酸化バリウム、酸化チタンなどが検討されている。 As one of the methods for installing the phosphor on the LED chip, a resin composition in which phosphor particles are dispersed is formed on the chip, and then a silicone-based resin having high transparency, good heat resistance and light resistance. The method of sealing with resin is performed. However, in such a method, the dispersibility of the phosphor cannot be controlled, and the light that is generated by the phosphor absorbing light generated from the LED chip is insufficiently extracted and the luminance of the LED package is low. was there. In order to improve this problem, for example, Patent Documents 1 and 2 discuss the addition of tetragonal zirconia particles having a high refractive index. Further, Patent Document 3, 1/10 or more at which silicon oxide having an average particle diameter D average particle diameter D 50 value of the phosphor 50 as a dispersant, aluminum oxide, epoxy resin, barium sulfate, calcium carbonate, Barium oxide, titanium oxide, and the like are being studied.
上記の通り、粒子の添加によって、より高輝度なＬＥＤパッケージが得られるが、蛍光体からの光取り出し性は不十分であり、ＬＥＤパッケージの輝度として満足いくものが得られていない。本発明は、上記課題に着目し、ＬＥＤパッケージの輝度を向上することを目的とする。 As described above, an LED package with higher brightness can be obtained by the addition of particles, but light extraction from the phosphor is insufficient, and a satisfactory brightness for the LED package has not been obtained. The present invention aims to improve the luminance of the LED package by paying attention to the above problems.
本発明は、シリコーン樹脂、蛍光体および無機粒子を含み、発光ダイオード用に用いられるシリコーン樹脂組成物であって、前記無機粒子がフッ化バリウムであり、前記無機粒子の密度が４．５ｇ／ｃｍ ３ 以上４．９ｇ／ｃｍ ３ 以下であり、前記無機粒子の屈折率が１．４５以上１．４７以下であることを特徴とするシリコーン樹脂組成物である。 The present invention is a silicone resin composition used for a light-emitting diode, including a silicone resin, a phosphor and inorganic particles, wherein the inorganic particles are barium fluoride , and the density of the inorganic particles is 4.5 g / cm. 3 or more 4.9 g / cm 3 or less, a silicone resin composition, wherein the refractive index of the inorganic particles is 1.45 or more 1.47 or less.
本発明のシリコーン樹脂組成物は、ＬＥＤパッケージの輝度を向上することができる。 The silicone resin composition of the present invention can improve the brightness of the LED package.
本発明は、シリコーン樹脂、蛍光体および無機粒子を含むシリコーン樹脂組成物であって、前記無機粒子の密度が４．５以上４．９以下であり、前記無機粒子の屈折率が１．４５以上１．４７以下であることを特徴とするシリコーン樹脂組成物である。本発明のシリコーン樹脂組成物を用いれば、ＬＥＤチップの近傍に存在する蛍光体について、蛍光体間に適度な隙間を設け、光路長を調整することができるため、蛍光体からの光取り出し性を向上させ、ＬＥＤパッケージの輝度を向上できることができる。 The present invention is a silicone resin composition comprising a silicone resin, a phosphor and inorganic particles, wherein the density of the inorganic particles is 4.5 or more and 4.9 or less, and the refractive index of the inorganic particles is 1.45 or more. It is a silicone resin composition characterized by being 1.47 or less. If the silicone resin composition of the present invention is used, the phosphor existing in the vicinity of the LED chip can be provided with an appropriate gap between the phosphors and the optical path length can be adjusted. The luminance of the LED package can be improved.
本発明者らは詳細な検討の結果、ＬＥＤパッケージ中において、特にＬＥＤチップの近傍に存在する蛍光体が輝度に影響を及ぼすことを見出した。ＬＥＤチップの近傍にある蛍光体は、ＬＥＤチップから発生する光を吸収しやすいため、発光もしやすい。しかし、ここで蛍光体同士が隣接しすぎていると、せっかく蛍光体から発生した光を隣接した蛍光体が再吸収してしまい、光取り出し性が低下する。更に検討を進めた結果、ＬＥＤチップの近傍にある蛍光体同士の間隔を設け、光路長を調整することで、蛍光体からの光取り出し性を向上させ、ＬＥＤパッケージの輝度を向上できることを見出した。以下、本発明のシリコーン樹脂組成物に含まれる成分について説明する。 As a result of detailed studies, the present inventors have found that phosphors existing in the vicinity of the LED chip in the LED package affect the luminance. Since the phosphor in the vicinity of the LED chip easily absorbs light generated from the LED chip, it easily emits light. However, if the phosphors are too close to each other, the light emitted from the phosphors is absorbed again by the adjacent phosphors, and the light extraction performance is deteriorated. As a result of further investigation, it was found that by adjusting the optical path length by providing an interval between the phosphors in the vicinity of the LED chip, the light extraction from the phosphor can be improved and the brightness of the LED package can be improved. . Hereinafter, the components contained in the silicone resin composition of the present invention will be described.
（無機粒子）
本発明における無機粒子の屈折率とは、２５℃におけるナトリウムＤ線（５８９．３ｎｍ）に対する屈折率である。屈折率の測定は、Ａｂｂｅ屈折率計、Ｐｕｌｆｒｉｃｈ屈折率計、液浸型屈折率計、液浸法、最小偏角法などを用いることができる無機粒子の屈折率が１．４５未満の場合、シリコーン樹脂との屈折率差が大きくなりすぎるため、光取り出し性が低下してしまう。一方、１．４７を超えると、無機粒子による光散乱効果が大きくなり、蛍光体の吸収ロスが生じてしまう。
(Inorganic particles)
The refractive index of the inorganic particles in the present invention is a refractive index with respect to sodium D-line (589.3 nm) at 25 ° C. The refractive index can be measured by using an Abbe refractometer, a Puffrich refractometer, an immersion refractometer, an immersion method, a minimum deflection method, or the like when the refractive index of inorganic particles is less than 1.45. Since the refractive index difference with the silicone resin becomes too large, the light extraction performance is lowered. On the other hand, if it exceeds 1.47, the light scattering effect by the inorganic particles becomes large, and absorption loss of the phosphor occurs.
本発明における無機粒子の密度は、ＪＩＳ Ｚ８８０７（２０１２）個体の密度及び比重の測定方法に準ずる方法によって測定される値のことである。無機粒子の密度が４．５ｇ／ｃｍ３以上４．９ｇ／ｃｍ３以下であることで、ＬＥＤパッケージ中で適度に沈降し、チップ付近の蛍光体間に挟まれる形になり適度な隙間を与える。無機粒子の密度が４．５ｇ／ｃｍ３未満であると、パッケージ内に均一に分散されるため、ＬＥＤチップ近傍付近で蛍光体間に入り込むことができず、適度な隙間を与えることができない。一方、４．９ｇ／ｃｍ３を超えると、先に無機粒子が沈降してしまうため、蛍光体間に入り込むことができず、輝度向上の効果が得られない。本発明においては、蛍光体の密度が４．５〜４．９ｇ／ｃｍ３である場合、最も効果が得られる。 The density of the inorganic particles in the present invention is a value measured by a method according to the method for measuring the density and specific gravity of JIS Z8807 (2012) individuals. When the density of the inorganic particles is 4.5 g / cm 3 or more and 4.9 g / cm 3 or less, the inorganic particles settle appropriately in the LED package, and are sandwiched between the phosphors near the chip to give an appropriate gap. . When the density of the inorganic particles is less than 4.5 g / cm 3, the inorganic particles are uniformly dispersed in the package, so that they cannot enter between the phosphors in the vicinity of the LED chip, and an appropriate gap cannot be provided. On the other hand, if it exceeds 4.9 g / cm 3 , the inorganic particles first settle, so that they cannot enter between the phosphors, and the effect of improving luminance cannot be obtained. In the present invention, the most advantageous effect is obtained when the density of the phosphor is 4.5 to 4.9 g / cm 3 .
無機粒子の粒径は、０．５μｍ以上８．０μｍ以下の範囲であることが好ましい。粒径は、平均粒径すなわちメジアン径（Ｄ５０）で表し、マイクロトラック法（日機装（株）製マイクロトラックレーザー回折式粒度分布測定装置による方法）で測定する。すなわち、レーザー回折散乱式粒度分布測定により測定して得られる体積基準粒度分布において、小粒径側からの通過分積算」５０％の粒子系をメジアン径（Ｄ５０）として求める。 The particle size of the inorganic particles is preferably in the range of 0.5 μm or more and 8.0 μm or less. The particle diameter is expressed by an average particle diameter, that is, a median diameter (D50), and is measured by a microtrack method (a method using a microtrack laser diffraction type particle size distribution measuring device manufactured by Nikkiso Co., Ltd.). That is, in the volume-based particle size distribution obtained by measurement by laser diffraction / scattering particle size distribution measurement, a particle system having a cumulative amount of passage from the small particle size side of 50% is obtained as the median diameter (D50).
また、既に組成物が硬化していて粒子を単離できない場合には、硬化物の断面を走査型電子顕微鏡（ＳＥＭ）によって測定画像を画像処理して粒径分布を求め、そこから得られる体積基準粒度分布において、小粒径側からの通過分積算５０％の粒子径をメジアン径Ｄ５０とする方法でも測定することが可能である。この方法で求められるＤ５０の値は、無機粒子を直接観察した場合よりも小さい値となるが、硬化物から測定する場合の平均粒子径は上記の測定方法で求められる値と定義される。なお、上記のＤ５０の値が蛍光体粉末を直接観察した場合よりも小さい値となる理由は、粉末を直接観察した場合には正しく直径が測定されるが、ＬＥＤパッケージの断面を測定した場合には無機粒子が必ず赤道面で切断されているとは限らないからである。無機粒子が球状であり、その任意の場所で切断されると仮定すると、その見かけの直径は、理論上は真の直径の７８．５％となる（直径１の円の面積と一辺１の正方形の面積の比に相当）。実際には蛍光体粒子は真球ではないので、経験的にはおおよそ７０％〜８５％となる。 If the composition is already hardened and the particles cannot be isolated, the cross section of the hardened material is image-processed with a scanning electron microscope (SEM) to obtain the particle size distribution, and the volume obtained therefrom. In the reference particle size distribution, the measurement can also be performed by a method in which the particle diameter of 50% of the accumulated amount from the small particle diameter side is the median diameter D50. Although the value of D50 calculated | required by this method becomes a value smaller than the case where an inorganic particle is observed directly, the average particle diameter in the case of measuring from hardened | cured material is defined as a value calculated | required by said measuring method. The reason why the value of D50 is smaller than when the phosphor powder is directly observed is that the diameter is correctly measured when the powder is directly observed, but when the cross section of the LED package is measured. This is because inorganic particles are not always cut at the equator plane. Assuming that the inorganic particles are spherical and are cut at any location, the apparent diameter is theoretically 78.5% of the true diameter (the area of a circle with a diameter of 1 and a square with a side of 1). Equivalent to the area ratio). Actually, since the phosphor particles are not true spheres, it is empirically about 70% to 85%.
本発明に用いられる無機粒子は、密度と屈折率が上記範囲を満たすものであれば特に制限はないが、透明性、耐熱性の観点から、フッ化バリウムが好ましい。無機粒子の封止用組成物における固形分濃度は、０．５ｖｏｌ％以上であることが好ましく、０．７ｖｏｌ％以上であることがより好ましい。これにより、無機粒子が蛍光体間に入り込みやすくなり、隙間を生じやすくなるため輝度がより向上する。また上限としては特に制限はないが、３．５ｖｏｌ％以下であることが好ましく、３．０ｖｏｌ％以下であることがより好ましく、２．５ｖｏｌ％以下であることがさらに好ましい。この濃度範囲であれば、蛍光体間に適度な隙間が生じ、最適な光路長が得られるため輝度がより向上する。なお、固形分とは溶媒を除いた全成分を指す。 The inorganic particles used in the present invention are not particularly limited as long as the density and refractive index satisfy the above ranges, but barium fluoride is preferable from the viewpoint of transparency and heat resistance. The solid content concentration in the composition for sealing inorganic particles is preferably 0.5 vol% or more, and more preferably 0.7 vol% or more. As a result, the inorganic particles easily enter between the phosphors, and a gap is easily generated, so that the luminance is further improved. Moreover, there is no restriction | limiting in particular as an upper limit, However, It is preferable that it is 3.5 vol% or less, It is more preferable that it is 3.0 vol% or less, It is further more preferable that it is 2.5 vol% or less. In this concentration range, an appropriate gap is generated between the phosphors, and an optimum optical path length is obtained, so that the luminance is further improved. In addition, solid content points out all the components except a solvent.
無機粒子の固形分濃度（ｖｏｌ％）は、封止用組成物の硬化物の断面を走査型電子顕微鏡観察（例えば、（株）日立製高分解能電界放出形走査電子顕微鏡“Ｓ４８００”）で観察し、面積比から求めることができる。例えば、５００μｍ×５００μｍの視野内にある微粒子の面積を測定し、視野面積でそれを除し、１００を乗じることで、濃度（ｖｏｌ％）を算出することができる。 The solid content concentration (vol%) of the inorganic particles is obtained by observing a cross section of the cured product of the sealing composition with a scanning electron microscope (for example, a high resolution field emission scanning electron microscope “S4800” manufactured by Hitachi, Ltd.). It can be obtained from the area ratio. For example, the concentration (vol%) can be calculated by measuring the area of fine particles in a 500 μm × 500 μm visual field, dividing it by the visual field area, and multiplying by 100.
無機粒子は、シリコーン樹脂との分散性を向上させるため、シランカップリング剤などで表面処理がなされていても良い。 The inorganic particles may be surface-treated with a silane coupling agent or the like in order to improve dispersibility with the silicone resin.
（シリコーン樹脂）
シリコーン樹脂としては、硬化型シリコーンゴムが好ましい。一液型、二液型（三液型）のいずれの液構成を使用してもよい。硬化型シリコーンゴムには、空気中の水分あるいは触媒によって縮合反応を起こすタイプとして脱アルコール型、脱オキシム型、脱酢酸型、脱ヒドロキシルアミン型などがある。また、触媒によってヒドロシリル化反応を起こすタイプとして付加反応型がある。これらのいずれのタイプの硬化型シリコーンゴムを使用してもよい。特に、付加反応型のシリコーンゴムは硬化反応に伴う副成物がなく、硬化収縮が小さい点、加熱により硬化を早めることが容易な点でより好ましい。
(Silicone resin)
As the silicone resin, curable silicone rubber is preferable. Either one liquid type or two liquid type (three liquid type) liquid structure may be used. Examples of the curable silicone rubber include a dealcohol-free type, a deoxime type, a deacetic acid type, and a dehydroxylamine type that cause a condensation reaction with moisture in the air or a catalyst. Moreover, there is an addition reaction type as a type that causes a hydrosilylation reaction with a catalyst. Any of these types of curable silicone rubber may be used. In particular, the addition reaction type silicone rubber is more preferable in that it has no by-product accompanying the curing reaction, has a small curing shrinkage, and can easily be cured by heating.
付加反応型のシリコーンゴムは、一例として、ケイ素原子に結合したアルケニル基を含有する化合物と、ケイ素原子に結合した水素原子を有する化合物のヒドロシリル化反応により形成される。このような材料としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、アリルトリメトキシシラン、プロペニルトリメトキシシラン、ノルボルネニルトリメトキシシラン、オクテニルトリメトキシシラン等のケイ素原子に結合したアルケニル基を含有する化合物と、メチルハイドロジェンポリシロキサン、ジメチルポリシロキサン-ＣＯ-メチルハイドロジェンポリシロキサン、エチルハイドロジェンポリシロキサン、メチルハイドロジェンポリシロキサン-ＣＯ-メチルフェニルポリシロキサン等のケイ素原子に結合した水素原子を有する化合物のヒドロシリル化反応により形成されるものが挙げられる。また、他にも、例えば特開２０１０−１５９４１１号公報に記載されているような公知のものを利用することができる。 As an example, the addition reaction type silicone rubber is formed by a hydrosilylation reaction of a compound containing an alkenyl group bonded to a silicon atom and a compound having a hydrogen atom bonded to a silicon atom. Such materials contain alkenyl groups bonded to silicon atoms such as vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, propenyltrimethoxysilane, norbornenyltrimethoxysilane, octenyltrimethoxysilane, etc. And hydrogen atoms bonded to silicon atoms such as methylhydrogenpolysiloxane, dimethylpolysiloxane-CO-methylhydrogenpolysiloxane, ethylhydrogenpolysiloxane, methylhydrogenpolysiloxane-CO-methylphenylpolysiloxane, etc. Examples thereof include those formed by hydrosilylation reaction of the compounds having them. In addition, for example, known ones as described in JP 2010-159411 A can be used.
また、市販されているものとしては、一般的なＬＥＤ用途のシリコーン封止材を使用することもできる。具体的には、ＯＥ−６６３０Ａ／Ｂ、ＯＥ−６３３６Ａ／Ｂ、ＯＥ−６３５１Ａ／Ｂ、ＯＥ−６２５０Ａ／Ｂ、ＥＧ−６３０１Ａ／Ｂ、ＪＣＲ−６１４０Ａ／Ｂ、ＪＣＲ−６１２５Ａ／Ｂ、ＪＣＲ−６１０１ＵＰ、ＯＥ−６４５０Ａ／Ｂ、ＯＥ−６５２０−Ａ／Ｂ、ＯＥ−６５５０Ａ／Ｂ、ＯＥ−６６３１Ａ／Ｂ、ＯＥ−６６３６Ａ／Ｂ、ＯＥ−６６３５Ａ／Ｂ、ＯＥ−６６６５Ｎ、ＳＲ−７０１０Ａ／Ｂ、ＯＥ−８００１（以上、東レ・ダウコーニング社製）、ＡＳＰ−１１１１Ａ／Ｂ、ＡＳＰ−１１２０Ａ／Ｂ、ＡＳＰ−１０３１Ａ／Ｂ、ＳＣＲ−１０１２Ａ／Ｂ、ＳＣＲ−１０１６Ａ／Ｂ、ＫＥＲ−６１１０Ａ／Ｂ、ＫＥＲ−２５００Ａ／Ｂ、ＫＥＲ−２５００Ｎ−Ａ／Ｂ、ＫＥＲ−２６００Ａ／Ｂ、ＫＥＲ−２７００Ａ／Ｂ、ＫＥＲ−３０００−Ｍ２、ＫＥＲ−３１００−Ｕ２、ＫＥＲ−３２００−Ｔ１、ＫＥＲ−６０００Ａ／Ｂ、ＫＥＲ−６０２０Ｆ、ＫＥＲ−６０７５Ｆ、ＫＥＲ−６１５０Ａ／Ｂ、ＫＥＲ−６２００Ａ／Ｂ、ＫＥＲ−４０００−ＵＶ（以上、信越化学（株）製）、ＩＶＳ−４３１２Ａ／Ｂ、ＩＶＳ−４５４２Ａ／Ｂ、ＩＶＳ−４５４６Ａ／Ｂ、ＩＶＳ−４６２２Ａ／Ｂ、ＩＶＳ−４６３２Ａ／Ｂ、ＩＶＳ−４７４２Ａ／Ｂ、ＩＶＳ−４７５２Ａ／Ｂ、ＸＥ１４−Ｃ２０４２Ａ／Ｂ、ＸＥ１４−Ｃ２８６０Ａ／Ｂ、ＸＥ１４−Ｃ３４５０Ａ／Ｂ、ＩＶＳ−５８５４Ａ／Ｂ、ＩＶＳ−Ｇ３４４５Ａ／Ｂ、ＩＶＳ−Ｇ５７７８Ａ／Ｂ、ＩＶＳ−Ｇ０８１０、ＩＶＳ−Ｍ４５００Ａ／Ｂ、ＸＥ１４−Ｃ２５０８Ａ／Ｂ、ＸＥ１３−Ｃ２４７６（以上、モメンティブパフォーマンスマテリアルズジャパン社製）、Ａ１０７０Ａ／Ｂ、Ａ２０２０Ａ／Ｂ、Ａ２０３０Ａ／Ｂ（以上、（株）ダイセル製）などが挙げられるが、これらに限定されるものではない。また、これら透明樹脂は単独で用いてもよいし、２種以上を混合してもよい。 Moreover, as what is marketed, the silicone sealing material for general LED use can also be used. Specifically, OE-6630A / B, OE-6336A / B, OE-6351A / B, OE-6250A / B, EG-6301A / B, JCR-6140A / B, JCR-6125A / B, JCR-6101UP OE-6450A / B, OE-6520-A / B, OE-6550A / B, OE-6431A / B, OE-6636A / B, OE-6635A / B, OE-6665N, SR-7010A / B, OE -8001 (above, manufactured by Toray Dow Corning), ASP-1111A / B, ASP-1120A / B, ASP-1031A / B, SCR-1012A / B, SCR-1016A / B, KER-6110A / B, KER -2500A / B, KER-2500NA / B, KER-2600A / B, KER-2700A / B, KER 3000-M2, KER-3100-U2, KER-3200-T1, KER-6000A / B, KER-6020F, KER-6075F, KER-6150A / B, KER-6200A / B, KER-4000-UV (above, Manufactured by Shin-Etsu Chemical Co., Ltd.), IVS-4312A / B, IVS-4542A / B, IVS-4546A / B, IVS-4622A / B, IVS-4632A / B, IVS-4742A / B, IVS-4852A / B, XE14-C2042A / B, XE14-C2860A / B, XE14-C3450A / B, IVS-5854A / B, IVS-G3445A / B, IVS-G5778A / B, IVS-G0810, IVS-M4500A / B, XE14-C2508A / B, XE13-C2476 (End of Momente Manufactured Bed Performance Materials Japan Inc.), A1070A / B, A2020A / B, A2030A / B (or, Inc. Although the like manufactured by Daicel), but it is not limited thereto. Moreover, these transparent resins may be used independently and may mix 2 or more types.
（蛍光体）
蛍光体は、ＬＥＤチップから放出される光を吸収して波長を変換し、ＬＥＤチップの光と異なる波長の光を放出するものである。これにより、ＬＥＤチップから放出される光の一部と、蛍光体から放出される光の一部とが混合して、白色を含む多色系のＬＥＤが得られる。具体的には、青色系ＬＥＤにＬＥＤからの光によって黄色系の発光色を発光する蛍光体を光学的に組み合わせることによって、単一のＬＥＤチップを用いて白色系を発光させることができる。
(Phosphor)
The phosphor absorbs light emitted from the LED chip, converts the wavelength, and emits light having a wavelength different from that of the LED chip. Thereby, a part of the light emitted from the LED chip and a part of the light emitted from the phosphor are mixed to obtain a multicolor LED including white. Specifically, a white LED can be emitted using a single LED chip by optically combining a blue LED with a phosphor that emits a yellow emission color by light from the LED.
上述のような蛍光体には、緑色に発光する蛍光体、青色に発光する蛍光体、黄色に発光する蛍光体、赤色に発光する蛍光体等の種々の蛍光体がある。本発明に用いられる具体的な蛍光体としては、無機蛍光体、有機蛍光体、蛍光顔料、蛍光染料等公知の蛍光体が挙げられる。有機蛍光体としては、アリルスルホアミド・メラミンホルムアルデヒド共縮合染色物やペリレン系蛍光体等を挙げることができ、長期間使用可能な点からペリレン系蛍光体が好ましく用いられる。本発明に特に好ましく用いられる蛍光物質としては、無機蛍光体が挙げられる。以下に本発明に用いられる無機蛍光体について記載する。 The phosphors as described above include various phosphors such as a phosphor that emits green light, a phosphor that emits blue light, a phosphor that emits yellow light, and a phosphor that emits red light. Specific phosphors used in the present invention include known phosphors such as inorganic phosphors, organic phosphors, fluorescent pigments, and fluorescent dyes. Examples of organic phosphors include allylsulfoamide / melamine formaldehyde co-condensed dyes and perylene phosphors. Perylene phosphors are preferably used because they can be used for a long time. Examples of the fluorescent material that is particularly preferably used in the present invention include inorganic phosphors. The inorganic phosphor used in the present invention is described below.
緑色に発光する蛍光体として、例えば、ＳｒＡｌ２Ｏ４：Ｅｕ、Ｙ２ＳｉＯ５：Ｃｅ，Ｔｂ、ＭｇＡｌ１１Ｏ１９：Ｃｅ，Ｔｂ、Ｓｒ７Ａｌ１２Ｏ２５：Ｅｕ、（Ｍｇ、Ｃａ、Ｓｒ、Ｂａのうち少なくとも１以上）Ｇａ２Ｓ４：Ｅｕなどがある。 Examples of phosphors that emit green light include SrAl 2 O 4 : Eu, Y 2 SiO 5 : Ce, Tb, MgAl 11 O 19 : Ce, Tb, Sr 7 Al 12 O 25 : Eu, (Mg, Ca, Sr , At least one of Ba) and Ga 2 S 4 : Eu.
青色に発光する蛍光体として、例えば、Ｓｒ５（ＰＯ４）３Ｃｌ：Ｅｕ、（ＳｒＣａＢａ）５（ＰＯ４）３Ｃｌ：Ｅｕ、（ＢａＣａ）５（ＰＯ４）３Ｃｌ：Ｅｕ、（Ｍｇ、Ｃａ、Ｓｒ、Ｂａのうち少なくとも１以上）２Ｂ５Ｏ９Ｃｌ：Ｅｕ，Ｍｎ、（Ｍｇ、Ｃａ、Ｓｒ、Ｂａのうち少なくとも１以上）（ＰＯ４）６Ｃｌ２：Ｅｕ，Ｍｎなどがある。 Examples of phosphors that emit blue light include Sr 5 (PO 4 ) 3 Cl: Eu, (SrCaBa) 5 (PO 4 ) 3 Cl: Eu, (BaCa) 5 (PO 4 ) 3 Cl: Eu, (Mg, 2 B 5 O 9 Cl: Eu, Mn, (Mg, Ca, Sr, Ba, at least one) (PO 4 ) 6 Cl 2 : Eu, Mn, etc. .
緑色から黄色に発光する蛍光体として、少なくともセリウムで賦活されたイットリウム・アルミニウム酸化物蛍光体、少なくともセリウムで賦括されたイットリウム・ガドリニウム・アルミニウム酸化物蛍光体、少なくともセリウムで賦活されたイットリウム・アルミニウム・ガーネット酸化物蛍光体、及び、少なくともセリウムで賦活されたイットリウム・ガリウム・アルミニウム酸化物蛍光体などがある（いわゆるＹＡＧ系蛍光体）。具体的には、Ｌｎ３Ｍ５Ｏ１２：Ｒ（Ｌｎは、Ｙ、Ｇｄ、Ｌａから選ばれる少なくとも１以上である。Ｍは、Ａｌ、Ｃａの少なくともいずれか一方を含む。Ｒは、ランタノイド系である。）、（Ｙ１−ｘＧａｘ）３（Ａｌ１−ｙＧａｙ）５Ｏ１２：Ｒ（Ｒは、Ｃｅ、Ｔｂ、Ｐｒ、Ｓｍ、Ｅｕ、Ｄｙ、Ｈｏから選ばれる少なくとも１以上である。０＜ｘ＜０．５、０＜ｙ＜０．５である。）を使用することができる。 As phosphors emitting green to yellow, at least cerium-activated yttrium / aluminum oxide phosphors, at least cerium-enriched yttrium / gadolinium / aluminum oxide phosphors, at least cerium-activated yttrium / aluminum There are garnet oxide phosphors and at least cerium activated yttrium gallium aluminum oxide phosphors (so-called YAG phosphors). Specifically, Ln 3 M 5 O 12 : R (Ln is at least one selected from Y, Gd, and La. M includes at least one of Al and Ca. R is a lanthanoid series. in a), (Y 1-x Ga x) 3 (Al 1-y Ga y) 5 O 12:. R (R is, Ce, Tb, Pr, Sm , Eu, Dy, at least 1 or more selected from Ho 0 <x <0.5, 0 <y <0.5) can be used.
赤色に発光する蛍光体として、例えば、Ｙ２Ｏ２Ｓ：Ｅｕ、Ｌａ２Ｏ２Ｓ：Ｅｕ、Ｙ２Ｏ３：Ｅｕ、Ｇｄ２Ｏ２Ｓ：Ｅｕなどがある。 Examples of phosphors that emit red light include Y 2 O 2 S: Eu, La 2 O 2 S: Eu, Y 2 O 3 : Eu, and Gd 2 O 2 S: Eu.
また、現在主流の青色ＬＥＤに対応し発光する蛍光体としては、Ｙ３（Ａｌ，Ｇａ）５Ｏ１２：Ｃｅ，（Ｙ,Ｇｄ）３Ａｌ５Ｏ１２：Ｃｅ，Ｌｕ３Ａｌ５Ｏ１２：Ｃｅ，Ｙ３Ａｌ５Ｏ１２：ＣｅなどのＹＡＧ系蛍光体、Ｔｂ３Ａｌ５Ｏ１２：ＣｅなどのＴＡＧ系蛍光体、（Ｂａ，Ｓｒ）２ＳｉＯ４：Ｅｕ系蛍光体やＣａ３Ｓｃ２Ｓｉ３Ｏ１２：Ｃｅ系蛍光体、（Ｓｒ，Ｂａ，Ｍｇ）２ＳｉＯ４：Ｅｕなどのシリケート系蛍光体、（Ｃａ，Ｓｒ）２Ｓｉ５Ｎ８：Ｅｕ、（Ｃａ，Ｓｒ）ＡｌＳｉＮ３：Ｅｕ、ＣａＳｉＡｌＮ３：Ｅｕ等のナイトライド系蛍光体、Ｃａｘ（Ｓｉ，Ａｌ）１２（Ｏ，Ｎ）１６：Ｅｕなどのオキシナイトライド系蛍光体、さらには（Ｂａ，Ｓｒ，Ｃａ）Ｓｉ２Ｏ２Ｎ２：Ｅｕ系蛍光体、Ｃａ８ＭｇＳｉ４Ｏ１６Ｃｌ２：Ｅｕ系蛍光体、ＳｒＡｌ２Ｏ４：Ｅｕ，Ｓｒ４Ａｌ１４Ｏ２５：Ｅｕ等の蛍光体が挙げられる。 As the phosphor corresponding to the current mainstream of the blue LED emission, Y 3 (Al, Ga) 5 O 12: Ce, (Y, Gd) 3 Al 5 O 12: Ce, Lu 3 Al 5 O 12: Ce, Y 3 Al 5 O 12 : YAG phosphor such as Ce, TAG phosphor such as Tb 3 Al 5 O 12 : Ce, (Ba, Sr) 2 SiO 4 : Eu phosphor and Ca 3 Sc 2 Si 3 O 12 : Ce phosphor, silicate phosphor such as (Sr, Ba, Mg) 2 SiO 4 : Eu, (Ca, Sr) 2 Si 5 N 8 : Eu, (Ca, Sr) AlSiN 3 : Eu, CaSiAlN 3 : Nitride phosphor such as Eu, Cax (Si, Al) 12 (O, N) 16 : Oxynitride phosphor such as Eu, and (Ba, Sr, Ca) Si 2 O 2 N 2 : E Examples include phosphors such as u-based phosphors, Ca 8 MgSi 4 O 16 Cl 2 : Eu-based phosphors, SrAl 2 O 4 : Eu, and Sr 4 Al 14 O 25 : Eu.
これらの中では、ＹＡＧ系蛍光体、ＴＡＧ系蛍光体、シリケート系蛍光体が、発光効率や輝度などの点で好ましく用いられる。上記以外にも、用途や目的とする発光色に応じて公知の蛍光体を用いることができる。 Among these, YAG-based phosphors, TAG-based phosphors, and silicate-based phosphors are preferably used in terms of light emission efficiency and luminance. In addition to the above, known phosphors can be used according to the intended use and the intended emission color.
（添加剤）
本発明の封止用組成物には、添加剤として塗布膜安定化のための分散剤やレベリング剤等を添加することも可能である。また、蛍光体沈降抑制剤としてアルミナ微粒子、シリカ微粒子、シリコーン微粒子等を添加することも可能である。
(Additive)
In the sealing composition of the present invention, it is also possible to add a dispersant, a leveling agent or the like for stabilizing the coating film as an additive. It is also possible to add alumina fine particles, silica fine particles, silicone fine particles and the like as the phosphor sedimentation inhibitor.
（作製方法）
本発明のシリコーン樹脂組成物について作製方法を説明する。なお、これらの作製は、その他の公知の方法を用いてもよく、後述する方法に限定されない。
(Production method)
A production method for the silicone resin composition of the present invention will be described. In addition, these productions may use other known methods, and are not limited to the methods described later.
シリコーン樹脂、無機粒子および蛍光体を所定量混合、分散する。混合、分散には、ホモジナイザー、自公転型攪拌機、３本ローラー、ボールミル、遊星式ボールミル、ビーズミル等の攪拌・混練機で均質に混合分散することによって、本発明のシリコーン樹脂組成物を作製することができる。混合分散後、もしくはその過程で、真空もしくは減圧により脱泡することも好ましい。付加反応型シリコーン樹脂を用いる場合は、ケイ素原子に結合したアルケニル基を含有する化合物と、ケイ素原子に結合した水素原子を有する化合物を混合すると、室温でも硬化反応が始まることがあるので、アセチレン化合物などのヒドロシリル化反応遅延剤を配合して、ポットライフを延長することも可能である。 A predetermined amount of silicone resin, inorganic particles and phosphor are mixed and dispersed. For the mixing and dispersion, the silicone resin composition of the present invention is prepared by homogeneously mixing and dispersing with a stirrer / kneader such as a homogenizer, self-revolving stirrer, three rollers, ball mill, planetary ball mill, or bead mill. Can do. It is also preferable to degas by vacuum or reduced pressure after mixing or dispersing. When an addition reaction type silicone resin is used, since a curing reaction may start even at room temperature when a compound containing an alkenyl group bonded to a silicon atom and a compound having a hydrogen atom bonded to a silicon atom are mixed, an acetylene compound It is also possible to extend the pot life by blending a hydrosilylation reaction retarder such as
（用途）
本発明のシリコーン樹脂組成物は種々の用途に適用できるが、発光ダイオードに好ましく適用することができる。一例として、本発明のシリコーン樹脂組成物の硬化物をＬＥＤチップ上に形成する方法を説明する。上記のようにして得られたシリコーン樹脂組成物をＬＥＤチップ上に射出成型、圧縮成型、注型成型、トランスファー成型、コーティング、ディスペンス、印刷、転写等の方法で膜形成した後、硬化させることにより、所望の形状の蛍光体分散体をＬＥＤチップ上に設置することができる。加熱硬化させる場合の硬化条件は、通常４０〜２５０℃で１分〜５時間、好ましくは１００℃〜２００℃で５分〜２時間である。こうして、シリコーン樹脂組成物の硬化物を備えた発光ダイオードが得られる。この後、蛍光体を含まない透明シリコーン樹脂で封止してもよいし、ＬＥＤチップ上だけでなく周辺部等もシリコーン樹脂組成物の硬化物で覆う等の方法により、本発明のシリコーン樹脂組成物自体を封止剤として利用しても良い。
(Use)
The silicone resin composition of the present invention can be applied to various uses, but can be preferably applied to a light emitting diode. As an example, a method for forming a cured product of the silicone resin composition of the present invention on an LED chip will be described. The silicone resin composition obtained as described above is formed on an LED chip by a method such as injection molding, compression molding, casting molding, transfer molding, coating, dispensing, printing, transfer, etc., and then cured. The phosphor dispersion having a desired shape can be placed on the LED chip. The curing conditions for heat curing are usually 40 to 250 ° C. for 1 minute to 5 hours, preferably 100 ° C. to 200 ° C. for 5 minutes to 2 hours. Thus, a light emitting diode provided with a cured product of the silicone resin composition is obtained. Thereafter, the silicone resin composition of the present invention may be sealed with a transparent silicone resin that does not contain a phosphor, or by a method such as covering not only the LED chip but also the peripheral portion with a cured product of the silicone resin composition. The object itself may be used as a sealant.
また、本発明のシリコーン樹脂組成物を直接ＬＥＤチップ上に設置するだけでなく、シート状成型物とした後、ＬＥＤチップ上に設置することもできる。本発明のシリコーン樹脂組成物を、予め剥離性を有するフレキシブルなベース基板上に塗布、乾燥、硬化もしくは半硬化させた後、ＬＥＤチップ上に剥離転写させることによって、さらに必要に応じて追加の加熱、硬化を行うことによって、所望の形状の蛍光体分散体をＬＥＤチップ上に設置することができる。ベース基板としては、ＰＥＴフィルム、ＰＰフィルム、ＰＰＳフィルム、ポリイミドフィルム、アラミドフィルムなどの他、コーティング処理が施された紙、アルミ箔もしくは板、スチール箔もしくは板を使用することができるが、経済性、取り扱い性の面でＰＥＴフィルムが好ましく、シリコーン組成物の硬化に高温を必要とする場合は、耐熱性の面でポリイミドフィルが好ましい。 In addition, the silicone resin composition of the present invention can be installed not only directly on the LED chip but also on the LED chip after forming a sheet-like molded product. The silicone resin composition of the present invention is applied on a flexible base substrate having peelability in advance, dried, cured, or semi-cured, and then peel-transferred onto the LED chip, thereby further heating as necessary. By performing curing, a phosphor dispersion having a desired shape can be placed on the LED chip. As the base substrate, PET film, PP film, PPS film, polyimide film, aramid film, etc., as well as coated paper, aluminum foil or plate, steel foil or plate can be used. A PET film is preferable in terms of handleability, and a polyimide film is preferable in terms of heat resistance when a high temperature is required for curing the silicone composition.
シート状成型物の厚さとしては、５〜５００μｍであることが好ましく、取り扱い性の点から５０〜２００μｍであることがさらに好ましい。また、厚さにバラツキがあると、ＬＥＤチップ上の蛍光体量に違いが生じ、結果として発光スペクトルにもバラツキが生じる。従って、厚さのバラツキは、好ましくは±５％、さらに好ましくは±３％である。 The thickness of the sheet-like molded product is preferably 5 to 500 μm, and more preferably 50 to 200 μm from the viewpoint of handleability. In addition, when the thickness varies, the amount of phosphor on the LED chip varies, and as a result, the emission spectrum also varies. Therefore, the thickness variation is preferably ± 5%, more preferably ± 3%.
ベース基板上への蛍光体分散シリコーン組成物の塗布は、リバースロールコーター、ブレードコーター、キスコーター、スリットダイコーター、スクリーン印刷等により行うことができるが、前述のような得られる蛍光体分散シリコーン組成物のシート状成型物の厚さが均一性を得るためにはスリットダイコーターで塗布することが好ましい。 The phosphor-dispersed silicone composition can be applied to the base substrate by a reverse roll coater, a blade coater, a kiss coater, a slit die coater, screen printing, or the like. The phosphor-dispersed silicone composition obtained as described above can be used. In order to obtain a uniform thickness of the sheet-like molded product, it is preferably applied by a slit die coater.
得られたシート状成型物は、ＬＥＤチップと同程度の大きさにカットされ、マウンターなどの装置によって、ＬＥＤチップ上に設置される。その後、蛍光体を含まない透明シリコーン樹脂で封止してもよいし、シート状成型物で覆う範囲をＬＥＤチップ上だけでなく周辺部にも広げる等の方法によりシート状成型物自体を封止剤として利用しても良い。 The obtained sheet-like molded product is cut into the same size as the LED chip, and placed on the LED chip by a device such as a mounter. Then, it may be sealed with a transparent silicone resin that does not contain a phosphor, or the sheet-shaped molded product itself may be sealed by a method such as extending the area covered with the sheet-shaped molded product not only to the LED chip but also to the periphery. It may be used as an agent.
以下に、本発明を実施例により具体的に説明する。ただし、本発明はこれに限定されるものではない。各実施例および比較例における組成物で用いた原料、各実施例および比較例における評価方法は以下の通りである。 Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to this. The raw materials used in the compositions in the examples and comparative examples, and the evaluation methods in the examples and comparative examples are as follows.
［シリコーン樹脂組成物］
（シリコーン樹脂）
シリコーン樹脂：東レ・ダウコーニング社製“ＯＥ６６３０”（屈折率：１．５３、密度：１．１７ｇ／ｃｍ３）。２液混合タイプのため、Ａ液、Ｂ液からなる。
[Silicone resin composition]
(Silicone resin)
Silicone resin: “OE6630” manufactured by Toray Dow Corning (refractive index: 1.53, density: 1.17 g / cm 3 ). Since it is a two-component mixed type, it consists of component A and component B.
（無機粒子）
無機粒子１：平岡特殊硝子製作（株）社製フッ化バリウムＡ（屈折率：１．４５、粒径：０．５μｍ、密度：４．５ｇ／ｃｍ３）
無機粒子２：平岡特殊硝子製作（株）社製フッ化バリウムＢ（屈折率：１．４７、粒径：０．５μｍ、密度：４．５ｇ／ｃｍ３）
無機粒子３：平岡特殊硝子製作（株）社製フッ化バリウムＣ（屈折率：１．４５、粒径：０．５μｍ、密度：４．９ｇ／ｃｍ３）
無機粒子４：平岡特殊硝子製作（株）社製フッ化バリウムＤ（屈折率：１．４７、粒径：０．５μｍ、密度：４．９ｇ／ｃｍ３）
無機粒子５：平岡特殊硝子製作（株）社製フッ化バリウムＥ（屈折率：１．４７、粒径：３．０μｍ、密度：４．９ｇ／ｃｍ３）
無機粒子６：平岡特殊硝子製作（株）社製フッ化バリウムＦ（屈折率：１．４７、粒径：６．０μｍ、密度：４．９ｇ／ｃｍ３）
無機粒子７：平岡特殊硝子製作（株）社製フッ化バリウムＧ屈折率：１．４７、粒径：８．０μｍ、密度：４．９ｇ／ｃｍ３）
無機粒子８：（株）アドマテックス社製高純度合成球状シリカ“ＳＯ−Ｃ６”（屈折率：１．４５、粒径：０．５μｍ、密度：２．２ｇ／ｃｍ３）
無機粒子９：第一稀元素化学工業（株）社製酸化ジルコニア“ＵＥＰ−１００”（屈折率：１．７６、粒径：０．５μｍ、密度：６．０ｇ／ｃｍ３）。
(Inorganic particles)
Inorganic particles 1: Barium fluoride A manufactured by Hiraoka Special Glass Co., Ltd. (refractive index: 1.45, particle size: 0.5 μm, density: 4.5 g / cm 3 )
Inorganic particles 2: Barium fluoride B manufactured by Hiraoka Special Glass Manufacturing Co., Ltd. (refractive index: 1.47, particle size: 0.5 μm, density: 4.5 g / cm 3 )
Inorganic particles 3: Barium fluoride C manufactured by Hiraoka Special Glass Manufacturing Co., Ltd. (refractive index: 1.45, particle size: 0.5 μm, density: 4.9 g / cm 3 )
Inorganic particles 4: Barium fluoride D manufactured by Hiraoka Special Glass Manufacturing Co., Ltd. (refractive index: 1.47, particle size: 0.5 μm, density: 4.9 g / cm 3 )
Inorganic particles 5: Barium fluoride E manufactured by Hiraoka Special Glass Manufacturing Co., Ltd. (refractive index: 1.47, particle size: 3.0 μm, density: 4.9 g / cm 3 )
Inorganic particles 6: Barium fluoride F manufactured by Hiraoka Special Glass Manufacturing Co., Ltd. (refractive index: 1.47, particle size: 6.0 μm, density: 4.9 g / cm 3 )
Inorganic particles 7: manufactured by Hiraoka Special Glass Co., Ltd. Barium fluoride G refractive index: 1.47, particle size: 8.0 μm, density: 4.9 g / cm 3 )
Inorganic particles 8: high purity synthetic spherical silica “SO-C6” manufactured by Admatechs Co., Ltd. (refractive index: 1.45, particle size: 0.5 μm, density: 2.2 g / cm 3 )
Inorganic particles 9: Zirconia oxide “UEP-100” (refractive index: 1.76, particle size: 0.5 μm, density: 6.0 g / cm 3 ) manufactured by Daiichi Rare Element Chemical Co., Ltd.
（蛍光体）
蛍光体：Ｉｎｔｅｍａｔｉｘ社製“ＮＹＡＧ−０２”（ＣｅドープのＹＡＧ系蛍光体、メジアン径（Ｄ５０）：７μｍ、密度：４．８ｇ／ｃｍ３）。
(Phosphor)
Phosphor: “NYAG-02” manufactured by Intematix (Ce-doped YAG phosphor, median diameter (D 50 ): 7 μm, density: 4.8 g / cm 3 ).
［各実施例および比較例における評価方法］
＜ＬＥＤパッケージの作製と輝度評価＞
実施例１〜１４、比較例１〜３におけるＬＥＤパッケージは以下の要領で作製した。まず、容積３００ｍＬのポリエチレン製容器に、表１〜３に示す濃度になるように所定量のシリコーン樹脂、無機粒子、蛍光体を秤量し、クラボウ社製遊星式攪拌脱泡装置“マゼルスターＫＫ−４００”を用い、１，０００ｒｐｍで１０分間攪拌、脱泡した。得られた組成物を、ＬＥＤチップ（昭和電工（株）製“ＧＭ２ＱＴ４５０Ｇ”、平均波長：４５３．４ｎｍ）が実装されたフレーム（エノモト社製フレーム“ＴＯＰ ＬＥＤ ＢＡＳＥ”）に、ディスペンサー（武蔵野エンジニアリング社製“ＭＰＰ−１”）を用いて流し込み、８０℃で１時間、１５０℃で２時間キュアすることによって、ＬＥＤパッケージを作製した。作製したＬＥＤパッケージを、２０ｍＡの電流を流して点灯させ、瞬間マルチ測光システム（大塚電子社製“ＭＣＰＤ−７７００”）を用いて、試験開始直後の輝度を測定し、１０個の平均値を輝度とした。比較例１に対する輝度の増加率を下式により計算し、増加率が２．０％以上であれば輝度向上に非常に効果あり（表中でＡと表記）、１．０％以上２．０％未満であれば、効果あり（表中でＢと表記）、０．１％以上１．０％未満であれば、少し効果あり（表中でＣと表記）、０．１％未満（マイナスとなる場合を含む）であれば輝度向上効果なし（表中でＮＧと表記）とした。
[Evaluation methods in Examples and Comparative Examples]
<Production of LED package and brightness evaluation>
The LED packages in Examples 1 to 14 and Comparative Examples 1 to 3 were produced as follows. First, a predetermined amount of silicone resin, inorganic particles, and phosphor are weighed in a polyethylene container having a volume of 300 mL so as to have the concentrations shown in Tables 1 to 3, and a planetary stirring and deaerator “Mazerustar KK-400” manufactured by Kurabo Industries Co., Ltd. is used. ”And stirred and degassed at 1,000 rpm for 10 minutes. The obtained composition was placed in a dispenser (Musashino Engineering Co., Ltd.) on a frame (Enomoto's frame “TOP LED BASE”) on which an LED chip (“GM2QT450G” manufactured by Showa Denko KK, average wavelength: 453.4 nm) was mounted. LED package was produced by pouring using “MPP-1”) and curing at 80 ° C. for 1 hour and 150 ° C. for 2 hours. The manufactured LED package was turned on by passing a current of 20 mA, and using an instantaneous multi-photometry system (“MCPD-7700” manufactured by Otsuka Electronics Co., Ltd.), the luminance immediately after the start of the test was measured. It was. The luminance increase rate relative to Comparative Example 1 is calculated by the following formula. If the increase rate is 2.0% or more, it is very effective in improving the luminance (denoted as A in the table), and 1.0% or more and 2.0. If it is less than%, there is an effect (denoted as B in the table), and if it is 0.1% or more and less than 1.0%, there is a little effect (denoted as C in the table), less than 0.1% (minus In other words, the brightness is not improved (denoted as NG in the table).
輝度の増加率（％）＝｛（各実施例、比較例の輝度）−（比較例１の輝度）｝／（比較例１の輝度）×１００。 Brightness increase rate (%) = {(luminance of each example, comparative example) − (luminance of comparative example 1)} / (luminance of comparative example 1) × 100.
（実施例１〜４、比較例１〜３）−無機粒子の屈折率、密度による輝度向上効果−
表１に示す無機粒子を用いて、ＬＥＤパッケージの作製と輝度測定および輝度の増加率の評価を行い、結果を表１に示した。実施例１〜４では、比較例１と比較して、輝度向上効果が得られた。比較例２では輝度はほぼ変わらず、比較例３では輝度は低下した。
(Examples 1 to 4, Comparative Examples 1 to 3)-Brightness improvement effect due to refractive index and density of inorganic particles-
Using the inorganic particles shown in Table 1, LED package fabrication, luminance measurement, and luminance increase rate evaluation were performed, and the results are shown in Table 1. In Examples 1 to 4, a brightness improvement effect was obtained as compared with Comparative Example 1. In Comparative Example 2, the luminance was not substantially changed, and in Comparative Example 3, the luminance was reduced.
（実施例５〜１１）−無機粒子の濃度による輝度向上効果−
無機粒子を無機粒子２に変更し、表２に記載の無機粒子の添加量に変更した以外は実施例１と同様の操作でＬＥＤパッケージを作製し評価を行った。結果を表２に示す。これらの結果から、無機粒子の固形分濃度によらず輝度向上効果は見られたが、その効果は０．５ｖｏｌ％以上のときがより大きく、０．７ｖｏｌ％以上２．５ｖｏｌ％以下の範囲であればさらに大きいことがわかった。
(Examples 5 to 11)-Brightness improvement effect by concentration of inorganic particles-
An LED package was prepared and evaluated in the same manner as in Example 1 except that the inorganic particles were changed to inorganic particles 2 and the addition amount of inorganic particles shown in Table 2 was changed. The results are shown in Table 2. From these results, although the brightness improvement effect was seen regardless of the solid content concentration of the inorganic particles, the effect was larger when the concentration was 0.5 vol% or more, and in the range of 0.7 vol% or more and 2.5 vol% or less. I found that it was even bigger.
（実施例１２〜１４）−無機粒子の粒径の効果−
表３に記載の無機粒子に変更した以外は実施例１と同様の操作でＬＥＤパッケージを作製し評価を行った。結果を表３に示す。これらの結果から、粒径に依存せず、輝度が向上することがわかった。
(Examples 12 to 14) -Effect of particle size of inorganic particles-
An LED package was prepared and evaluated in the same manner as in Example 1 except that the inorganic particles listed in Table 3 were changed. The results are shown in Table 3. From these results, it was found that the luminance was improved without depending on the particle diameter.
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