JPWO2013047606A1 - 表面実装型発光装置用樹脂成形体およびその製造方法ならびに表面実装型発光装置 - Google Patents
表面実装型発光装置用樹脂成形体およびその製造方法ならびに表面実装型発光装置 Download PDFInfo
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- MHFJYSOKRPQWNF-UHFFFAOYSA-N silane triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-3-yl)ethyl]silane Chemical class [SiH4].CCO[Si](CCC1CCC2OC2C1)(OCC)OCC MHFJYSOKRPQWNF-UHFFFAOYSA-N 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
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- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 238000006227 trimethylsilylation reaction Methods 0.000 description 1
- DTBRTYHFHGNZFX-UHFFFAOYSA-N trioctyl borate Chemical compound CCCCCCCCOB(OCCCCCCCC)OCCCCCCCC DTBRTYHFHGNZFX-UHFFFAOYSA-N 0.000 description 1
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 description 1
- IYGPXXORQKFXCZ-UHFFFAOYSA-N tris(2-methoxyethyl) borate Chemical compound COCCOB(OCCOC)OCCOC IYGPXXORQKFXCZ-UHFFFAOYSA-N 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 description 1
- FRZSCIVUSFMNBX-UHFFFAOYSA-L zinc;12-hydroxyoctadecanoate Chemical compound [Zn+2].CCCCCCC(O)CCCCCCCCCCC([O-])=O.CCCCCCC(O)CCCCCCCCCCC([O-])=O FRZSCIVUSFMNBX-UHFFFAOYSA-L 0.000 description 1
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- 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
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- 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
- H01L33/62—Arrangements for conducting electric current to or from the semiconductor body, e.g. lead-frames, wire-bonds or solder balls
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- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
- B29C45/14639—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles for obtaining an insulating effect, e.g. for electrical components
- B29C45/14655—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles for obtaining an insulating effect, e.g. for electrical components connected to or mounted on a carrier, e.g. lead frame
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- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
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- B29C45/372—Mould cavity walls, i.e. the inner surface forming the mould cavity, e.g. linings provided with means for marking or patterning, e.g. numbering articles
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Abstract
Description
(b)上側合わせ面の凹部とリードフレームおよび/または下側合わせ面とにより形成された内部空間に、樹脂注入孔から液状の熱硬化性樹脂を注入する工程。
(c)金型を加熱することにより、注入された液状の熱硬化性樹脂を硬化させ、樹脂硬化体をリードフレームの所定位置に接着させる工程。
(d)金型を脱型し、リードフレームと樹脂硬化体とが一体成形され、底部にリードフレームが露出する凹部を有する樹脂成形体を得る工程。
(e)凹部の底部に露出するリードフレームに発光素子を通電可能に実装する工程。
(f)凹部に透明性樹脂を充填して発光素子を封止する工程。
1.樹脂硬化体と複数のリードとが一体成形され、底部に複数のリードが露出する凹部を有する表面実装型発光装置用樹脂成形体であって、凹部の開口面の十点平均粗さ(Rz)が1μm以上、10μm以下であり、樹脂硬化体のガラス転移温度が10℃以上であり、ガラス転移温度が、熱機械分析装置(TMA)を用い、温度範囲−50〜250℃、昇温速度5℃/分および試料サイズ長1〜5mmの条件で測定された値であり、かつ、凹部の開口面の460nmにおける光反射率が80%以上であり、樹脂成形体を180℃で72時間加熱した後の開口面における光反射率の保持率が90%以上である表面実装型発光装置用樹脂成形体。
5.金属層は、最表面層、および、リードの表面と最表面層との間に介在する第2金属層を有し、第2金属層は、Ag層、Pd層又はAg層とPd層との積層体である上記4に記載の表面実装型発光装置用樹脂成形体。
6.金属層がめっき層である上記4または5に記載の表面実装型発光装置用樹脂成形体。
9.第1リードは、凹部の底部に露出する第1インナーリード部と、樹脂硬化体に接触する第1アウターリード部とを含み、かつ、第2リードは、凹部の底部に露出する第2インナーリード部と、樹脂硬化体に接触する第2アウターリード部とを含む上記8に記載の表面実装型発光装置用樹脂成形体。
10.外側面に、第1アウターリード部および/または第2アウターリード部が露出する上記9に記載の表面実装型発光装置用樹脂成形体。
12.第1インナーリード部および第2インナーリード部はその表面に前記金属層を有し、第1アウターリード部および第2アウターリード部はその表面に金属層を有していない上記9〜11のいずれかに記載の表面実装型発光装置用樹脂成形体。
13.複数のリードは、樹脂硬化体が充填されている切り欠き部を有する上記1〜12のいずれかに記載の表面実装型発光装置用樹脂成形体。
16.上側凹部が上側合わせ面の所定位置に形成された上金型と、平坦な下側合わせ面を有する下金型と、所定の間隔を空けて縦横に切り欠き部が形成された複数のリードと、を用いることにより、複数のリードの切り欠き部で囲まれた領域毎に樹脂硬化体を形成し、次いで切り欠き部に沿って複数のリードを切断することにより、複数個の樹脂成形体を得る上記14または15に記載の表面実装型発光装置用樹脂成形体の製造方法。
18.複数のリードの切り欠き部が、上側合わせ面の上側凹部が形成されていない領域と、下側合わせ面と、により挟持される上記16または17に記載の表面実装型発光装置用樹脂成形体の製造方法。
19.上記1〜13のいずれかに記載の表面実装型発光装置用樹脂成形体と、樹脂成形体の凹部底部に実装され、複数のリードと通電可能に接続される発光素子と、発光素子を封止する透明樹脂層と、を備える表面実装型発光装置。
20.複数個の発光素子が実装される上記19に記載の表面実装型発光装置。
本発明の樹脂成形体は、樹脂硬化体と複数のリードとが一体成形され、底部に複数のリードが露出する凹部を有し、凹部の開口面の十点平均粗さ(以下単に「Rz」とすることがある)が1μm以上、10μm以下であることを特徴の一つとする。
本実施形態では、第1リード10および第2リード11という一対のリードを用いているが、これに限定されず、3本以上の任意の数のリードを用いても良い。
樹脂成形体1の立体形状は本実施形態ではほぼ平板状であるが、それに限定されず、発光装置の設計などに応じて各種形状から適宜選択される。
このような構成を採ることによっても、第1リード10および第2リード11を確実に保護し、樹脂成形体4を用いた表面実装型発光装置の信頼性を高めることができる。
さらに、本実施形態においても、樹脂成形体の底部に露出する第1リードおよび第2リードの少なくとも一部にもめっき層を形成してもよい。
(A)成分はSiH基と反応性を有する炭素−炭素二重結合を1分子中に少なくとも2個含有する有機化合物であれば特に限定されない。
有機重合体系化合物である(A)成分としては、たとえば、ポリエーテル系、ポリエステル系、ポリアリレート系、ポリカーボネート系、飽和炭化水素系、不飽和炭化水素系、ポリアクリル酸エステル系、ポリアミド系、フェノール−ホルムアルデヒド系(フェノール樹脂系)、ポリイミド系の骨格を有するものを挙げることができる。
上記一般式(III)のR1は、得られる樹脂硬化体の耐熱性がより高くなりうるという観点からは、好ましくは炭素数1〜20の一価の有機基であり、より好ましくは炭素数1〜10の一価の有機基であり、さらに好ましくは炭素数1〜4の一価の有機基である。これらの好ましいR1の例としては、メチル基、エチル基、プロピル基、ブチル基、フェニル基、ベンジル基、フェネチル基、ビニル基、アリル基、グリシジル基、下記[化15]に例示される各一価基などが挙げられる。
CH2=C(R4)−R3− (V)
〔式中R3は直接結合または炭素数1〜48の二価の有機基を表し、R4は水素原子またはメチル基を表す。〕
で表される有機化合物であることがさらに好ましい。
ただし、上記のような一般式(III)で表される有機化合物の好ましい例においても、SiH基に対して反応性を有する炭素−炭素二重結合を1分子中に少なくとも2個含有することは必要である。耐熱性をより向上させるという観点からは、SiH基に対して反応性を有する炭素−炭素二重結合を1分子中に3個以上含有する有機化合物であることがより好ましい。
一般式(VI)で表される化合物中の置換基R1は、好ましくはC、H、O以外の構成元素を含まない基であり、より好ましくは炭化水素基であり、さらに好ましくはメチル基である。また、入手容易性などから、一般式(VI)で表わされる化合物は、1,3,5,7−テトラメチルシクロテトラシロキサンであることが好ましい。
上記したような各種(β)成分は1種を単独でまたは2種以上を組み合わせて使用できる。
このヒドロシリル化反応において、SiH基に対して反応性を有する炭素−炭素二重結合を1分子中に少なくとも2個含有する有機化合物と(β)成分との混合比率は、特に限定されないが、反応中のゲル化が抑制できるという点においては、一般に、前者におけるSiH基に対して反応性を有する炭素−炭素二重結合の総数(X)と後者におけるSiH基の総数(Y)との比が、好ましくはX/Y≧2、より好ましくはX/Y≧3である。また(A)成分の(B)成分に対する相溶性がよくなりやすいという観点からは、好ましくは10≧X/Y、より好ましくは5≧X/Yである。
これらの触媒の中では、触媒活性の観点から塩化白金酸、白金−オレフィン錯体、白金−ビニルシロキサン錯体などが好ましい。また、これらの触媒は1種を単独でまたは2種以上を組み合わせて使用できる。
反応時間、反応時の圧力も必要に応じ種々設定できる。
その他、反応性を制御する目的などのために種々の添加剤を用いてもよい。
(A)成分は、1種を単独でまたは2種以上を組み合わせて使用できる。
(B)成分としては、1分子中に少なくとも2個のSiH基を含有する化合物であれば特に制限がなく、たとえば、国際公開WO96/15194に記載される化合物で、1分子中に少なくとも2個のSiH基を有するものなどが使用できる。
一般式(VI)で表される化合物中の置換基R1は、好ましくはC、H、Oから構成されるものであり、より好ましくは炭化水素基であり、さらに好ましくはメチル基である。また、一般式(VI)で表される化合物としては、入手容易性の観点からは、1,3,5,7−テトラメチルシクロテトラシロキサンであることが好ましい。
(B)成分は、一種を単独でまたは2種以上を組み合わせて使用できる。
重合体系化合物としては、たとえば、ポリシロキサン系、ポリエーテル系、ポリエステル系、ポリアリレート系、ポリカーボネート系、飽和炭化水素系、不飽和炭化水素系、ポリアクリル酸エステル系、ポリアミド系、フェノール−ホルムアルデヒド系(フェノール樹脂系)、ポリイミド系の化合物などが挙げられる。
(β)成分のその他の例として、ビスジメチルシリルベンゼンなどのSiH基を有する化合物が挙げられる。
上記した各種(β)成分は、1種を単独でまたは2種以上を組み合わせて使用できる。
Rn(CH2=CH)mSiO(4-n-m)/2
(式中、Rは水酸基、メチル基あるいはフェニル基から選ばれる基であり、n、mは0≦n<4、0<m≦4、0<n+m≦4を満たす数)
無機充填材の比表面積についても、エポキシ系などの従来の封止材の充填材として使用および/または提案されているものをはじめ、各種設定できる。
上記した各種の無機充填材は、1種を単独でまたは2種以上を組み合わせて使用できる。
(F)成分としては種々のものを用いることができ、たとえば、酸化チタン、酸化亜鉛、酸化マグネシウム、酸化アンチモン、酸化ジルコニウム、酸化ストロンチウム、酸化ニオブ、窒化ホウ素、チタン酸バリウム、硫化亜鉛、硫酸バリウム、炭酸マグネシウム、無機中空粒子などが挙げられる。無機中空粒子としては、たとえば、珪酸ソーダガラス、アルミ珪酸ガラス、硼珪酸ソーダガラス、シラスなどが挙げられる。これらの中でも、取り扱いの容易性や入手性、コストの観点から酸化チタンまたは酸化亜鉛が好ましい。
平均粒径は、レーザー回折散乱式粒度分布計を用いて測定することができる。
(E)成分および(F)成分の合計量が少ないと、強度や硬度を高くする効果や、線膨張率を低減化する効果が得られにくくなる。
(G)成分は金属石鹸であり、熱硬化性樹脂組成物(X)の離型性をはじめとする成形性を改良するために添加される。
B(OR1)3 (VII)
B(OCOR1)3 (VIII)
(式中R1は炭素数1〜48の有機基を表す。)
これらのシラノール縮合触媒は1種を単独でまたは2種以上を組み合わせて使用できる。
ヒンダートフェノール系老化防止剤としては、チバスペシャリティーケミカルズ社から入手できるイルガノックス1010をはじめとして、各種のものが用いられる。
これらの老化防止剤は1種を単独でまたは2種以上を組み合わせて使用できる。
熱可塑性樹脂は1種を単独でまたは2種以上を組み合わせて使用できる。
保持率(%)=[(耐熱試験後の光反射率)/(初期の光反射率)]×100
保持率は、電子材料として用いた場合に信頼性が高いといった観点からは、好ましくは80%以上、より好ましくは85%以上、さらに好ましくは90%以上である。
本発明の樹脂成形体は、たとえば、複数のリードを金型で挟持して固定する工程(1)と、金型内に液状の熱硬化性樹脂を注入する工程(2)と、金型内に注入された液状の熱硬化性樹脂を硬化させる工程(3)と、金型から樹脂成形体を脱型する工程(4)を含む製造方法により製造できる。金型としては、上金型と下金型とを有し、上金型における樹脂成形体の凹部開口面に対応する面が所定の十点平均粗さ(Rz)を有する以外は、従来のトランスファモールド成形用金型と同じものを使用できる。以下に、工程(1)〜(4)について、詳細に説明する。
上金型30は、下金型35の鉛直方向上方に配置され、図示しない駆動手段により上下動可能に支持されている。上金型30の上側合わせ面31には、複数の第1凸部32が所定の位置に形成されている。上金型30の上側合わせ面31には、複数の第1凸部32を有する上側凹部33が形成され、第1凸部32は、所定の間隔を空けて、縦方向および横方向にほぼ等間隔に形成されていることが好ましい。
リードフレーム21は、上側合わせ面31と下側合わせ面36とを重ねたときに、上側凹部33とフレーム単位22とが所定の位置で重なるように下側合わせ面36に載置される。
本発明の表面実装型発光装置(以下単に「発光装置」とする)は、樹脂硬化体と複数のリードとが一体成形され、底部に複数のリードが露出する凹部を有し、凹部の開口面のRzが1μm以上、10μm以下であり、所定のガラス転移温度、光反射率および光反射率の保持率を有する樹脂成形体と、樹脂成形体の凹部底部に実装され、複数のリードと通電可能に接続される発光素子と、発光素子を封止する透明樹脂層と、を備えている。なお、樹脂成形体の凹部底部には、複数個の発光素子が実装されていても良い。
また、発光素子としては、従来から用いられている発光素子をいずれも使用でき、たとえば、発光ダイオード(LED)、レーザダイオード(LD)などが挙げられる。前記発光ダイオードには、たとえば、青色LEDチップ、紫外線LEDチップ、赤色LEDチップ、緑色LEDチップ、黄緑色LEDチップなどがあり、PN接合構造またはNPN接合構造を有するチップ、2つの電極が水平型または垂直型に配置されるチップなどを含む。
本発明の発光装置は、従来公知の各種の用途に用いることができる。具体的には、たとえば、液晶表示装置などのバックライト、照明、センサー光源、車両用計器光源、信号灯、表示灯、表示装置、面状発光体の光源、ディスプレイ、装飾、各種ライトなどが挙げられる。
樹脂成形体の凹部開口面の十点平均粗さ(Rz)を、輪郭形状測定器(サーフコム500DX、株式会社東京精密製)を用いて、JISB0633:01/ISO04288:96に基づき、触針R:2μmの条件で測定した。
ELP社製手術用メスを用いて、樹脂成形体から、長手方向2〜5mm×幅方向0.5〜1mm×厚み0.5〜1mmの寸法を有する樹脂試料を切り出した。この試料を熱機械分析装置(商品名:TMA、型式:TMA/SS6100、エスアイアイ・ナノテクノロジー(株)製)に投入し、窒素ガスフロー下、−50℃から250℃の範囲を昇降温速度5℃/分、圧縮加重29.4mNで膨張率の変化を測定し、ガラス転移温度を算出した。また、上記測定時の23℃〜150℃の平均の熱膨張係数を平均線膨張係数とする。
微小面分光色差計(商品名:VSS400、日本電色工業(株)製)を用い、波長400nm〜700nm(20nm間隔)における反射率を測定し、光反射率とした。ここでは、各波長において、樹脂成形体の凹部開口面の任意の4箇所(測定面積0.1mmφ)で測定を行ない、得られた測定値の平均値をその波長における光反射率とした。
また、耐熱試験(180℃のオーブンで72時間加熱する試験)後の光反射率(B)の、初期の光反射率(A)に対する保持率(%)は、下記式により算出した。
保持率(%)=[光反射率(B)/光反射率(A)]×100
樹脂成形体から樹脂試料0.5gを切り出し、乳鉢ですり潰して、3.2mmφの固体NMR試料管に詰めた。この試料管をVARIAN NMR装置(600MHz)に装填し、マジックアングルスピニング速度20kHzで13C CP/MAS NMR測定を実施し、試料の固体13CNMRスペクトルを求めた。
5Lの四つ口フラスコに、攪拌装置、滴下漏斗および冷却管をセットした。このフラスコにトルエン1800gおよび1,3,5,7−テトラメチルシクロテトラシロキサン1440gを入れ、120℃のオイルバス中で加熱および攪拌した。これに、トリアリルイソシアヌレート200g、トルエン200gおよび白金ビニルシロキサン錯体のキシレン溶液(白金として3重量%含有)1.44mlの混合液を50分かけて滴下した。得られた溶液をそのまま6時間加温および攪拌した後、未反応の1,3,5,7−テトラメチルシクロテトラシロキサンおよびトルエンを減圧留去した。得られた化合物は、1H−NMRの測定により、1,3,5,7−テトラメチルシクロテトラシロキサンのSiH基の一部がトリアリルイソシアヌレートと反応した下記[化33]に示す構造を有するものであることがわかった。
2Lオートクレーブにトルエン720gおよび1,3,5,7−テトラメチルシクロテトラシロキサン240gを入れ、気相部を窒素で置換した後、ジャケット温50℃で加熱および攪拌した。これに、アリルグリシジルエーテル171g、トルエン171gおよび白金ビニルシロキサン錯体のキシレン溶液(白金として3重量%含有)0.049gの混合液を90分かけて滴下した。滴下終了後にジャケット温を60℃に上げてさらに40分間反応させ、1H−NMRでアリル基の反応率が95%以上であることを確認した。
表1の内容に従って各成分を配合して、熱硬化性樹脂組成物A〜Dを調製した。
表1に示す配合例で得られた熱硬化性樹脂組成物C 50重量部、下記(D)成分27重量部、下記(E)成分557重量部、および下記(F)成分239重量部を均一に混合し、熱硬化性樹脂組成物(Xa)を調製した。なお、前記各成分の比率で、トータル100gになるように秤取り、均一に混合した。以下の実施例でも同様である。
(E)成分:球状シリカ(商品名:MSR?2212?TN、(株)龍森製、比重2.2、平均粒径24.8μm、12μm以下の粒子の割合:28%)
(F)成分:酸化チタン(商品名:タイペークPC?3、石原産業(株)製、ルチル型、比重4.2、塩素法、表面有機:Al、Si、ポリメチルハイドロジェンシロキサン、平均粒径0.21μm、12μm以下の粒子の割合:100%)
厚み3μmのAgメッキを表面に施した縦50mm、横55mm、厚み0.25mmのCu製のリードフレームを準備する。リードフレームは、図14に示すフレーム単位22が縦15列、横12列にわたって平行に並んだ一体成形品である。このリードフレームの各フレーム単位22に、縦横方向の間隔を1.1mmにして樹脂成形体(リフレクター)180個を形成した。各樹脂成形体は、凹部の内部空間の形状が逆円錐台状であり、凹部開口面の径が2.1mm、凹部底部の径が1.8mm、凹部内壁面の凹部底面に対する傾斜角度が75°、高さ0.55mmであり、凹部底部の横方向直径に沿って右端から0.45mmのところに縦方向に延びる幅約0.2mmの絶縁部を有し、フレーム単位22の第1、第2リード23,24を電気的に絶縁していた。
得られた樹脂成形体について、十点平均粗さ(Rz)、ガラス転移温度(Tg)、光反射率および固体13CNMRスペクトルを調べた。結果を表2に示す。
樹脂硬化体付リードフレームを、表面粗さ(Rz)が0.8μm、平面度0.01mm、サイズ320mm×212mm×18mmの鋼鉄製定盤の上に、樹脂硬化体を上側に向け、リードフレームを定盤側に向けて置き、樹脂硬化体付リードフレームと定盤との隙間に対して直定規(シンワ測定株式会社製、ステン直尺 150mm)を直角にあて、その隙間の距離を計測し、反り値とした。または、すきまゲージ(永井ゲージ製作所製、0.1mm〜1.0mm:0.1mm間隔)を隙間に差し込んで、隙間に挿入できる最大ゲージの値を反り値とした。樹脂硬化体付リードフレームの4辺のうちで定盤から最も距離がある値(mm)をその樹脂硬化体付リードフレームの反り値とした。樹脂成形体を真横から見た状態で凹になっている場合を順反り(+)、凸になっている場合を逆反り(−)と定義した。
表1に示す配合例で得られた熱硬化性樹脂組成物D 5.25重量部、下記(D)成分2.81重量部、下記(E)成分58.23重量部、下記(F)成分33.51重量部、および下記(G)成分0.20重量部を混合し、熱硬化性樹脂組成物(Xb)を調製した。
(E)成分:シリカ(MSR?2212?TN)
(F)成分:酸化亜鉛(酸化亜鉛1種、比重5.6、平均粒径0.6μm、堺化学工業(株)製)
(G)成分:ステアリン酸カルシウム
なお、実施例1において熱硬化性樹脂組成物Cに代えて表1に示す熱硬化性樹脂組成物AまたはBを用いても、実施例1と同様の結果が得られた。
メチルトリクロロシラン100重量部、トルエン200重量部を1Lのフラスコに入れ、氷冷下で水8重量部およびイソプロピルアルコール60重量部の混合液を、内温を−5〜0℃とし、5〜20時間かけて液中滴下した。その後、反応混合物を加熱して還流温度で20分間撹拌した。それから室温まで冷却し、水12重量部を30℃以下、30分間で滴下し、20分間撹拌した。更に水25重量部を滴下後、40〜45℃で60分間撹拌した。その後水200重量部を加えて有機層を分離した。この有機層を中性になるまで洗浄し、その後共沸脱水、濾過、減圧ストリップをすることにより、下記式で示される無色透明の固体(融点76℃)36.0質量部の熱硬化性オルガノポリシロキサンを得た。
(CH3)1.0Si(OC3H7)0.06(OH)0.11O1.4
市販の白色LED電球(商品名:EVERREDS、パナソニック(株)製)から、発光装置を取り出し、樹脂成形体の十点平均粗さ(Rz)、ガラス転移温度(Tg)、光反射率および固体13CNMRスペクトルを調べた。結果を表2に示す。
また、表2における実施例1および2と、比較例1および2との比較から、熱硬化性樹脂組成物(X)を用いることにより、光反射率、耐熱性および反射保持率が顕著に向上することが分かる。また、比較例1は、良好な光反射率を示すが、ガラス転移温度が−2℃と低いため、金型からの離型時に強度が十分でなく、樹脂成形体の個片化に伴う切削加工をする際、機械的強度が不十分となり、樹脂成形部の欠けなど製品として十分な品質を満たさなくなる。
精密ホットプレス(商品名:CYPF−10、新東工業(株)製)の上下プレス板の上型に、表面ラフネスの異なる金型入子[(十点平均粗さ(Rz)=0.9、2.5、5.8、10.6、15.6(μm)]を装着し、下型に十点平均粗さ(Rz)=0.9の金型を装着した。この装置を用い、熱硬化性樹脂組成物(Xa)または(Xb)を、170℃×硬化時間2分、離型速度0.2mm/s、サンプル形状:φ30×厚み1mmとなるようにプレス成形した。その後、金型をオープンした際の成形物の剥離モードを評価した。
実施例3〜6および比較例3の結果を表3に示す。実施例7〜10および比較例4の結果を表4に示す。
このように成形体表面のRzを規定することで、優れた光反射率を有する樹脂成形体が得られる条件が明らかとなった。
下記表5に示す各成分を、表5に示す配合割合で均一に混合し、熱硬化性樹脂組成物(Xc)および(Xd)を調製した。
実施例3〜10および比較例3〜4と同様の条件で、次のようにしてプレス成形を実施した。精密ホットプレス(CYPF−10)の上下プレス板の上型に、表面ラフネスの異なる金型入子[(十点平均粗さ(Rz)=0.9、2.5、5.8、10.6、15.6(μm)]を装着し、下型に十点平均粗さ(Rz)=0.9の金型を装着した。この装置を用い、熱硬化性樹脂組成物(X)を、170℃×硬化時間2分、離型速度0.2mm/s、サンプル形状:φ30×厚み1mmとなるようにプレス成形した。その後、金型をオープンした際の成形物の剥離モードを評価し、また固体13CNMRスペクトルを評価した。参考例1〜5の結果を表6に示し、参考例6〜10の結果を表7に示す。
熱硬化性樹脂組成物D:5.25重量部、下記(D)成分2.81重量部、下記(E)成分58.23重量部、下記(F)成分33.51重量部、および下記(G)成分0.20重量部を混合し、実施例2と同様にして、熱硬化性樹脂組成物(Xb)を調製した。この熱硬化性樹脂組成物(Xb)を用い、下記のようにして樹脂成形体の集合体を作製した。
(E)成分:シリカ(MSR-2212-TN)
(F)成分:酸化亜鉛(酸化亜鉛1種、比重5.6、平均粒径0.6μm、堺化学工業(株)製)
(G)成分:ステアリン酸カルシウム
縦50mm、横55mm、厚み0.25mmのCu製のリードフレームを準備する。リードフレームは、図14に示すフレーム単位22が縦15列、横12列にわたって平行に並んだ一体成形品である。このリードフレーム表面に厚み3μmのAgめっき層を形成し、さらにAgめっき層の表面に厚み0.005μm〜0.006μmの範囲でAuめっき層を形成した。このリードフレームの各フレーム単位22に、縦横方向の間隔を1.1mmにして樹脂成形体(リフレクター)180個を形成した。各樹脂成形体は、凹部の内部空間の形状が逆円錐台状であり、凹部開口面の径が2.1mm、凹部底部の径が1.8mm、凹部内壁面の凹部底面に対する傾斜角度が75°、高さ0.55mmであり、凹部底部の横方向直径に沿って右端から0.45mmのところに縦方向に延びる幅約0.2mmの絶縁部を有し、フレーム単位22の第1、第2リード23,24を電気的に絶縁していた。
縦50mm、横55mm、厚み0.25mmのCu製リードフレームの表面に、Auめっき層が最表面層になるように、Ni−Pd−Auの3層めっき層を形成した。Niめっき層の厚みは0.5〜2.0μmの範囲とした。Pdめっき層の厚みは0.01〜0.15μmの範囲とした。Auめっき層の厚みは0.003〜0.01μmの範囲とした。このリードフレームを用いる以外は、実施例11と同様にして、樹脂成形体の集合体を作製した。
厚みが2〜5μmの範囲であるAgめっき層を表面に形成した縦50mm、横55mm、厚み0.25mmのCu製のリードフレームを用いる以外は、実施例11と同様にして、樹脂成形体の集合体を作製した。
実施例11〜13で得られた樹脂成形体について、凹部開口面の十点平均粗さ(Rz)、ガラス転移温度(Tg)、光反射率、発光素子を実装した発光装置の初期輝度および使用したリードフレームの耐硫化性を調べた。結果を表8に示す。
上記で得られた樹脂成形体の集合体(リードフレーム付き樹脂成形体)の各凹部に、ダイボンダー装置及びエポキシ性ダイボンド剤(商品名:DX−20C、ヘンケル社製)を用いて、発光素子(商品名:B1213、Genetits社製)を接合し、ワイヤーボンダー装置により各凹部の底部に露出する第1、第2インナーリード部と発光素子とを結線した。続いて、各凹部に対し、シリコーン系封止剤(東レ・ダウコーニング社製OE6630、A剤およびB剤をそれぞれ1:4の割合で混合した透明硬化性樹脂)をディスペンサ―装置によりディスペンスし、発光素子がマウントされた部位を封止した。その後、150℃2時間のキュアを実施し、表面実装型発光装置の集合基板を得た。これを、ダイシング装置により30mm×30mmのサイズにダイシングして、個片化された表面実装型発光装置を得た。発光特性の評価は、光度測定装置を使用し、CIE127(ConditionB)に準拠して実施した。また、表面実装発光装置を通電評価用プリント基板に実装し、定電流20mAを通電しその時の初期輝度(cd:カンデラ相当)を計測した。
Agめっき、Au−AgめっきおよびAu−Pd−Niめっきを施したCu製のリードフレームの耐硫化性を次の手法で評価した。あらかじめのリードフレーム表面の光沢度(値)を計測しておいた。続いてビーカー(1L)に純水200mL、多硫化硫黄含有成分(商品名:湯の素、村上商会製)を5mL入れ、マグネチックスターラーつきヒーターで攪拌しながら80℃に加温した。それぞれのリードフレームをアクリル板に貼り付け、リードフレームがビーカーの開口部の中に入るようにふたをした。この間、硫化水素が発生してリードフレームに暴露させた。30分後ふたをはずし、リードフレームサンプルの反射濃度(BLK値)を微小面分光色差計(商品名:VSS400、日本電色工業株式会社製)を用い測定した。
個片化された表面実装型発光装置を60℃、湿度80%、硫化水素3ppmの環境下で96時間放置した。その後、該発光装置を取り出し、リードフレームの色変化(目視)および上記の手法で初期輝度を測定した。
図10に示す金型20において、第1凸部32の外周面32bを、第1凸部32の頂面32aに続く第1外周面と第1外周面に続く第2外周面とに分けた。第1外周面の頂面32aに対する傾斜角(頂面32aと第1外周面とがなす角の角度)を90°(実施例14および15)又は120°(実施例16)、第2外周面の頂面32に対する傾斜角(頂面32aと第2外周面の延長線とがなす角の角度)を140°(実施例14)又は150°(実施例15、16)とし、第1外周面と第2外周面との境界を、外周面32bにおける頂面32aから高さ100μm(実施例14、15)又は50μm(実施例16)の領域とした。なお、第1外周面と第2外周面とからなる外周面32bを有する第1凸部32と、底面32aに対する傾斜角が140°と一定である外周面32bを有する第1凸部32とを、縦横に交互に設けた。また、上側凹部33の底面33aの十点平均粗さRzを6.0μmに調整した。
第1凸部32の外周面32bを第1外周面と第2外周面とに分けず、頂面32aと外周面32bとがなす角の角度を150°(実施例17)又は140°(実施例18)とする以外は、実施例14と同様にして、MAP状リードフレーム付樹脂成形体を作製した。得られた樹脂成形体を上金型から脱型する際に、樹脂成形体の変形や界面剥離による破壊は発生しなかった。本実施例により、内壁面13bの底面13aに対する傾斜角が表9に示す値である凹部を有する樹脂成形体の集合体を得た。
1a,4a,4b,4c,4d 外側面
10,56a 第1リード
10a 第1インナーリード部、10b 第1アウターリード部
11,56b 第2リード
11a 第2インナーリード部、11b 第2アウターリード部
12,14,16,17,57 樹脂硬化体
12a 反射部、12b,17b 絶縁部、12c,17c 凹部開口面
13,15 凹部
13a 底部、13b 内壁面
18 めっき層
18a 最表面層、18b 第2金属層
20 金型
21 リードフレーム、22 フレーム単位、23 第1リード、24 第2リード
25 樹脂硬化体付リードフレーム
30 上金型、31 上側合わせ面、32 第1凸部、34 第2凸部
33 上側凹部、33a 底面
35 下金型、36 下側合わせ面
40 樹脂注入孔、41 プランジャー、42 ランナー、43 貫通孔
44 プランジャーポット、45 熱硬化性樹脂タブレットまたは液状の熱硬化性樹脂
50 表面実装型発光装置、51 発光素子
52a 第1金線、52b 第2金線
55 従来の樹脂成形体
58 樹脂バリ、59 樹脂欠け
60 第2斜面、61 第1斜面
Claims (20)
- 樹脂硬化体と複数のリードとが一体成形され、底部に前記複数のリードが露出する凹部を有する表面実装型発光装置用樹脂成形体であって、
前記凹部の開口面の十点平均粗さ(Rz)が1μm以上、10μm以下であり、
前記樹脂硬化体のガラス転移温度が10℃以上であり、前記ガラス転移温度が、熱機械分析装置(TMA)を用い、温度範囲−50〜250℃、昇温速度5℃/分および試料サイズ長1〜5mmの条件で測定された値であり、かつ、
前記凹部の開口面の460nmにおける光反射率が80%以上であり、前記樹脂成形体を180℃で72時間加熱した後の前記開口面における光反射率の保持率が90%以上である表面実装型発光装置用樹脂成形体。 - 前記樹脂硬化体の固体13C−核磁気共鳴スペクトルにおけるピークトップが、−1ppm〜2ppmおよび13ppm〜18ppmの範囲に少なくとも1つ存在する請求項1に記載の表面実装型発光装置用樹脂成形体。
- 前記樹脂硬化体が、(A)SiH基と反応性を有する炭素−炭素二重結合を1分子中に少なくとも2個含有する有機化合物、(B)1分子中に少なくとも2個のSiH基を含有する化合物、(C)ヒドロシリル化触媒、(D)SiH基と反応性を有する炭素−炭素二重結合を1分子中に少なくとも1個含有するシリコーン化合物、および(E)無機充填材を含有する熱硬化性樹脂組成物(X)の硬化物である請求項1または2に記載の表面実装型発光装置用樹脂成形体。
- 前記複数のリードの少なくとも1つがその表面に金属層を有し、前記金属層がその表面側に最表面層を有し、前記最表面層が厚み0.003〜0.05μmのAu層、Au系合金層または光沢Ni層である請求項1〜3のいずれか1項に記載の表面実装型発光装置用樹脂成形体。
- 前記金属層は、前記最表面層、および、前記リードの表面と前記最表面層との間に介在する第2金属層を有し、前記第2金属層は、Ag層、Pd層又はAg層とPd層との積層体である請求項4に記載の表面実装型発光装置用樹脂成形体。
- 前記金属層がめっき層である請求項4または5に記載の表面実装型発光装置用樹脂成形体。
- 前記凹部は、前記底部に露出する前記複数のリードの表面である底面を有し、
前記凹部の内壁面は、前記底面に連続して前記底面の周縁から立ち上がり、前記底面に対する傾斜角が45°〜90°である第2斜面と、前記第2斜面に連続して前記第2斜面の周縁から前記開口面に向けて立ち上がり、前記底面に対する傾斜角が0°を超え45°以下である第1斜面と、を含み、前記第1斜面と前記第2斜面との境界が、前記内壁面における前記底面から高さ0μmを超え100μm以下の位置にある請求項1〜6のいずれか1項に記載の表面実装型発光装置用樹脂成形体。 - 前記複数のリードは、互いに離隔するように配置される第1リードと第2リードとを含み、
前記樹脂硬化体は、前記第1リードと前記第2リードとの間に介在してこれらを絶縁する絶縁部を含み、前記絶縁部は、前記第1リードと前記第2リードとにより挟まれた状態で前記凹部の底部に露出する請求項1〜7のいずれか1項に記載の表面実装型発光装置用樹脂成形体。 - 前記第1リードは、前記凹部の底部に露出する第1インナーリード部と、前記樹脂硬化体に接触する第1アウターリード部とを含み、かつ、前記第2リードは、前記凹部の底部に露出する第2インナーリード部と、前記樹脂硬化体に接触する第2アウターリード部とを含む請求項8に記載の表面実装型発光装置用樹脂成形体。
- 外側面に、前記第1アウターリード部および/または前記第2アウターリード部が露出する請求項9に記載の表面実装型発光装置用樹脂成形体。
- 前記外側面において、前記樹脂硬化体の露出面と、前記第1アウターリード部および/または前記第2アウターリード部の露出面とが、ほぼ同一平面上に存在する請求項10に記載の表面実装型発光装置用樹脂成形体。
- 前記第1インナーリード部および前記第2インナーリード部はその表面に前記金属層を有し、前記第1アウターリード部および前記第2アウターリード部はその表面に金属層を有していない請求項9〜11のいずれか1項に記載の表面実装型発光装置用樹脂成形体。
- 前記複数のリードは、前記樹脂硬化体が充填されている切り欠き部を有する請求項1〜12のいずれか1項に記載の表面実装型発光装置用樹脂成形体。
- 樹脂硬化体と複数のリードとが一体成形され、底部に前記複数のリードが露出する凹部を有し、前記樹脂硬化体における前記凹部の開口面の十点平均粗さ(Rz)が1μm以上、10μm以下である表面実装型発光装置用樹脂成形体の製造方法であって、
(1)前記樹脂硬化体の立体形状に対応する内部空間を有し、底面の十点平均粗さ(Rz)が0.5μm以上、15μm以下である上側凹部が所定位置に形成された上側合わせ面を有する上金型と、平坦な下側合わせ面を有する下金型と、樹脂注入孔と、を備える金型を用い、前記上側合わせ面と前記下側合わせ面とにより複数のリードを挟持して固定する工程と、
(2)前記金型内における前記上側凹部と前記複数のリードおよび/または前記下側合わせ面とにより形成される内部空間に、前記樹脂注入孔から液状の熱硬化性樹脂を注入する工程と、
(3)前記金型を所定の温度に加熱することにより、前記液状の熱硬化性樹脂を硬化させて、前記複数のリードの所定位置に前記熱硬化性樹脂の硬化物からなる樹脂硬化体が一体成形された前記樹脂成形体を作製する工程と、
(4)前記金型から前記樹脂成形体を脱型する工程と、
を含む表面実装型発光装置用樹脂成形体の製造方法。 - 前記複数のリードが、互いに離隔するように配置される、第1リードと第2リードとを含み、前記工程(2)において、前記第1リードと前記第2リードとの間の空間に液状の前記熱硬化性樹脂が注入される請求項14に記載の表面実装型発光装置用樹脂成形体の製造方法。
- 前記上側凹部が前記上側合わせ面の所定位置に形成された上金型と、平坦な前記下側合わせ面を有する前記下金型と、所定の間隔を空けて縦横に切り欠き部が形成された複数のリードと、を用いることにより、前記複数のリードの前記切り欠き部で囲まれた領域毎に前記樹脂硬化体を形成し、次いで前記切り欠き部に沿って前記複数のリードを切断することにより、複数個の前記樹脂成形体を得る請求項14または15に記載の表面実装型発光装置用樹脂成形体の製造方法。
- 前記複数のリードの少なくとも1つは表面に金属層を有している請求項16に記載の表面実装型発光装置用樹脂成形体の製造方法。
- 前記複数のリードの前記切り欠き部が、前記上側合わせ面の前記上側凹部が形成されていない領域と、前記下側合わせ面と、により挟持される請求項16または17に記載の表面実装型発光装置用樹脂成形体の製造方法。
- 請求項1〜13のいずれか1項に記載の表面実装型発光装置用樹脂成形体と、前記樹脂成形体の凹部底部に実装され、複数のリードと通電可能に接続される発光素子と、前記発光素子を封止する透明樹脂層と、を備える表面実装型発光装置。
- 複数個の前記発光素子が実装される請求項19に記載の表面実装型発光装置。
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