JP2018090770A - Transparent epoxy resin composition and optical semiconductor device - Google Patents
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 66
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 66
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 239000004065 semiconductor Substances 0.000 title claims abstract description 17
- 230000003287 optical effect Effects 0.000 title claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 18
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003566 sealing material Substances 0.000 claims abstract description 10
- 239000002530 phenolic antioxidant Substances 0.000 claims description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 3
- 229930185605 Bisphenol Natural products 0.000 claims 1
- 238000004383 yellowing Methods 0.000 abstract description 14
- 239000000126 substance Substances 0.000 description 23
- 239000011342 resin composition Substances 0.000 description 14
- 239000003963 antioxidant agent Substances 0.000 description 13
- 230000003078 antioxidant effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 150000008301 phosphite esters Chemical class 0.000 description 8
- 229910000679 solder Inorganic materials 0.000 description 8
- 238000007789 sealing Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 238000012423 maintenance Methods 0.000 description 6
- 230000002950 deficient Effects 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 101001014562 Homo sapiens Male-specific lethal 3 homolog Proteins 0.000 description 4
- 102100032515 Male-specific lethal 3 homolog Human genes 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000003635 deoxygenating effect Effects 0.000 description 3
- 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 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- -1 alicyclic acid anhydrides Chemical class 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Natural products CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 1
- HLBZWYXLQJQBKU-UHFFFAOYSA-N 4-(morpholin-4-yldisulfanyl)morpholine Chemical compound C1COCCN1SSN1CCOCC1 HLBZWYXLQJQBKU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Led Device Packages (AREA)
Abstract
Description
本発明は、はんだ耐熱性に優れ、かつ高温放置耐熱性に優れた透明エポキシ樹脂組成物および該透明エポキシ樹脂組成物を封止材として用いた光半導体装置に関する。 The present invention relates to a transparent epoxy resin composition excellent in solder heat resistance and excellent in high temperature storage heat resistance, and an optical semiconductor device using the transparent epoxy resin composition as a sealing material.
電子部品の封止用途として使用されているエポキシ樹脂組成物は、そのままでは熱による黄変により色味が変わりやすいため、一般にはカーボンブラックなどの濃い色の着色材を添加して、樹脂組成物としての黄変を分かりにくくしている。 Epoxy resin compositions used for sealing electronic components are easy to change in color due to yellowing due to heat, so generally add a dark colorant such as carbon black to add resin composition It is difficult to understand the yellowing.
着色材を含まない透明樹脂組成物や淡色系の樹脂組成物においては、熱による黄変抑制には酸化防止剤の添加が必須である。ところで、その汎用性の高さから、エポキシ樹脂の酸化防止剤として幅広く使用されているフェノール系の酸化防止剤は、その酸化防止の性能が完璧とは言い難く、特に、電子部品の組立工程における高温短時間のベークや、２６０℃はんだ実装時に黄変が起こってしまうという欠点があった。 In a transparent resin composition or a light-colored resin composition that does not contain a colorant, it is essential to add an antioxidant to suppress yellowing due to heat. By the way, because of its versatility, phenolic antioxidants that are widely used as antioxidants for epoxy resins are not perfect for their antioxidant performance, especially in the assembly process of electronic components. There was a drawback that yellowing occurred during high-temperature short-time baking or 260 ° C. solder mounting.
そのため、酸化防止剤の添加量を増やす必要があるが、酸化防止剤の添加量を増やすと成形性の悪化や信頼性の低下を招くばかりでなく、酸化防止剤自身の黄変が目立ちやすくなり、耐光性も劣化する欠点があった。 Therefore, it is necessary to increase the amount of addition of the antioxidant, but increasing the amount of addition of the antioxidant not only deteriorates the moldability and decreases the reliability, but also makes the antioxidant itself noticeable. The light resistance also deteriorated.
また、電子部品には様々な熱膨張係数を有する構成材料で組立を行うため、その熱膨張係数差から、電子部品の組立工程やはんだ実装、さらには実使用時に材料間での剥離を生じさせないため、樹脂材料には密着付与剤を添加することが一般的である。 In addition, because electronic parts are assembled with component materials having various thermal expansion coefficients, the difference in thermal expansion coefficient does not cause separation between materials during the assembly process of electronic parts, solder mounting, and actual use. Therefore, it is common to add an adhesion-imparting agent to the resin material.
密着付与剤としては、表面の濡れ性を向上させるための相溶化剤、密着を保持するための低応力剤もある程度の効果があるが、化学的に密着させる密着付与剤は非常に効果が高い。そのため、特に近年、腐食抑制のために貴金属にてめっきされたリードフレームでの剥離抑制には、樹脂材料への化学的密着付与剤の添加が不可欠となっている。特に、透明樹脂組成物で封止された電子部品では、剥離があると超音波探傷装置などを用いなくても肉眼で確認できるため、その重要性がより高いものになっている。 As the adhesion-imparting agent, a compatibilizing agent for improving the wettability of the surface and a low-stress agent for maintaining the adhesion have some effects, but the adhesion-imparting agent for chemically adhering is very effective. . Therefore, especially in recent years, it is indispensable to add a chemical adhesion imparting agent to the resin material in order to suppress peeling in a lead frame plated with a noble metal in order to suppress corrosion. In particular, an electronic component sealed with a transparent resin composition is more important because it can be confirmed with the naked eye without using an ultrasonic flaw detector or the like when it is peeled off.
しかし、フェノール系の酸化防止剤のみを添加する従来の処方では剥離の抑制効果はなく、特に貴金属にてめっきされたリードフレームにはモールド後に剥離するものさえあった。 However, the conventional formulation in which only the phenolic antioxidant is added does not have an effect of suppressing peeling, and in particular, a lead frame plated with a noble metal even peels after molding.
そのため、貴金属に対する密着付与剤として、ジスルフィド結合（Ｓ−Ｓ結合）を含有する化合物の添加などが検討されている。このジスルフィド結合（Ｓ−Ｓ結合）を含有する化合物は、少量の添加で密着力の向上が期待できるものの、パッケージあたりの貴金属めっきの面積が大きくなると、やはり剥離が生じてしまう傾向にある。 Therefore, addition of a compound containing a disulfide bond (S—S bond) has been studied as an adhesion promoter for noble metals. Although the compound containing this disulfide bond (SS bond) can be expected to improve adhesion when added in a small amount, peeling tends to occur when the area of the precious metal plating per package increases.
これに対して、ジスルフィド結合（Ｓ−Ｓ結合）を含有する化合物の添加量を増やすことで剥離抑制効果を向上できるものの、この場合、それと同時に硬化直後の材料であっても黄色みを帯びてきてしまう問題がある。この黄変は、Ｓ−Ｓ結合を含有する化合物自体が濃い黄色であるために生じる現象であり、透明樹脂に用いる場合、所定以上に添加量を増やすことができない。 On the other hand, although the peeling suppression effect can be improved by increasing the amount of the compound containing a disulfide bond (SS bond), in this case, the material immediately after curing becomes yellowish at the same time. There is a problem. This yellowing is a phenomenon that occurs because the compound containing an S—S bond itself is a deep yellow color, and when used in a transparent resin, the amount added cannot be increased beyond a predetermined level.
また、Ｓ−Ｓ結合を含有する化合物は、樹脂組成物の硬化性を低下させてしまうことがしばしばあり、そのために硬化促進剤を増やすと、これもまた黄変の原因となってしまうことがあった。 In addition, a compound containing an SS bond often reduces the curability of the resin composition. For this reason, when the curing accelerator is increased, this may also cause yellowing. there were.
そこで、本発明は、上記問題を解消しようとなされたものである。
従って、本発明の目的は、リードフレームや部材との密着性に優れ、熱による黄変などが抑制された透明エポキシ樹脂組成物、およびその硬化物を封止材として用いた光半導体装置を提供しようとするものである。
Accordingly, the present invention has been made to solve the above problems.
Accordingly, an object of the present invention is to provide a transparent epoxy resin composition that has excellent adhesion to a lead frame and a member and is suppressed from yellowing due to heat, and an optical semiconductor device using the cured product as a sealing material. It is something to try.
本発明者らは、上記の目的を達成しようと鋭意研究を重ねた結果、ジスルフィド結合（Ｓ−Ｓ結合）を含有する化合物を少量添加するとともに、亜リン酸エステルを用いることにより、高密着性の発現および黄変の抑制が両立できることを見出し、本発明を完成させたものである。 As a result of intensive research aimed at achieving the above object, the present inventors have added a small amount of a compound containing a disulfide bond (SS bond), and by using a phosphite ester, And the present invention has been completed.
すなわち、本発明の透明エポキシ樹脂組成物は、（Ａ）透明エポキシ樹脂と、（Ｂ）酸無水物硬化剤と、（Ｃ）硬化促進剤と、（Ｄ）ジスルフィド結合を含有する化合物と、（Ｅ）亜リン酸エステルと、を必須成分として含有することを特徴とする。 That is, the transparent epoxy resin composition of the present invention comprises (A) a transparent epoxy resin, (B) an acid anhydride curing agent, (C) a curing accelerator, (D) a compound containing a disulfide bond, E) Phosphite ester is contained as an essential component.
本発明の光半導体装置は、基板上に設けられた光半導体素子と、前記光半導体素子を本発明の透明エポキシ樹脂組成物の硬化物により封止した封止材と、を有することを特徴とする。 An optical semiconductor device of the present invention includes an optical semiconductor element provided on a substrate, and a sealing material in which the optical semiconductor element is sealed with a cured product of the transparent epoxy resin composition of the present invention. To do.
本発明の透明エポキシ樹脂組成物によれば、熱による黄変が抑制され、耐光性に優れた硬化物を得ることができ、特に、光半導体の封止材料として好適な樹脂組成物を提供できる。この透明エポキシ樹脂組成物を封止材料として用いることで得られる光半導体装置は、その製造後の封止部の剥離を有効に抑制でき、信頼性の高い装置となる。 According to the transparent epoxy resin composition of the present invention, yellowing due to heat is suppressed, and a cured product excellent in light resistance can be obtained, and in particular, a resin composition suitable as a sealing material for optical semiconductors can be provided. . An optical semiconductor device obtained by using this transparent epoxy resin composition as a sealing material can effectively suppress peeling of the sealing portion after the manufacture, and becomes a highly reliable device.
本発明の透明エポキシ樹脂組成物は、上記の通り、（Ａ）透明エポキシ樹脂と、（Ｂ）酸無水物硬化剤と、（Ｃ）硬化促進剤と、（Ｄ）ジスルフィド結合（Ｓ−Ｓ結合）を含有する化合物と、（Ｅ）亜リン酸エステルと、を必須成分として含有するものである。以下、本発明の透明エポキシ樹脂組成物を構成する各成分について詳細に説明する。 As described above, the transparent epoxy resin composition of the present invention comprises (A) a transparent epoxy resin, (B) an acid anhydride curing agent, (C) a curing accelerator, and (D) a disulfide bond (SS bond). ) And a compound containing (E) phosphite as essential components. Hereinafter, each component which comprises the transparent epoxy resin composition of this invention is demonstrated in detail.
本発明に用いる（Ａ）透明エポキシ樹脂は、その分子中にエポキシ基を少なくとも２個有する化合物であり、硬化させた際、透明性の硬化物が得られるエポキシ樹脂である。この（Ａ）透明エポキシ樹脂は、このような特性を有するものであれば、分子構造および分子量など特に制限はなく、一般に封止用材料として使用されるものを広く包含することができる。この（Ａ）透明エポキシ樹脂としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、ｏ−クレゾールノボラック型エポキシ樹脂、多官能エポキシ樹脂、脂環式エポキシ樹脂、シリコーンハイブリッドエポキシ樹脂などが挙げられる。このうちビスフェノールＦ型エポキシ樹脂は成形品の吸湿処理後のはんだ耐熱性が優れる。この（Ａ）透明エポキシ樹脂は、１つを単独又は２つ以上を混合して用いることもでき、さらに、その他の公知のエポキシ樹脂を併用することもできる。多官能エポキシ樹脂を併用することにより半田耐熱性を向上させることができる。 The (A) transparent epoxy resin used in the present invention is a compound having at least two epoxy groups in the molecule, and is a epoxy resin that can obtain a transparent cured product when cured. If this (A) transparent epoxy resin has such a characteristic, there will be no restriction | limiting in particular in molecular structure and molecular weight, and what is generally used as a sealing material can be included widely. Examples of the transparent epoxy resin (A) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, o-cresol novolac type epoxy resin, polyfunctional epoxy resin, and alicyclic epoxy resin. And silicone hybrid epoxy resin. Among these, the bisphenol F type epoxy resin has excellent solder heat resistance after moisture absorption treatment of the molded product. This (A) transparent epoxy resin can be used alone or in combination of two or more, and other known epoxy resins can be used in combination. Solder heat resistance can be improved by using a polyfunctional epoxy resin in combination.
本発明に用いる（Ｂ）酸無水物硬化剤は、（Ａ）透明エポキシ樹脂の硬化剤としての作用を有する酸無水物である。この（Ｂ）酸無水物硬化剤としては、従来公知の酸無水物が挙げられ、例えば、脂環式酸無水物、脂肪族酸無水物、芳香族酸無水物などが挙げられる。この（Ｂ）酸無水物硬化剤は、１つを単独又は２つ以上を混合して用いることもでき、さらに、その他の公知の酸無水物硬化剤を併用することもできる。 The (B) acid anhydride curing agent used in the present invention is an acid anhydride having an action as a curing agent for the (A) transparent epoxy resin. Examples of the (B) acid anhydride curing agent include conventionally known acid anhydrides such as alicyclic acid anhydrides, aliphatic acid anhydrides, and aromatic acid anhydrides. One (B) acid anhydride curing agent can be used alone, or two or more can be used in combination, and other known acid anhydride curing agents can be used in combination.
（Ａ）透明エポキシ樹脂と（Ｂ）酸無水物硬化剤の質量比は、それぞれの当量を考慮して決定することができ、（酸無水物硬化剤の配合量／酸無水物硬化剤の当量）／（エポキシ樹脂の配合量／エポキシ樹脂の当量）が、好ましくは１．０〜１．２の範囲である。１．０以上であれば硬化物の透明性が良好であるため輝度が低下することなく、１．２以下であればガラス転移温度が低くなることなく、硬化性が良好である。 The mass ratio of (A) transparent epoxy resin and (B) acid anhydride curing agent can be determined in consideration of the equivalents of each, and (the amount of acid anhydride curing agent / equivalent of acid anhydride curing agent) ) / (Blended amount of epoxy resin / equivalent amount of epoxy resin) is preferably in the range of 1.0 to 1.2. If it is 1.0 or more, the transparency of the cured product is good, so the luminance does not decrease. If it is 1.2 or less, the glass transition temperature does not decrease and the curability is good.
本発明に用いる（Ｃ）硬化促進剤は、上記した（Ａ）透明エポキシ樹脂と（Ｂ）酸無水物硬化剤との硬化系に使用される硬化促進剤である。この（Ｃ）硬化促進剤としては、従来公知の硬化促進剤が挙げられ、不純物濃度が低いものが好ましい。この硬化促進剤としては、例えば、Ｕ−ＣＡＴなどの公知のＤＢＵ系硬化促進剤、イミダゾール系硬化促進剤、リン系硬化促進剤などが挙げられる。この（Ｃ）硬化促進剤は、１つを単独又は２つ以上を混合して用いることもでき、さらに、その他の硬化促進剤を併用することもできる。 The (C) curing accelerator used in the present invention is a curing accelerator used in the curing system of the above-described (A) transparent epoxy resin and (B) acid anhydride curing agent. As this (C) hardening accelerator, a conventionally well-known hardening accelerator is mentioned, A thing with a low impurity concentration is preferable. As this hardening accelerator, well-known DBU type hardening accelerators, such as U-CAT, an imidazole type hardening accelerator, a phosphorus hardening accelerator, etc. are mentioned, for example. This (C) hardening accelerator can also be used individually or in mixture of 2 or more, Furthermore, other hardening accelerators can also be used together.
この（Ｃ）硬化促進剤の使用量は、樹脂組成物中、好ましくは０．１〜１．０質量％である。硬化促進剤の使用割合量が０．１質量％以上であれば、透明樹脂組成物の硬化時間を短縮することできる。また、硬化促進剤の使用割合が１．０質量％以下であれば、適度な流動性となるため充填性が良好となり、常温においても可使時間が短すぎることがない。 The amount of the (C) curing accelerator used is preferably 0.1 to 1.0% by mass in the resin composition. If the usage-amount amount of a hardening accelerator is 0.1 mass% or more, the hardening time of a transparent resin composition can be shortened. Moreover, if the usage-amount of a hardening accelerator is 1.0 mass% or less, since it becomes moderate fluidity | liquidity, a filling property will become favorable and a pot life will not be too short also at normal temperature.
本発明に用いる（Ｄ）ジスルフィド結合（Ｓ−Ｓ結合）を含有する化合物は、ジスルフィド結合を有する有機化合物であればよく、この有機化合物のＳ−Ｓ結合の比率は、２０〜４０％が好ましい。なお、ここでＳ−Ｓ比率とは、分子量あたりのＳ−Ｓ結合に関与する硫黄原子の質量の比率である。この（Ｄ）ジスルフィド結合（Ｓ−Ｓ結合）を含有する化合物としては、例えば、次の化学式で表される化合物が挙げられる。 The compound containing (D) disulfide bond (SS bond) used in the present invention may be an organic compound having a disulfide bond, and the ratio of SS bond of this organic compound is preferably 20 to 40%. . Here, the S—S ratio is the ratio of the mass of sulfur atoms involved in the S—S bond per molecular weight. Examples of the compound containing (D) a disulfide bond (SS bond) include compounds represented by the following chemical formula.
この（Ｄ）ジスルフィド結合（Ｓ−Ｓ結合）を含有する化合物は、不純物濃度が低く色味が薄いものの方が良い。また、その配合割合は、樹脂組成物全体に対して０．０１〜０．３質量％であり、好ましくは０．０２〜０．２質量％である。その割合が０．０１質量％未満では密着性の向上効果に劣り、０．３質量％を超えると硬化直後に黄色みを帯びるため好ましくない。 The compound containing the (D) disulfide bond (SS bond) is preferably a compound having a low impurity concentration and a light color. Moreover, the mixture ratio is 0.01-0.3 mass% with respect to the whole resin composition, Preferably it is 0.02-0.2 mass%. If the ratio is less than 0.01% by mass, the effect of improving the adhesiveness is inferior, and if it exceeds 0.3% by mass, it becomes yellowish immediately after curing.
ジスルフィド結合（Ｓ−Ｓ結合）を有する化合物として、分子量あたり、または繰り返し単位あたりのＳ−Ｓ結合の比率が高く、本発明に用いるエポキシ樹脂や酸無水物の少なくともいずれかと相溶性のあるものが好ましい。 As a compound having a disulfide bond (SS bond), a compound having a high ratio of SS bond per molecular weight or per repeating unit and compatible with at least one of the epoxy resin and acid anhydride used in the present invention. preferable.
例えば上記［化１］で表される化合物は分子量が２９７であるため、Ｓ−Ｓ結合の比率としては、３２×２÷２９７×１００≒２１．５となり、２１．５％と算出される。
また、上記［化２］で表される化合物は分子量が３８５であるため、Ｓ−Ｓ結合の比率としては、テトラスルフィドとして計算され、３２×４÷３８５×１００≒３３．２となり、３３．２％と算出される。
For example, since the compound represented by [Chemical Formula 1] has a molecular weight of 297, the S—S bond ratio is 32 × 2 ÷ 297 × 100≈21.5, which is calculated as 21.5%.
Further, since the compound represented by [Chemical Formula 2] has a molecular weight of 385, the S—S bond ratio is calculated as tetrasulfide and becomes 32 × 4 ÷ 385 × 100≈33.2. Calculated as 2%.
このＳ−Ｓ結合の比率としては、２０〜４０％程度が良く、低すぎると貴金属に対する密着付与剤としての効果が期待できず、高すぎると樹脂成分と相溶性が低くなる傾向にある。中でも、４，４’−ジチオジモルホリン、スルフィドカップリング剤はＳ−Ｓ結合の貴金属面への配位し易さから密着性の向上と、エポキシ樹脂への相溶性の両面で優れている。 The S—S bond ratio is preferably about 20 to 40%. If it is too low, the effect as an adhesion-imparting agent for noble metals cannot be expected, and if it is too high, the compatibility with the resin component tends to be low. Among these, 4,4'-dithiodimorpholine and sulfide coupling agents are excellent in both adhesion and compatibility with epoxy resins because of the ease of coordination of SS bonds to the noble metal surface.
本発明に用いる（Ｅ）亜リン酸エステルは、脱酸素効果のある酸化防止剤として使用される亜リン酸の３個の水素が有機基で置換された化合物であり、例えば、リン原子にアルコキシル基、フェノキシ基等が結合した化合物が挙げられる。この（Ｅ）亜リン酸エステルとしては、例えば、次の化学式で表されるものが挙げられる。 The (E) phosphite used in the present invention is a compound in which three hydrogen atoms of phosphorous acid used as an antioxidant having a deoxygenating effect are substituted with an organic group. A compound having a group, a phenoxy group or the like bonded thereto. Examples of this (E) phosphite include those represented by the following chemical formula.
この（Ｅ）亜リン酸エステルとしては、不純物濃度が低いものが好ましい。（Ｅ）亜リン酸エステルは、１つを単独で又は２つ以上を混合して用いることができる。また、（Ｅ）亜リン酸エステルの融点は１５０℃以下が好ましい。この融点が１５０℃を超える場合、分解温度が高くなるために黄変抑制の効果が出にくくなる傾向がある。 As this (E) phosphite, one having a low impurity concentration is preferable. (E) Phosphite ester can be used alone or in combination of two or more. The melting point of (E) phosphite is preferably 150 ° C. or lower. When this melting point exceeds 150 ° C., the decomposition temperature tends to be high, so that the effect of suppressing yellowing tends to be difficult to obtain.
この（Ｅ）亜リン酸エステルは、脱酸素作用により、ラジカルを安定化させる作用があるが、密着付与についても、この脱酸素作用は重要な役割を果たしている。具体的には、酸化されることで表面が不活性になっている被着部材から、脱酸素作用により部材表面を活性にするため、密着力の向上効果が出るものである。 This (E) phosphite has an action of stabilizing radicals by a deoxygenating action, but this deoxygenating action also plays an important role in providing adhesion. Specifically, since the surface of the member is activated by the deoxidation action from the adherent member whose surface is inactivated by being oxidized, the effect of improving the adhesion is obtained.
この（Ｅ）亜リン酸エステルの配合割合は、樹脂組成物全体において０．０５〜３質量％であり、好ましくは０．１〜２質量％である。その配合割合が０．０５質量％未満では密着性の向上効果および黄変抑制効果に劣り、３質量％を超えると硬化時に表面ブリードが発生するため好ましくない。 The blending ratio of (E) phosphite is 0.05 to 3% by mass, preferably 0.1 to 2% by mass in the entire resin composition. If the blending ratio is less than 0.05% by mass, the adhesion improving effect and the yellowing suppressing effect are inferior, and if it exceeds 3% by mass, surface bleeding occurs during curing, which is not preferable.
本発明に用いる（Ｆ）フェノール系酸化防止剤は、樹脂組成物中に添加される公知のフェノール系酸化防止剤が挙げられ、好ましくは融点が１５０℃以下である。（Ｆ）酸化防止剤が機能するためには、酸化防止剤自身が分解されなければならないが、融点が高すぎるとその機構が働かなくなるためである。 The (F) phenolic antioxidant used in the present invention includes known phenolic antioxidants added to the resin composition, and preferably has a melting point of 150 ° C. or lower. (F) For the antioxidant to function, the antioxidant itself must be decomposed, but if the melting point is too high, the mechanism will not work.
この（Ｆ）フェノール系酸化防止剤としては、不純物濃度が低いものが好ましく、例えば、次の化学式に示す公知のフェノール系酸化防止剤化合物が挙げられる。 As this (F) phenolic antioxidant, the thing with low impurity concentration is preferable, For example, the well-known phenolic antioxidant compound shown to following Chemical formula is mentioned.
この（Ｆ）フェノール系酸化防止剤は、１つを単独でまたは２つ以上を混合して用いてもよい。さらに、その他の公知のフェノール系酸化防止剤を併用することもできる。 This (F) phenolic antioxidant may be used alone or in admixture of two or more. Furthermore, other known phenolic antioxidants can be used in combination.
この（Ｆ）フェノール系酸化防止剤の配合割合は、樹脂組成物全体において、０．０５〜３質量％であり、好ましくは０．１〜２質量％である。その割合が０．０５質量％未満では密着性の向上効果および黄変抑制効果に劣り、３質量％を超えると硬化時に表面ブリードが発生するため好ましくない。 The blending ratio of the (F) phenolic antioxidant is 0.05 to 3% by mass, preferably 0.1 to 2% by mass in the entire resin composition. If the ratio is less than 0.05% by mass, the adhesion improving effect and the yellowing suppressing effect are inferior, and if it exceeds 3% by mass, surface bleeding occurs during curing, which is not preferable.
本発明の透明エポキシ樹脂組成物は、上述した（Ａ）透明エポキシ樹脂、（Ｂ）酸無水物硬化剤、（Ｃ）硬化促進剤、（Ｄ）ジスルフィド結合（Ｓ−Ｓ結合）を含有する化合物、（Ｅ）亜リン酸エステル、を必須成分とするが、本発明の目的に反しない限度において、また必要に応じて、（Ｆ）フェノール系酸化防止剤や、例えば、天然ワックス類、合成ワックス類等の離型剤、ゴム系やシリコーン系ポリマーの低応力付与剤、アミン変性およびエポキシ変性シリコーンオイル等のカップリング剤、染料または顔料などの淡色着色材、反応性または非反応性の希釈剤等を適宜添加配合することができる。 The transparent epoxy resin composition of the present invention comprises (A) a transparent epoxy resin, (B) an acid anhydride curing agent, (C) a curing accelerator, and (D) a compound containing a disulfide bond (SS bond). (E) Phosphite ester is an essential component, but as long as it does not contradict the purpose of the present invention, and if necessary, (F) a phenolic antioxidant, for example, natural wax, synthetic wax Release agents such as rubber, low stress imparting agents for rubber and silicone polymers, coupling agents such as amine-modified and epoxy-modified silicone oils, light colorants such as dyes or pigments, reactive or non-reactive diluents Etc. can be suitably added and blended.
本発明の透明エポキシ樹脂組成物を常温で固形の封止材料として調製する場合、その方法は従来公知の方法で行えばよい。このような方法としては、例えば、上述した（Ａ）透明エポキシ樹脂、（Ｂ）酸無水物硬化剤、（Ｃ）硬化促進剤、（Ｄ）ジスルフィド結合（Ｓ−Ｓ結合）を含有する化合物、（Ｅ）亜リン酸エステル、（Ｆ）フェノール系酸化防止剤、およびその他の成分を、それぞれ配合し、ロールまたはニーダ等により加熱溶融混合処理を行い、ついで冷却固化させ、固化した透明エポキシ樹脂組成物を適当な大きさに粉砕する方法が挙げられる。この方法によって、所望の特性を有する封止が可能な封止材料を得ることができる。 When preparing the transparent epoxy resin composition of this invention as a solid sealing material at normal temperature, the method should just be performed by a conventionally well-known method. As such a method, for example, (A) transparent epoxy resin, (B) acid anhydride curing agent, (C) curing accelerator, (D) a compound containing a disulfide bond (SS bond), (E) Phosphite ester, (F) Phenol antioxidant, and other components are blended, heated and mixed with a roll or kneader, etc., then cooled and solidified, and solidified transparent epoxy resin composition There is a method of pulverizing an object to an appropriate size. By this method, a sealing material capable of being sealed having desired characteristics can be obtained.
本発明の透明エポキシ樹脂組成物は、各種電気部品、又は半導体素子等の各種電子部品の、被覆、絶縁、封止等に用いることができる。この透明エポキシ樹脂組成物の硬化は、従来公知の方法により行えばよい。なお、ここで得られる硬化物は、透明な硬化物であり、本明細書において「透明」とは、１ｍｍ厚の試験片において、可視光の波長領域３８０〜７８０ｎｍの間のいずれかの波長帯で透過率が７０％以上である状態を言う。 The transparent epoxy resin composition of the present invention can be used for coating, insulation, sealing and the like of various electric parts or various electronic parts such as semiconductor elements. The transparent epoxy resin composition may be cured by a conventionally known method. In addition, the hardened | cured material obtained here is a transparent hardened | cured material, and "transparent" in this specification is a 1 mm-thick test piece, and is any wavelength range between wavelength regions 380-780 nm of visible light. And the transmittance is 70% or more.
また、本発明の光半導体装置は、基板上に固定した光半導体素子を、上記の材料を用いて封止することにより、容易に製造することができる。封止の一般的な方法としては、トランスファー成形、射出成形、圧縮成形、などが挙げられ、金型とプレス装置を用いた成形方法の場合は、必要に応じて真空成形することにより隙間の充填性向上やボイドを低減させることができる。封止および後硬化の温度は１５０℃以上にすることが望ましい。 In addition, the optical semiconductor device of the present invention can be easily manufactured by sealing an optical semiconductor element fixed on a substrate using the above material. General methods of sealing include transfer molding, injection molding, compression molding, etc. In the case of a molding method using a mold and a press device, filling the gap by vacuum forming as necessary. Property improvement and voids can be reduced. The temperature for sealing and post-curing is desirably 150 ° C. or higher.
次に、本発明を実施例および比較例によって説明するが、本発明はこれら実施例によって限定されるものではない。以下の実施例および比較例において「部」とは「質量部」を意味する。 Next, although an example and a comparative example explain the present invention, the present invention is not limited by these examples. In the following Examples and Comparative Examples, “part” means “part by mass”.
（実施例１）
エポキシ樹脂として、ビスフェノールＡ型エポキシ樹脂（商品名：ｊＥＲ１００１、三菱化学（株）製） ４１．５部およびトリアジン骨格含有エポキシ樹脂（商品名：ＴＥＰＩＣ−Ｓ、日産化学工業（株）製） １５．０部、酸無水物硬化剤（商品名：リカシッドＴＨ；新日本理化（株）製） ４０．０部、硬化促進剤（商品名：ＵＣＡＴ５００３、サンアプロ（株）製） ０．４部、ジスルフィド結合含有化合物１（商品名：ＡＣＴＯＲ−Ｒ、川口化学工業（株）製；［化３］に記載の化合物） ０．１部、亜リン酸エステル１（商品名：ＪＰ−３６０、城北化学工業（株）製；［化５］に記載の化合物） ０．１部、フェノール系酸化防止剤１（商品名：ＢＨＴ、東京化成工業（株）製の試薬；［化１０］に記載の化合物） ０．５部、ヒドロキシステアリン酸（商品名：ＫＯＷ、川研ファインケミカル（株）製） ２．０部、を常温で混合し、エポキシ樹脂組成物を得た。このエポキシ樹脂組成物を、さらに７０〜１００℃で混練した後、これを冷却、固化し、粉砕して封止用の成形材料を製造した。
Example 1
As epoxy resin, 41.5 parts of bisphenol A type epoxy resin (trade name: jER1001, manufactured by Mitsubishi Chemical Corporation) and triazine skeleton-containing epoxy resin (trade name: TEPIC-S, manufactured by Nissan Chemical Industries, Ltd.) 15. 0 parts, acid anhydride curing agent (trade name: Ricacid TH; manufactured by Shin Nippon Rika Co., Ltd.) 40.0 parts, curing accelerator (trade name: UCAT5003, manufactured by San Apro Co., Ltd.) 0.4 part, disulfide bond Containing compound 1 (trade name: ACTOR-R, manufactured by Kawaguchi Chemical Industry Co., Ltd .; compound described in [Chemical Formula 3]) 0.1 part, phosphite 1 (trade name: JP-360, Johoku Chemical Industry ( Manufactured by Co., Ltd .; compound described in [Chemical Formula 5]) 0.1 part, phenolic antioxidant 1 (trade name: BHT, reagent manufactured by Tokyo Chemical Industry Co., Ltd .; compound described in Chemical Formula 10) 0 .5 parts, hydroxy 2.0 parts of stearic acid (trade name: KOW, manufactured by Kawaken Fine Chemical Co., Ltd.) was mixed at room temperature to obtain an epoxy resin composition. The epoxy resin composition was further kneaded at 70 to 100 ° C., and then cooled, solidified, and pulverized to produce a molding material for sealing.
こうして製造した成形材料を用いてトランスファー成形機により１６５℃に加熱した金型内で２分間成形し、さらに１５０℃で２時間アフターキュアして試験成形品を得た。 The molding material thus produced was molded in a mold heated to 165 ° C. by a transfer molding machine for 2 minutes, and further aftercured at 150 ° C. for 2 hours to obtain a test molded product.
（実施例２〜１２、比較例１〜４）
表１〜３に示した原料および含有割合とした以外は、実施例１と同様の操作により、各例において、エポキシ樹脂組成物、成形材料および試験成形品を製造した。ここで使用した原料は、以下の通りである。
(Examples 2 to 12, Comparative Examples 1 to 4)
Except for the raw materials and content ratios shown in Tables 1 to 3, an epoxy resin composition, a molding material, and a test molded article were produced in the same manner as in Example 1 by the same operation. The raw materials used here are as follows.
（Ａ）成分
・ビスフェノールＦ型エポキシ樹脂（商品名：ｊＥＲ４００４Ｐ、三菱化学（株）製）
（Ｄ）成分
・ジスルフィド結合含有化合物２（商品名：ＫＢＥ−８４６、信越化学工業（株）製；［化４］に記載の化合物）
（Ｅ）成分
・亜リン酸エステル２（商品名：ＰＥＰ−８、（株）ＡＤＥＫＡ製；［化７］に記載の化合物）
・亜リン酸エステル３（商品名：ＪＰＰ−１００、城北化学工業（株）製；［化８］に記載の化合物）
・亜リン酸エステル４（商品名：ＪＰ−６５０、城北化学工業（株）製；［化９］に記載の化合物）
（Ｆ）成分
・フェノール系酸化防止剤２（商品名：ＩＲＧＡＮＯＸ １０１０、ＢＡＳＦ社製；［化１４］に記載の化合物）
・フェノール系酸化防止剤３（商品名：ＡＯ−４０、（株）ＡＤＥＫＡ製；［化１５］に記載の化合物）
その他成分
・ヒドロキシステアリン酸（商品名：ＫＯＷ、川研ファインケミカル（株）製；離型剤）
・ＤＯＰＯ（商品名：ＥＰＯＣＬＥＡＮ、三光（株）製；酸化防止剤）
(A) Component / Bisphenol F type epoxy resin (trade name: jER4004P, manufactured by Mitsubishi Chemical Corporation)
Component (D) Compound 2 containing disulfide bond (trade name: KBE-846, manufactured by Shin-Etsu Chemical Co., Ltd .; compound described in [Chemical Formula 4])
Component (E) Phosphite ester 2 (trade name: PEP-8, manufactured by ADEKA Corporation; compound described in [Chemical Formula 7])
Phosphite 3 (trade name: JPP-100, manufactured by Johoku Chemical Industry Co., Ltd .; compound described in [Chemical Formula 8])
Phosphite ester 4 (trade name: JP-650, manufactured by Johoku Chemical Industry Co., Ltd .; compound described in [Chemical 9])
Component (F): Phenol antioxidant 2 (trade name: IRGANOX 1010, manufactured by BASF; compound described in [Chemical Formula 14])
Phenol antioxidant 3 (trade name: AO-40, manufactured by ADEKA Corporation; compound described in [Chemical 15])
Other ingredients ・ Hydroxystearic acid (trade name: KOW, manufactured by Kawaken Fine Chemical Co., Ltd .; mold release agent)
・ DOPO (trade name: EPOCLEAN, manufactured by Sanko Co., Ltd .; antioxidant)
（試験例）
実施例１〜１２および比較例１〜４で得られた試験成形品について、透過率、密着力、はんだ耐熱性、輝度維持率について、次の通り試験を行い、その結果を表１〜３に併せて示した。
(Test example)
About the test molded article obtained in Examples 1-12 and Comparative Examples 1-4, it tested as follows about the transmittance | permeability, adhesive force, solder heat resistance, and a brightness maintenance factor, and the result is shown to Tables 1-3. Also shown.
（透過率）
樹脂組成物を１６５℃×２分（硬化条件）で硬化させ、厚さ１．０ｍｍの成形品を形成した。１．０ｍｍ厚成形品を分光光度計（Ｊａｓｃｏ製、商品名：Ｖ−５７０）によって４６０ｎｍ波長の透過率を測定した。
また、この１．０ｍｍ厚成形品を、１５０℃、１６８時間処理後、同様に４６０ｎｍ波長の透過率を測定した。
(Transmittance)
The resin composition was cured at 165 ° C. for 2 minutes (curing conditions) to form a molded product having a thickness of 1.0 mm. The transmittance at a wavelength of 460 nm was measured on a 1.0 mm-thick molded product using a spectrophotometer (Jasco, trade name: V-570).
Further, after the 1.0 mm-thick molded product was treated at 150 ° C. for 168 hours, the transmittance at a wavelength of 460 nm was measured in the same manner.
（密着力）
Ａｇめっきフレーム（サイズ：２９ｍｍ×９ｍｍ×０．１７ｍｍ）に、接着面である底面直径がφ３．４ｍｍになるように、１６５℃、２分で台形又は円柱状に樹脂組成物を成形し、１００℃でのせん断接着力を測定した。
(Adhesion)
A resin composition is formed into a trapezoidal shape or a cylindrical shape at 165 ° C. for 2 minutes so that the bottom surface diameter as an adhesive surface becomes φ3.4 mm on an Ag plating frame (size: 29 mm × 9 mm × 0.17 mm). The shear adhesive strength at 0 ° C. was measured.
（はんだ耐熱性）
ＳＯＰ１６（サイズ：２９ｍｍ×９ｍｍ×０．１７ｍｍ、Ａｇめっき）に１６５℃、２分で成形し、３０℃、７０％、１６８時間（ＭＳＬ３条件）、および６０℃、６０％、１２０時間（ＭＳＬ２ａ条件）で、吸湿処理後にＭａｘ温度が２６０℃リフロー試験を行った。超音波探傷装置で剥離を確認し、５０％以上の面積が剥離しているものを不良とカウントして、［不良パッケージ数／総パッケージ数］を求め、次の基準により評価した。なお、実施例１〜１０ではＭＬＳ２ａ条件での試験は行わなかった。
◎：ＭＳＬ３条件、ＭＳＬ２ａ条件ともに不良パッケージなし、
○：ＭＳＬ３条件で不良パッケージなし、
×：ＭＳＬ３条件、ＭＳＬ２ａ条件ともに不良パッケージあり
(Solder heat resistance)
Molded on SOP16 (size: 29 mm x 9 mm x 0.17 mm, Ag plating) at 165 ° C for 2 minutes, 30 ° C, 70%, 168 hours (MSL3 conditions), and 60 ° C, 60%, 120 hours (MSL2a conditions) ), The Max temperature was 260 ° C. after the moisture absorption treatment. Peeling was confirmed with an ultrasonic flaw detector, and those with an area of 50% or more peeled were counted as defective, and [number of defective packages / total number of packages] was determined and evaluated according to the following criteria. In Examples 1 to 10, the test under the MLS2a condition was not performed.
A: No defective package for both MSL3 and MSL2a conditions
○: No defective package under MSL3 condition
×: Both MSL3 and MSL2a conditions have defective packages
（輝度維持率）
青色ＬＥＤ素子を搭載してワイヤボンディングされたＳＯＰ１６（Ａｇめっき）に、１２０ｍＷになるように通電して５００時間の点灯試験を行った。ＳＯＰ１６より発せられる光を一定距離３．５ｍｍからフォトダイオード（浜松ホトニクス製、商品名：Ｓ１２２６−８ＢＱ）に当てた際の電流値を輝度とし、イニシャルからの輝度維持率を次の式で計算し、次の基準により評価した。
維持率＝（測定輝度値／初期輝度値）×１００
○：維持率７０％以上、×：維持率７０％未満
(Luminance maintenance rate)
A lighting test was conducted for 500 hours by energizing SOP16 (Ag plating) mounted with a blue LED element and wire-bonded to 120 mW. The current value when the light emitted from SOP16 is applied to a photodiode (product name: S1226-8BQ, manufactured by Hamamatsu Photonics) from a certain distance of 3.5 mm is defined as luminance, and the luminance maintenance ratio from the initial is calculated by the following formula. Evaluation was made according to the following criteria.
Maintenance rate = (measured luminance value / initial luminance value) × 100
○: Maintenance rate 70% or more, ×: Maintenance rate less than 70%
本発明のエポキシ樹脂組成物は、２６０℃はんだ実装時の剥離を抑制し、さらに実装後に長期にわたる熱による黄変を抑制し、耐光性、剥離抑制に優れたものであり、従来にない顕著な効果を奏することが確認できた。 The epoxy resin composition of the present invention suppresses peeling at 260 ° C. solder mounting, further suppresses yellowing due to heat for a long time after mounting, and is excellent in light resistance and peeling suppression, which is not remarkable in the past. It was confirmed that there was an effect.
以上より、本発明の透明エポキシ樹脂組成物は、ジスルフィド結合（Ｓ−Ｓ結合）を含有する化合物、亜リン酸エステルを併用することで、またフェノール系酸化防止剤をさらに併用することで、少量の添加量でもそれらの相乗効果により、熱による黄変抑制および耐光性に優れた硬化物が得られることがわかった。よって、この透明エポキシ樹脂組成物で封止された光半導体装置は、組立時・組立後の剥離が抑制された信頼性の高い装置となる。 From the above, the transparent epoxy resin composition of the present invention can be used in a small amount by using a compound containing a disulfide bond (SS bond) and a phosphite ester in combination with a phenolic antioxidant. It was found that a cured product excellent in suppression of yellowing due to heat and excellent in light resistance can be obtained due to the synergistic effect even with the addition amount of. Therefore, the optical semiconductor device sealed with this transparent epoxy resin composition is a highly reliable device in which peeling during and after assembly is suppressed.
Claims (7)
（Ｂ）酸無水物硬化剤と、
（Ｃ）硬化促進剤と、
（Ｄ）ジスルフィド結合を含有する化合物と、
（Ｅ）亜リン酸エステルと、
を必須成分として含有することを特徴とする透明エポキシ樹脂組成物。 (A) a transparent epoxy resin;
(B) an acid anhydride curing agent;
(C) a curing accelerator;
(D) a compound containing a disulfide bond;
(E) a phosphite,
A transparent epoxy resin composition comprising:
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| TW106135050A TWI651363B (en) | 2016-11-29 | 2017-10-13 | Transparent epoxy resin composition and optical semiconductor device |
| CN201710992489.9A CN108117721A (en) | 2016-11-29 | 2017-10-23 | transparent epoxy resin composition and optical semiconductor device |
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| CN113088224A (en) * | 2021-02-26 | 2021-07-09 | 广东美的白色家电技术创新中心有限公司 | Protection composition applied to packaging product, power module and preparation method of power module |
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| JP6427116B2 (en) * | 2014-02-07 | 2018-11-21 | 日本化薬株式会社 | Epoxy resin mixture, epoxy resin composition, cured product thereof, and semiconductor device |
| JP6274093B2 (en) * | 2014-12-03 | 2018-02-07 | 信越化学工業株式会社 | Thermosetting epoxy resin composition for optical semiconductor element sealing and semiconductor device using the same |
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| JP2003221490A (en) * | 2002-01-30 | 2003-08-05 | Sumitomo Chem Co Ltd | Resin composition for use in encapsulation of light emitting diode |
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