JPS60137046A - Light emitting/light receiving element sealer - Google Patents
Light emitting/light receiving element sealerInfo
- Publication number
- JPS60137046A JPS60137046A JP59231815A JP23181584A JPS60137046A JP S60137046 A JPS60137046 A JP S60137046A JP 59231815 A JP59231815 A JP 59231815A JP 23181584 A JP23181584 A JP 23181584A JP S60137046 A JPS60137046 A JP S60137046A
- Authority
- JP
- Japan
- Prior art keywords
- light
- epoxy resin
- imidazoles
- curing
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003822 epoxy resin Substances 0.000 claims abstract description 32
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 32
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 12
- 238000007789 sealing Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims abstract description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 10
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 239000004593 Epoxy Substances 0.000 claims 1
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- 150000007942 carboxylates Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 9
- 150000008064 anhydrides Chemical class 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract 2
- 230000002087 whitening effect Effects 0.000 abstract 2
- NGZXDRGWBULKFA-NSOVKSMOSA-N (+)-Bebeerine Chemical compound C([C@@H]1N(C)CCC=2C=C(C(=C(OC3=CC=C(C=C3)C[C@H]3C=4C=C(C(=CC=4CCN3C)OC)O3)C=21)O)OC)C1=CC=C(O)C3=C1 NGZXDRGWBULKFA-NSOVKSMOSA-N 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 34
- 238000002845 discoloration Methods 0.000 description 13
- 239000007788 liquid Substances 0.000 description 10
- 238000005266 casting Methods 0.000 description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 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 7
- 230000007423 decrease Effects 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 238000005562 fading Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- FKBMTBAXDISZGN-UHFFFAOYSA-N 5-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1C(C)CCC2C(=O)OC(=O)C12 FKBMTBAXDISZGN-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000001044 red dye Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- DJKGDNKYTKCJKD-BPOCMEKLSA-N (1s,4r,5s,6r)-1,2,3,4,7,7-hexachlorobicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic acid Chemical compound ClC1=C(Cl)[C@]2(Cl)[C@H](C(=O)O)[C@H](C(O)=O)[C@@]1(Cl)C2(Cl)Cl DJKGDNKYTKCJKD-BPOCMEKLSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- KKKDZZRICRFGSD-UHFFFAOYSA-N 1-benzylimidazole Chemical compound C1=CN=CN1CC1=CC=CC=C1 KKKDZZRICRFGSD-UHFFFAOYSA-N 0.000 description 1
- MJNWXQVKQCOEHA-UHFFFAOYSA-K C(C=CCCCCC)(=O)[O-].[Al+3].C(C=CCCCCC)(=O)[O-].C(C=CCCCCC)(=O)[O-] Chemical compound C(C=CCCCCC)(=O)[O-].[Al+3].C(C=CCCCCC)(=O)[O-].C(C=CCCCCC)(=O)[O-] MJNWXQVKQCOEHA-UHFFFAOYSA-K 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- -1 alicyclic carboxylic acid Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0203—Containers; Encapsulations, e.g. encapsulation of photodiodes
Abstract
Description
【発明の詳細な説明】
この発明は透明性にすぐれる注型用エポキシ樹脂組成物
を用いて発光素子または受光素子を封止してなる発光素
子または受光素子封止体に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a light-emitting element or light-receiving element sealed body formed by sealing a light-emitting element or a light-receiving element using a casting epoxy resin composition having excellent transparency.
従来、エポキシ樹脂は電気特性、耐湿性、 １ｌｊＪ熱
特性などにずくれる樹脂として知られ、一般に硬化剤と
してアミン系硬化剤および酸無水物系硬化剤を使用した
ものが広く利用されている。Epoxy resins have heretofore been known as resins with excellent electrical properties, moisture resistance, thermal properties, etc., and those using amine-based curing agents and acid anhydride-based curing agents are generally widely used.
しかし、アミン系硬化剤を使用したエポキシ樹脂組成物
はその硬化時もしくは硬化後の餓用時に、とくに高温下
に放置されたときに著しい紗色がおこり、前記の特性の
ほかに光透過率が良好であることが要求される発光素子
や受光素子などの素子ないし部品の封止材料としては適
用できなかっな一方、酸無水物系硬化剤を使用したエポ
キシ樹脂組成物は一般的に硬化連間がおそいためこれに
さらに硬化触媒（硬化促進剤）を配合するのが普ｊ＋７
＋であり、このような硬化系によるとアミン系硬化剤に
おけるような著しい変色はそれほど認められない。また
酸無水物が無色透明であってこれを通猟エポキシ基と同
当量程度の多量使用するために、樹脂の茶色（淡黄色）
さえも消失した無色透明に近い成形品を得ることができ
る。したがってアミン系硬化剤とは異なって発光素子な
どの封止＋ａ Ｉｔとしても充分適用可能である。However, epoxy resin compositions using amine-based curing agents develop a significant gauze color during curing or during starvation after curing, especially when left under high temperatures, and in addition to the above characteristics, light transmittance is also reduced. Epoxy resin compositions using acid anhydride curing agents are generally not suitable for use as encapsulating materials for devices or components such as light-emitting devices and light-receiving devices that require good performance. Since curing is slow, it is common to add a curing catalyst (curing accelerator) to this.
+, and with such a curing system, the remarkable discoloration that occurs with amine-based curing agents is not so observed. In addition, the acid anhydride is colorless and transparent, and because it is used in a large amount, about the same amount as the epoxy group, the resin becomes brown (light yellow).
It is possible to obtain molded products that are nearly colorless and transparent and have no visible color. Therefore, unlike amine curing agents, it is fully applicable to sealing of light emitting devices and the like.
ところが、この種の酸無水物系硬化剤からなる組成物に
おいてとくにエポキシ樹脂として常温で液状のものを（
重用した注型用組成物とする場合、注型後加熱硬化させ
る際に大気表面に露出する表面部の酸無水物が気化蒸発
して硬化不充分となるためか、得られる注型品を高温高
湿下に放置したとき表面側が白濁化し全体としての透明
性が損なわれるという問題があった。また組成物中に着
色剤を添加したものでは」上記の条件下で退色ないし変
色してしまう問題もあった。However, in compositions made of this type of acid anhydride curing agent, epoxy resins that are liquid at room temperature (
When making a heavily used casting composition, the resulting cast product is heated at high temperatures, perhaps because the acid anhydride on the surface exposed to the atmosphere evaporates when it is heated and cured after casting, resulting in insufficient curing. There was a problem in that when left under high humidity, the surface side became cloudy and the overall transparency was impaired. Additionally, compositions containing colorants have the problem of fading or discoloration under the above conditions.
この発明は、このような問題を解消するために鋭意検討
した結果、酸無水物系１１９化剤とともに使用する硬化
触媒として、従来公知のものの中からと（に特定の化合
物を選定しかつこれを二種以上混合使用したときに、非
常に好結果が得られることが判り、なされたものである
。As a result of intensive studies to solve these problems, this invention selected a specific compound from among conventionally known curing catalysts to be used with an acid anhydride-based 119izing agent. This was done because it was found that very good results could be obtained when two or more types were used in combination.
すなわち、この発明は、常温で液状のエポキシ樹脂に硬
化剤として酸無水物を配合し、かつ硬−化触媒としてイ
ミダゾール類とともにカルボン酸金属塩を配合してなる
透明性にすくれる注型用エポキシ樹脂組成物を用いて、
発光素子または受光素子を封止してなる発光素子または
受光素子封止体に係るものである。That is, the present invention provides a highly transparent casting epoxy resin, which is made by blending an acid anhydride as a curing agent into an epoxy resin that is liquid at room temperature, and blending a carboxylic acid metal salt with an imidazole as a curing catalyst. Using a resin composition,
This invention relates to a light-emitting element or light-receiving element sealed body formed by sealing a light-emitting element or a light-receiving element.
このように、この発明においてはイミダゾール類とカル
ボン酸金属塩とを混合使用することか重要てδ５つて、
これによって始めて高温高湿下におかれたときの表面側
の白濁化や、着色剤を加えた場合の退色ないし変色を防
止でき、全体としての透明性にすぐれ、また耐変色性に
もすぐれる注型品としての発光素子または受光素子対正
体を製造できるという効果が得られる。Thus, in this invention, it is important to use a mixture of imidazoles and carboxylic acid metal salts.
This prevents the surface from becoming cloudy when exposed to high temperature and high humidity for the first time, and from fading or discoloration when a coloring agent is added, resulting in excellent overall transparency and excellent discoloration resistance. The effect of manufacturing a light emitting element or a light receiving element as a cast product can be obtained.
一方、この発明によらないで、上記の硬化触媒のうちそ
の一方だけを使用したのではいずれもこの究明の目的を
達成することはできない。まず、硬化触媒としてイミダ
ゾール類だけを使用した場合、注型品表面側の白濁化な
いし変色などを防止するにはとんと効果を示さない。ま
たカルボン酸金属塩だけを使用した場合、上述の問題を
解消できても、酸無水物系硬化剤を用いることの特徴と
される前記４ｊ１（色透明に近い成形品を得るという本
来の利点が失われ、結果として全体的に透明性の良好な
Ｌｌ−型品を得ることかできなくなる。On the other hand, if only one of the above-mentioned curing catalysts is used without following the present invention, the object of this investigation cannot be achieved. First, when only imidazoles are used as a curing catalyst, they are not very effective in preventing clouding or discoloration on the surface of the cast product. Furthermore, if only carboxylic acid metal salts are used, even if the above-mentioned problems can be solved, the characteristic of using an acid anhydride curing agent in 4j1 (the original advantage of obtaining a molded product with almost transparent color) As a result, it becomes impossible to obtain an Ll-type product with good overall transparency.
一般に、カルボン酸金属塩は酸無水物とエポキシ樹脂と
の反応に対する活性作用に較へてエポキシ樹脂自体に対
する活性作用の方が大であるため、この系において硬化
剤としての酸無水物を多くすると成形品中に未反応物が
残留しこれが成形品の嗣湿持性などを大きく低下させる
結果となる。このためカルホン酸金属塩だけを硬化触媒
として使用する場合、酸力（（水物の使用量はエポキシ
基に対して通常０５当量以下、好適には０２〜０３当量
程反の少量にしなければならず、これでは無色透明であ
る酸無水物の樹脂の茶色消失効果を充分に発揮できなく
なる。In general, carboxylic acid metal salts have a greater active effect on the epoxy resin itself than on the reaction between the acid anhydride and the epoxy resin, so if the amount of acid anhydride used as a curing agent in this system is increased, Unreacted substances remain in the molded article, resulting in a significant decrease in the moisture retention of the molded article. For this reason, when only carbonic acid metal salts are used as curing catalysts, the amount of acid power ((water) used must be as small as 0.05 equivalents or less, preferably 0.2 to 0.3 equivalents, based on the epoxy group. However, in this case, the acid anhydride resin, which is colorless and transparent, cannot fully exhibit its brown disappearing effect.
これに対してこの発明によれば硬化触媒のひとつである
イミダゾール類が酸無水物とエポキシ樹脂との反応に対
して充分に高い活性を示すから、酸無水物の使用量を上
記の反応に必要な多量にすることができ、結果として樹
脂の茶色消失効果を充分に発現させうるものであり、ま
たその一方においてイノ１用するカルボン酸金属塩によ
って注型品表面側の白濁化ないし変色を抑止できるため
、全体として透明性にすくれ、また耐変色性の良好な樹
脂注型品つまり発光素子または受光素子対正体を製造で
きるものである。On the other hand, according to the present invention, imidazoles, which are one of the curing catalysts, show sufficiently high activity for the reaction between acid anhydride and epoxy resin, so the amount of acid anhydride used is not necessary for the above reaction. As a result, the effect of eliminating the brown color of the resin can be fully expressed, and at the same time, the carboxylic acid metal salt used in Inno 1 prevents clouding or discoloration on the surface of the cast product. Therefore, it is possible to manufacture a resin cast product, that is, a light-emitting element or a light-receiving element counter body, which has excellent transparency as a whole and good discoloration resistance.
この発明において用いられるエポキシ樹脂は、常温で液
状であるものであれば広く適用でき、液状ヒスフェノー
ルＡ系エポキシ樹脂、液状ノボラック系エポキシ樹脂、
液状脂環族系エポキシ樹脂など種々のタイプのものを使
用できる。なおこれらの液状のエポキシ樹脂とともに必
要なら常温で固形のエポキシ樹脂を注型作業性を害しな
い程度の少量であれは併用してもよい。The epoxy resin used in this invention can be widely applied as long as it is liquid at room temperature, such as liquid hisphenol A-based epoxy resin, liquid novolac-based epoxy resin,
Various types of resins such as liquid alicyclic epoxy resins can be used. If necessary, an epoxy resin that is solid at room temperature may be used together with these liquid epoxy resins in a small amount that does not impair casting workability.
常温で液状のエポキシ樹脂の市販品の代表例としては、
エピコート＃８２７、エピコート＃８２８、エピコート
＃８３４（シェル社製の液状ビスフエ／−ル系エポキシ
樹脂）、ＤＥＮ４３８（ダウケミカル社製の液状／ボラ
ック系エポキシ樹脂）、アラルタイトｃＹ］７５（チバ
社製液状脂環族エポキシ樹脂）などが挙げられる。これ
らのエポキシ樹脂は単独で使用してもよいし二種以上２
Ｎ ｅして使用してもよい。Typical examples of commercially available epoxy resins that are liquid at room temperature include:
Epicoat #827, Epicoat #828, Epicoat #834 (liquid bisphere/ol epoxy resin manufactured by Shell), DEN438 (liquid/borac epoxy resin manufactured by Dow Chemical), Arartite cY75 (liquid manufactured by Ciba) Examples include alicyclic epoxy resins). These epoxy resins may be used alone or in combination of two or more.
You may use it as Ne.
この発明において硬化剤として用いられる酸無水物には
、無水フタル酸、無水テトラヒドロフタル酸、無水へキ
サヒドロフタル酸、無水４−メチルへキサヒドロフタル
酸、無水マレイン酸、ｆｌｌｕ水トリメトリメリット酸
へキサクロロエンドメチレンテトラヒドロフタル酸など
が含まれる。これらの無水物は単独でもしくは二種以」
ニ混合して使用できるが、使用量はエポキシ樹脂に対し
て通常０６〜１５当世、好適には０８〜１２当量となる
ような割合とすればよい。Acid anhydrides used as a curing agent in this invention include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, maleic anhydride, flluhydrium trimellitic acid. Includes hexachloroendomethylenetetrahydrophthalic acid. These anhydrides may be used alone or in combination of two or more.
They can be used as a mixture, but the amount used should be such that it is usually 0.6 to 15 equivalents, preferably 0.8 to 12 equivalents, based on the epoxy resin.
この発明において硬化触媒のひとつとして用いられるイ
ミダゾール類の例としては、２−エチル−４−メチルイ
ミダゾール、２−メチルイミダゾール、１−ベンジル−
２−メチルイミダゾールなどが挙げられる。Examples of imidazoles used as one of the curing catalysts in this invention include 2-ethyl-4-methylimidazole, 2-methylimidazole, and 1-benzyl-imidazole.
Examples include 2-methylimidazole.
なお、上記のイミダゾール類と同様に酸無水物とエポキ
シ樹脂との反応に対して高い活性を示すものとして三級
アミン類がある。しかるに、この三級アミン類は一般に
臭気が強いため実用性の面でイミダゾールに較へてかな
り劣り、また加熱下での耐変色性上好結果を与えないも
のが多い。これに対し、前記のイミダゾール類にはかか
る欠点がなく、透明性にすくれまた耐変色性の良好な樹
脂注型品を工業的有利に得るために用いる硬化触媒とし
てよりすくれたものである。Note that, similar to the imidazoles mentioned above, tertiary amines exhibit high activity in the reaction between acid anhydrides and epoxy resins. However, these tertiary amines generally have a strong odor and are therefore considerably inferior to imidazole in terms of practicality, and many do not provide good results in color fastness under heating. On the other hand, the imidazoles described above do not have such drawbacks and are better suited as curing catalysts for industrially advantageous production of resin cast products with poor transparency and good discoloration resistance. .
イミダゾール類の使用量は、酸無水物系硬化剤１００重
量部に対して通常０．０５〜５重量部、好ｉには０１〜
１重量部とするのがよい。この量が少なくなりすきると
ゲル化時間が長くなり硬化作業性を著しく低下させるお
それがある。また逆に多くなりすきると硬化が急激に進
む結果硬化時の発熱が犬となって注型品にクラックを生
じさせたり変色させるおそれがある。The amount of imidazoles used is usually 0.05 to 5 parts by weight, preferably 0.01 to 5 parts by weight, per 100 parts by weight of the acid anhydride curing agent.
The amount is preferably 1 part by weight. If this amount becomes too small, the gelation time will become longer and curing workability may be significantly reduced. On the other hand, if the amount is too large, the curing will proceed rapidly and the heat generated during curing will increase, which may cause cracks or discoloration in the cast product.
この発明においてもうひとつの硬化触媒として用いられ
るカルボン酸金属塩には、脂肪族、芳香族および脂環族
の各種カルボン酸の金属塩が広（含まれる。代表的なも
のとしてはオクチル酸スズ、オクテン酸アルミニウムな
どが挙げられるが、もつとも好適なものはオクチル酸ス
ズである。The carboxylic acid metal salts used as another curing catalyst in this invention include a wide variety of aliphatic, aromatic, and alicyclic carboxylic acid metal salts.Typical examples include tin octylate, Examples include aluminum octenoate, but the most preferred one is tin octylate.
このようなカルボン酸金属塩の使用割合は、酸無水物硬
化剤１００重量部に対して通常０５〜１０■ｉ量部、好
適にＬｌ： １〜３重量部とするのがよい。The proportion of such carboxylic acid metal salt to be used is usually 05 to 10 parts by weight, preferably 1 to 3 parts by weight, per 100 parts by weight of the acid anhydride curing agent.
この量が少なくなりすきると表面硬化性が悪くなりｔ１
ユ型品表面の白濁化や着色剤を加えたときの変色ないし
退色を抑止できなくなる。また逆に多くしすきると硬化
樹脂のガラス転移温度が低下してくるため注型品として
の発光素子または受光素子封止体の用途に支障をきたす
。If this amount decreases and becomes too much, the surface hardening property will deteriorate and t1
It becomes impossible to prevent the surface of the U-shaped product from becoming cloudy and from discoloration or fading when a coloring agent is added. On the other hand, if too much is used, the glass transition temperature of the cured resin will decrease, which will impede its use as a cast molded product as a light emitting device or a light receiving device sealed body.
この発明に係る注型用エポキシ樹脂組成物は、上述した
ようなエポキシ樹脂、硬化剤および硬化触媒を含むもの
であるが、これにはさらに各種の染料、顔料などの着色
剤を配合でき、この着色剤として淡色のものを使用すれ
ば着色透明の注型品の製造が可能となる。その他配合剤
としては従来公知の充填剤、可塑剤、酸化防止剤などが
あり、この発明の効果に悪影響を与えない割合で添加し
てもよい。The epoxy resin composition for casting according to the present invention contains the above-mentioned epoxy resin, curing agent, and curing catalyst, but it can further contain coloring agents such as various dyes and pigments. If a light-colored one is used, it becomes possible to produce a colored and transparent cast product. Other compounding agents include conventionally known fillers, plasticizers, antioxidants, etc., and may be added in proportions that do not adversely affect the effects of the present invention.
このようにして得られるこの発明に係るエポキシ樹脂組
成物は、これを公知の方法に阜して発光素子または受光
素子に対してＩＥ型し、加熱硬化処理することによって
、全体の透明性にすくれる注型品としての発光素子また
は受光素子封止体を得ることかできる。The epoxy resin composition according to the present invention obtained in this manner is applied to a light emitting element or a light receiving element by a known method, and is heat-cured to improve the overall transparency. It is possible to obtain a light-emitting device or a light-receiving device sealed body as a molded product.
以下に、この発明の実施例を記載する。Examples of this invention will be described below.
実施例１
エピコート＃８２７ （前出） ｉ Ｏ０グと、リカジ
ッドＭＨ−７００（新日本理化社製無水４−メチルへキ
サヒドロフタル酸） ］ ０ ｏＨ１３，２−エチル−
４−メチルイミダゾール０．１−０．５ Ｎｍ部および
オクチル酸スズ１０〜５．ＯＭ量部がらなる混合物９２
２とを、均一に混合してこの発明に係る数種の注型用エ
ポキシ樹脂組成物を得た。Example 1 Epicote #827 (mentioned above) i O0g and Rikazid MH-700 (4-methylhexahydrophthalic anhydride manufactured by Shin Nihon Rika Co., Ltd.)] 0 oH13,2-ethyl-
0.1-0.5 Nm parts of 4-methylimidazole and 10-5 Nm parts of tin octylate. Mixture 92 consisting of parts of OM
2 were uniformly mixed to obtain several kinds of epoxy resin compositions for casting according to the present invention.
これらの組成物を発光素子のセラミック基材（高さ１．
５〜２０Ｍ）上に約１００〜注入し、これを１２０ ’
Ｃの乾燥機中で１６時間放置して加熱硬化させた。この
ようにして得られた透明性にすぐれる各硬化物をｎ１シ
騰水中に入れ２００時間放置したのち引き上げたところ
、各硬化物にはいずれも白濁が全くみられず透明性の低
下は認められなかった。These compositions were applied to a ceramic substrate of a light emitting device (height: 1.
5-20M) and inject this into 120'
It was left to stand for 16 hours in a dryer (C) for heat curing. When each of the cured products with excellent transparency obtained in this way was placed in boiling water for 200 hours and then pulled out, there was no visible cloudiness in any of the cured products, and no decrease in transparency was observed. I couldn't.
なお、上記の実施例１に係る組成物において、２−エチ
ル−４−メチルイミダゾールの使用部数（酸無水物１０
０重量部に対して）を０５重風部に設定し、かつオクチ
ル酸スズの使用部数を０５重量部および０２重量部にし
たときの前記と同様の試験結果によれば、オクチル酸ス
ズ０５重量部ではやや白濁化し透明性の変化が僅かに認
められ、また０２重量部にすると白濁化が目立ち透明性
もかなり低下してくることが判った。In addition, in the composition according to Example 1 above, the number of parts of 2-ethyl-4-methylimidazole used (acid anhydride 10
According to the same test results as above, when the amount of tin octylate (relative to 0 parts by weight) was set to 05 parts by weight, and the numbers of tin octylate used were 05 parts by weight and 02 parts by weight, tin octylate was 05 parts by weight. It was found that at 0.2 parts by weight, the mixture became slightly cloudy and a slight change in transparency was observed, and at 0.2 parts by weight, the clouding became noticeable and the transparency decreased considerably.
実施例２
実施例１に係る注型用エポキシ樹脂組成物に赤色染料を
ごく少量加え、実施例１と同様にして加熱硬化させたと
ころ、赤色透明の硬化物が得られた。この硬化物につき
実施例１と同様の沸騰水試験を行ったところ、硬化物の
透明性の低下や退色ないし変色は全く認められなかった
。Example 2 A very small amount of red dye was added to the casting epoxy resin composition according to Example 1, and the mixture was heated and cured in the same manner as in Example 1, to obtain a red transparent cured product. When this cured product was subjected to the same boiling water test as in Example 1, no decrease in transparency, fading or discoloration of the cured product was observed.
一方、この例においてもオクチル酸スズの使用部数を少
なくした実施例１に記載と同様の追加試験を行ったとこ
ろ、オクチル酸スズ０５重量部では変色ないし透明性の
低下が僅かに認められ、また０２重量部では白濁化ない
し変色が目立ち透明性かかなり低下してきた。On the other hand, in this example, an additional test similar to that described in Example 1 was conducted using a smaller amount of tin octylate, and it was found that 05 parts by weight of tin octylate caused slight discoloration or a decrease in transparency. At 02 parts by weight, clouding or discoloration was noticeable and the transparency was considerably reduced.
比較例
実施例１，２に記載の注型用エポキシ樹脂組成物におい
て、オクチル酸スズを全く使用しなかったところ、実施
例１，２と同様の沸騰水試験により著しく白濁化し、ま
た赤色染料を使用したものはその色が消失して黄色に変
化し、透明性が極端に損なわれてもはや発光素子として
利用することができなかった。Comparative Example When the casting epoxy resin compositions described in Examples 1 and 2 did not contain any tin octylate, they turned significantly cloudy in the same boiling water test as in Examples 1 and 2, and red dye was not added. The one used lost its color and turned yellow, and its transparency was so severely impaired that it could no longer be used as a light emitting device.
Claims (1)
無水物を配合し、かつ硬化触媒としてイミダゾール類と
ともにカルボン酸金属塩を配合してなる透明性にすくれ
る注型用エポキシ樹脂組成物を用いて、発光素子または
受光素子を封止してなる発光素子または受光素子封止体
。 （２）酸無水物の配合割合が、エポキシ樹脂に対して０
６〜１５エポキシ当量となるようにした特許請求の範囲
第（１）項記載の発光素子または受光素子封止体。 （：））硬化触媒の配合割合が、酸無水物１００重量部
に対してイミダゾール類００５〜５重量部およびカルボ
ン酸金属塩０５〜１０重量部となるようにした特許請求
の範囲第（１）項または第（２）項記載の発光素子また
は受光素子封止体。 （４）カルボン酸金属塩がオクチル酸スズである特許請
求の範囲第＋１１項ないし第（３）項のいずれかに記載
の発光素子または受光素子封止体。[Scope of Claims] (1) A highly transparent adhesive made of a liquid epoxy resin containing an acid anhydride as a curing agent and a carboxylic acid metal salt together with imidazoles as a curing catalyst. A light-emitting element or light-receiving element sealed body formed by sealing a light-emitting element or a light-receiving element using an epoxy resin composition for molds. (2) The blending ratio of acid anhydride is 0 to epoxy resin.
The light emitting device or light receiving device sealed body according to claim (1), wherein the epoxy equivalent is 6 to 15. (:)) Claim (1) wherein the curing catalyst is blended in a proportion of 0.5 to 5 parts by weight of imidazoles and 0.5 to 10 parts by weight of metal carboxylates to 100 parts by weight of acid anhydride. The light-emitting device or light-receiving device sealed body according to item (2) or item (2). (4) The light emitting device or light receiving device sealed body according to any one of claims 11 to 3, wherein the carboxylic acid metal salt is tin octylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59231815A JPS60137046A (en) | 1984-11-02 | 1984-11-02 | Light emitting/light receiving element sealer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59231815A JPS60137046A (en) | 1984-11-02 | 1984-11-02 | Light emitting/light receiving element sealer |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12584779A Division JPS5649726A (en) | 1979-09-29 | 1979-09-29 | Epoxy resin composition having excellent transparency for casting |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60137046A true JPS60137046A (en) | 1985-07-20 |
| JPS6262058B2 JPS6262058B2 (en) | 1987-12-24 |
Family
ID=16929453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59231815A Granted JPS60137046A (en) | 1984-11-02 | 1984-11-02 | Light emitting/light receiving element sealer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60137046A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0466950B1 (en) * | 1990-07-16 | 1998-10-07 | Nitto Denko Corporation | Method for producing an epoxy resin composition for use in molding photosemiconductor |
| US6617401B2 (en) * | 2001-08-23 | 2003-09-09 | General Electric Company | Composition comprising cycloaliphatic epoxy resin, 4-methylhexahydrophthalic anhydride curing agent and boron catalyst |
| US6617400B2 (en) * | 2001-08-23 | 2003-09-09 | General Electric Company | Composition of cycloaliphatic epoxy resin, anhydride curing agent and boron catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5121680A (en) * | 1974-08-19 | 1976-02-20 | Mitsubishi Heavy Ind Ltd | KISOSOCHI |
| JPS51129499A (en) * | 1975-04-04 | 1976-11-11 | Hitachi Chem Co Ltd | Epoxy resin composition |
-
1984
- 1984-11-02 JP JP59231815A patent/JPS60137046A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5121680A (en) * | 1974-08-19 | 1976-02-20 | Mitsubishi Heavy Ind Ltd | KISOSOCHI |
| JPS51129499A (en) * | 1975-04-04 | 1976-11-11 | Hitachi Chem Co Ltd | Epoxy resin composition |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0466950B1 (en) * | 1990-07-16 | 1998-10-07 | Nitto Denko Corporation | Method for producing an epoxy resin composition for use in molding photosemiconductor |
| US6617401B2 (en) * | 2001-08-23 | 2003-09-09 | General Electric Company | Composition comprising cycloaliphatic epoxy resin, 4-methylhexahydrophthalic anhydride curing agent and boron catalyst |
| US6617400B2 (en) * | 2001-08-23 | 2003-09-09 | General Electric Company | Composition of cycloaliphatic epoxy resin, anhydride curing agent and boron catalyst |
| US6809162B2 (en) * | 2001-08-23 | 2004-10-26 | General Electric Company | Solid state device with encapsulant of cycloaliphatic epoxy resin, 4-methylhexahydrophthalic anhydride and boron catalyst |
| US6878783B2 (en) * | 2001-08-23 | 2005-04-12 | General Electric Company | Solid state device with encapsulant of cycloaliphatic epoxy resin, anhydride, and boron catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6262058B2 (en) | 1987-12-24 |
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