JP2007039521A - Thermosetting resin composition, translucent cured product obtained by thermosetting said composition, and light emitting diode sealed with said cured product - Google Patents
Thermosetting resin composition, translucent cured product obtained by thermosetting said composition, and light emitting diode sealed with said cured productDownload PDFInfo
- Publication number
- JP2007039521A JP2007039521AJP2005223852AJP2005223852AJP2007039521AJP 2007039521 AJP2007039521 AJP 2007039521AJP 2005223852 AJP2005223852 AJP 2005223852AJP 2005223852 AJP2005223852 AJP 2005223852AJP 2007039521 AJP2007039521 AJP 2007039521A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- light
- cured product
- composition
- light emitting
- 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.)
- Pending
Links
Landscapes
- Epoxy Resins (AREA)
- Led Device Packages (AREA)
Abstract
Description
Translated fromJapanese本発明は、熱硬化性樹脂組成物、該組成物を熱硬化してなる透光性硬化物、該硬化物で封止された発光ダイオードに関する。 The present invention relates to a thermosetting resin composition, a translucent cured product obtained by thermosetting the composition, and a light-emitting diode sealed with the cured product.
近年、発光波長が３５０ｎｍ〜５５０ｎｍの青色発光あるいは紫外線発光の発光ダイオードに関しては、ＧａＮ、ＧａＡｌＮ、ＩｎＧａＮ及びＩｎＡｌＧａＮ等のＧａＮ系化合物半導体を利用した高輝度のものが得られるようになり、これらの発光ダイオードと蛍光体を組み合わせた白色発光ダイオードも実用化されている。
これらの短波長発光ダイオードの封止樹脂としては、青色光から紫外光に対する透過率が高いこと、および動作時の発熱や発光ダイオードチップからの短波長光によって透過率が低下しないことが求められている。赤色や緑色の発光ダイオードの発光素子の封止材あるいはモールド材として従来広く用いられてきた酸無水物系硬化剤を使ったビスフェノール系エポキシ透明樹脂は、接着性が高く力学的な耐久性は有しているものの、短波長の光に対する光線透過性が低いために耐光耐久性が低い、あるいは光劣化や熱劣化により着色するという欠点を有していた。In recent years, blue or ultraviolet light emitting diodes having an emission wavelength of 350 nm to 550 nm have been obtained with high brightness using GaN-based compound semiconductors such as GaN, GaAlN, InGaN, and InAlGaN. White light emitting diodes combining diodes and phosphors have also been put into practical use.
The sealing resin for these short wavelength light emitting diodes is required to have high transmittance from blue light to ultraviolet light and that the transmittance does not decrease due to heat generated during operation or short wavelength light from the light emitting diode chip. Yes. Bisphenol-based epoxy transparent resins using acid anhydride-based curing agents that have been widely used as sealing materials or molding materials for light-emitting elements of red and green light-emitting diodes have high adhesiveness and mechanical durability. However, since the light transmittance with respect to the light of a short wavelength is low, it had the fault that light resistance is low, or it colors by light deterioration or heat deterioration.
そこで短波長発光ダイオードを封止するための樹脂組成物として、非芳香族エポキシ樹脂を有効成分とする樹脂組成物が提案され、具体的には３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレートとメチルヘキサヒドロフタル酸無水物を有効成分とする発光ダイオード封止用樹脂組成物（特許文献１）や水素添加ビスフェノールＡ型エポキシ樹脂とメチルヘキサヒドロフタル酸無水物を主成分とする発光ダイオード封止用樹脂組成物（特許文献１および２）などが開示されている。これらの非芳香族エポキシ樹脂を主体として脂環式カルボン酸無水物で硬化させたエポキシ樹脂硬化物は、光劣化の原因となる炭素―炭素二重結合が重合体にほとんど存在しないため、長時間におよぶ光照射の後も比較的良好な可視光透過性を維持できる。 Therefore, a resin composition containing a non-aromatic epoxy resin as an active ingredient has been proposed as a resin composition for encapsulating a short wavelength light emitting diode, specifically, 3,4-epoxycyclohexylmethyl-3,4-epoxy. Light-emitting diode encapsulating resin composition containing cyclohexanecarboxylate and methylhexahydrophthalic anhydride as active ingredients (Patent Document 1), hydrogenated bisphenol A type epoxy resin and methylhexahydrophthalic anhydride as main components A resin composition for sealing a light emitting diode (Patent Documents 1 and 2) and the like are disclosed. Epoxy resin cured products mainly composed of these non-aromatic epoxy resins and cured with alicyclic carboxylic acid anhydrides have a long period of time because the carbon-carbon double bonds that cause photodegradation are hardly present in the polymer. A relatively good visible light transmittance can be maintained even after the light irradiation.
しかしながら、近年需要が伸びている表面実装型発光ダイオード（発光素子を基板表面に直接実装するタイプ）では、封止樹脂を薄膜状に形成する必要があるが、酸無水物硬化剤は揮発性・吸湿性が高く、かつ硬化速度も遅いため、表面実装型発光ダイオードに適用すると揮発や吸湿の影響で硬化物の特性が変動し十分な封止効果が得られない場合があるため、酸無水物硬化系のエポキシ樹脂の使用が敬遠される場合がある。 However, in surface-mounted light-emitting diodes (in which light-emitting elements are directly mounted on the substrate surface), the demand for which is increasing in recent years, it is necessary to form a sealing resin in a thin film, but acid anhydride curing agents are volatile and Because of its high hygroscopicity and slow curing speed, when applied to a surface-mounted light emitting diode, the properties of the cured product may fluctuate due to the effects of volatilization and moisture absorption, and a sufficient sealing effect may not be obtained. Use of curable epoxy resin may be avoided.
このような場合には、酸無水物硬化剤に代えて、芳香族スルホニウム塩などのカチオン性硬化剤が用いられる。カチオン性硬化剤は揮発性が低く、酸無水物系硬化剤に比べれば速やかなエポキシ樹脂の硬化を誘起する。しかしながら、カチオン性硬化剤は、芳香族環などの炭素−炭素二重結合を分子の基本骨格として有しているものが多く、青色以下の短波長の光を吸収しやすく熱的にも不安定である。即ち、カチオン性硬化剤で得られる硬化物は、短波長の光の照射や高温下で黄変を起こしやすい。また、カチオン性硬化剤によるエポキシ樹脂硬化物は可撓性に乏しく、このような樹脂を発光ダイオードの封止材とした場合、加熱や冷却時に発光素子と封止樹脂の間などで大きな応力が生じる。この応力は、樹脂クラックの発生・基材からの封止樹脂の剥離・ボンディングワイヤー切れなどを誘発し発光ダイオードの出力低下や不良の要因となる。 In such a case, a cationic curing agent such as an aromatic sulfonium salt is used instead of the acid anhydride curing agent. Cationic curing agents have low volatility and induce rapid epoxy resin curing compared to acid anhydride curing agents. However, many cationic curing agents have a carbon-carbon double bond such as an aromatic ring as the basic skeleton of the molecule, and they easily absorb light of short wavelengths below blue and are thermally unstable. It is. That is, a cured product obtained with a cationic curing agent is likely to be yellowed under irradiation with light having a short wavelength or under high temperature. In addition, epoxy resin cured products with a cationic curing agent have poor flexibility, and when such a resin is used as a sealing material for a light emitting diode, a large stress is generated between the light emitting element and the sealing resin during heating or cooling. Arise. This stress induces the occurrence of resin cracks, peeling of the sealing resin from the base material, cutting of the bonding wire, and the like, which causes a decrease in output and failure of the light emitting diode.
そこで本発明者らが、カチオン硬化エポキシ樹脂と比較して比較的良好な熱硬化物を与える非芳香族エポキシ樹脂と脂環式カルボン酸無水物とからなる透明性樹脂組成物の耐紫外線性について検討したところ、青色光・紫外光に長時間晒された場合の光透過性に優れ、すなわち耐紫外線性に優れる硬化物が得られた。しかしながらこれらの硬化物は、ビスフェノールＡ型エポキシ樹脂に代表される芳香族エポキシ樹脂と脂環式カルボン酸無水物とからなる硬化物と比較して、特に温度変化を繰り返し与えた場合に、一般的に硬く脆い樹脂特性を示すものであった。このような樹脂を発光ダイオードの封止材とした場合、大きな応力が生じ、上記カチオン性硬化剤によるエポキシ樹脂硬化物と同様に、クラックの発生、基材からの封止樹脂の剥離、ボンディングワイヤー切れなどを誘発する可能性が高くなる。
最近、発光素子により多くの電流を流し、より高い輝度を得ることで光源として使用するパワーＬＥＤとしての用途が広がりつつある。ＬＥＤの発光効率は著しく改善されているものの、まだまだ熱として捨てられるエネルギーは大きく、特にパワーＬＥＤを封止する樹脂にはさらに高い耐熱安定性が要求されている。したがって本発明の目的は、青色光・紫外光に長時間さらされたり、高温で長時間使用されたりしても優れた光透過性を維持し得、すなわち耐紫外線性に優れ、さらに温度変化を繰り返し与えた場合にも耐クラック性を有し、すなわち耐熱衝撃性にも優れる硬化物を与える熱硬化性樹脂組成物を提供することである。 Recently, the application as a power LED used as a light source is spreading by passing a larger amount of current through the light emitting element to obtain higher luminance. Although the luminous efficiency of the LED is remarkably improved, the energy that is discarded as heat is still large. In particular, the resin that seals the power LED is required to have higher heat stability. Therefore, the object of the present invention is to maintain excellent light transmittance even when exposed to blue light / ultraviolet light for a long time or used at a high temperature for a long time. An object of the present invention is to provide a thermosetting resin composition that provides a cured product having crack resistance even when repeatedly applied, that is, excellent in thermal shock resistance.
本発明者らは、上記目的を達成するため、耐紫外線性および耐熱性を考慮して、炭素−炭素二重結合を有しない各種エポキシ樹脂と各種酸無水物系硬化剤との組み合わせを鋭意検討した。その結果、1,4-シクロヘキサンジメタノールと3,4-エポキシシクロヘキサンカルボン酸とのジエステル化合物をエポキシ樹脂画分の主成分とし、水素添加トリメリット酸無水物を酸無水物系硬化剤画分の主成分とする組成物の熱硬化物が、良好な耐紫外線性と共に、優れた耐熱衝撃性を示すことを見出し、本発明を完成した。 In order to achieve the above-mentioned object, the present inventors have intensively studied combinations of various epoxy resins having no carbon-carbon double bond and various acid anhydride curing agents in consideration of ultraviolet resistance and heat resistance. did. As a result, a diester compound of 1,4-cyclohexanedimethanol and 3,4-epoxycyclohexanecarboxylic acid is the main component of the epoxy resin fraction, and hydrogenated trimellitic anhydride is used as the acid anhydride-based curing agent fraction. The present invention was completed by finding that the thermosetting product of the composition containing the main component exhibits excellent thermal shock resistance as well as good ultraviolet resistance.
したがって本発明は、エポキシ樹脂成分として下記式（１）で表される1,4-シクロヘキサンジメタノールと3,4-エポキシシクロヘキサンカルボン酸とのジエステル化合物を含有し、酸無水物系硬化剤成分として下記式（２）で表される水素添加トリメリット酸無水物を含有する熱硬化性樹脂組成物を提供するものである。
本発明の組成物において、式（２）で表される水素添加トリメリット酸無水物の含有量は、組成物に含有される酸無水物系硬化剤成分全体に対して、好ましくは１０〜１００重量％、より好ましくは２５〜１００重量％、さらに好ましくは５０〜１００重量％である。 In the composition of the present invention, the content of the hydrogenated trimellitic anhydride represented by the formula (2) is preferably 10 to 100 with respect to the entire acid anhydride-based curing agent component contained in the composition. % By weight, more preferably 25 to 100% by weight, still more preferably 50 to 100% by weight.
本発明の組成物において、式（１）で表される1,4-シクロヘキサンジメタノールと3,4-エポキシシクロヘキサンカルボン酸とのジエステル化合物の含有量は、組成物に含有されるエポキシ樹脂成分全体に対して、好ましくは３３〜１００重量％であり、より好ましくは５０〜１００重量％であり、さらに好ましくは６７〜１００重量％である。 In the composition of the present invention, the content of the diester compound of 1,4-cyclohexanedimethanol and 3,4-epoxycyclohexanecarboxylic acid represented by the formula (1) is the entire epoxy resin component contained in the composition. On the other hand, it is preferably 33 to 100% by weight, more preferably 50 to 100% by weight, and further preferably 67 to 100% by weight.
また本発明は、上記の本発明の熱硬化性樹脂組成物を硬化して得られる透光性樹脂硬化物を提供する。
さらに本発明は、上記の本発明の透光性樹脂硬化物により発光素子が封止されている発光ダイオードを提供する。本発明の発光ダイオードは、発光素子の主発光ピーク波長が５５０ｎｍ以下であるものであることが好ましい。
また本発明は、主発光ピーク波長が５５０ｎｍ以下である発光素子から発光される光の少なくとも一部を吸収して蛍光を発光することが可能な蛍光物質をさらに含有する上記本発明の熱硬化性樹脂組成物を硬化して得られる透光性樹脂硬化物により発光素子が封止されている発光ダイオードを提供する。Moreover, this invention provides the translucent resin hardened | cured material obtained by hardening | curing said thermosetting resin composition of this invention.
Furthermore, this invention provides the light emitting diode by which the light emitting element is sealed by the translucent resin cured material of said invention. The light emitting diode of the present invention preferably has a main light emission peak wavelength of 550 nm or less.
In addition, the present invention provides the thermosetting property of the present invention, further comprising a fluorescent material capable of emitting fluorescence by absorbing at least a part of light emitted from a light emitting device having a main emission peak wavelength of 550 nm or less. Provided is a light-emitting diode in which a light-emitting element is sealed with a light-transmitting resin cured product obtained by curing a resin composition.
本発明によれば、耐紫外線性および耐熱衝撃性のいずれにも優れた樹脂硬化物を与える熱硬化性樹脂組成物、および該硬化物を封止材とした発光ダイオードを提供することができ、また該熱硬化性樹脂組成物は十分な硬化速度を有するので、表面実装型発光ダイオードにも好適に使用できる。 According to the present invention, it is possible to provide a thermosetting resin composition that gives a cured resin product excellent in both ultraviolet resistance and thermal shock resistance, and a light-emitting diode using the cured product as a sealing material, Further, since the thermosetting resin composition has a sufficient curing rate, it can be suitably used for a surface-mounted light emitting diode.
以下、本発明を詳細に説明する。
本発明の樹脂組成物は、エポキシ樹脂成分として上記式（１）で表される1,4-シクロヘキサンジメタノールと3,4-エポキシシクロヘキサンカルボン酸とのジエステル化合物を含有し、酸無水物系硬化剤成分として上記式（２）で表される水素添加トリメリット酸無水物を含有することを特徴とする熱硬化性樹脂組成物エポキシ樹脂であり、実質的に硬化促進剤を含有しなくても十分な硬化速度が得られ、しかも耐紫外線性および耐熱衝撃性に優れた硬化物を与えることを特徴とする。Hereinafter, the present invention will be described in detail.
The resin composition of the present invention contains a diester compound of 1,4-cyclohexanedimethanol represented by the above formula (1) and 3,4-epoxycyclohexanecarboxylic acid as an epoxy resin component, and is an acid anhydride-based curing. It is a thermosetting resin composition epoxy resin characterized by containing a hydrogenated trimellitic anhydride represented by the above formula (2) as an agent component, and substantially does not contain a curing accelerator. A sufficient curing rate is obtained, and a cured product excellent in ultraviolet resistance and thermal shock resistance is provided.
以下、本発明の熱硬化性樹脂組成物の各成分について説明する。
本発明の熱硬化性樹脂組成物は、酸無水物系硬化剤成分として上記式（１）で表される水素添加トリメリット酸無水物を含む。
通常、酸無水物硬化型のエポキシ樹脂組成物は、エポキシ樹脂、カルボン酸無水物（エポキシ基当量と酸無水物基当量との化学量論比で０．５〜１前後の量）、硬化促進剤（エポキシ樹脂重量の０.数〜数％を含む）および必要に応じて添加される各種添加剤から構成される。これらの成分のうち硬化促進剤が硬化物の耐紫外線性や耐熱安定性に大きく影響している。硬化促進剤や硬化開始剤は化学的に不安定で、得られる硬化物の紫外線や熱による黄変の主要な要因となっている。実際、エポキシ樹脂成分および酸無水物成分を一定とし種々の硬化促進剤の存在下で熱硬化させた硬化物の耐紫外線性や耐熱安定性は、硬化促進剤の種類に依存して大きく異なる。特に、アミン系あるいはイミダゾール系の硬化促進剤を使用すると、深刻な着色が生じる場合がある。硬化促進剤が存在しなくとも熱硬化が可能な組成物も存在するものの、一般的には長時間の加熱が必要である。硬化剤として使われる酸無水物の多くは揮発性・吸湿性が高く、長時間の加熱のより組成が経時変化し、硬化不良や樹脂物性のロット間変動が誘起される。Hereinafter, each component of the thermosetting resin composition of the present invention will be described.
The thermosetting resin composition of this invention contains the hydrogenated trimellitic anhydride represented by the said Formula (1) as an acid anhydride type hardening | curing agent component.
Usually, an acid anhydride curable epoxy resin composition is an epoxy resin, a carboxylic acid anhydride (amount in the stoichiometric ratio of epoxy group equivalent to acid anhydride group equivalent of about 0.5 to 1), curing acceleration. It is comprised from the additive (it contains 0.3 to several percent of epoxy resin weight) and various additives added as needed. Among these components, the curing accelerator greatly affects the ultraviolet resistance and heat stability of the cured product. Curing accelerators and curing initiators are chemically unstable and are a major cause of yellowing due to ultraviolet rays and heat in the resulting cured product. Actually, the ultraviolet resistance and heat stability of a cured product obtained by thermosetting in the presence of various curing accelerators with a constant epoxy resin component and an acid anhydride component vary greatly depending on the type of the curing accelerator. In particular, when an amine-based or imidazole-based curing accelerator is used, serious coloring may occur. Although there are compositions that can be thermally cured even in the absence of a curing accelerator, generally, heating for a long time is required. Many of the acid anhydrides used as curing agents are highly volatile and hygroscopic, and the composition changes with time due to prolonged heating, which leads to poor curing and lot-to-lot variations in resin properties.
これに対し、本発明の樹脂組成物において必須の成分とされる水素添加トリメリット酸無水物は、エポキシ樹脂硬化に対する自己触媒能（自発的硬化促進能）を有し、硬化促進剤が存在する場合と同程度か、それ以上の硬化速度を付与する。硬化物の耐紫外線性や耐熱安定性に悪影響を与える硬化促進剤を必要としないことから、水素添加トリメリット酸無水物を配合することによりこれらの特性が大きく改善される。また、水素添加トリメリット酸無水物は吸湿性はあるものの揮発性はほとんど無く、硬化物特性の変動要因を低減させることができる。 On the other hand, the hydrogenated trimellitic anhydride, which is an essential component in the resin composition of the present invention, has a self-catalytic ability (spontaneous curing promoting ability) for curing an epoxy resin, and a curing accelerator exists. A curing rate equal to or higher than the case is given. Since a curing accelerator that adversely affects the ultraviolet resistance and heat stability of the cured product is not required, these characteristics are greatly improved by blending the hydrogenated trimellitic anhydride. Moreover, although hydrogenated trimellitic anhydride has hygroscopicity, it has almost no volatility, and can reduce the variation factor of cured product characteristics.
水素添加トリメリット酸無水物含量は、酸無水物系硬化剤成分全体に対して重量パーセントで好ましくは１０〜１００％、より好ましくは２５〜１００％、さらに好ましくは５０〜１００％である。酸無水物系硬化剤成分のうち水素添加トリメリット酸無水物含量が１０％未満では、上記の水素添加トリメリット酸無水物が示す自己触媒能（自己硬化促進能）が発揮されにくく、良好な硬化が得られにくい。共存する酸無水物に依存するものの、実質的に熱硬化に伴う樹脂ビケ（酸無水物の揮発などによる樹脂の体積減少）を抑制するためには５０％以上の水素添加トリメリット酸無水物を含有することが望ましい。このような水素添加トリメリット酸無水物含量を有する本発明の樹脂組成物は、表面実装型発光ダイオードの封止にも適用できる。 The content of hydrogenated trimellitic anhydride is preferably 10 to 100%, more preferably 25 to 100%, and still more preferably 50 to 100% by weight percent with respect to the whole acid anhydride curing agent component. If the content of hydrogenated trimellitic anhydride is less than 10% of the acid anhydride-based curing agent component, the self-catalytic ability (self-curing promoting ability) exhibited by the above-mentioned hydrogenated trimellitic anhydride is difficult to be exhibited and good. Hard to be cured. Although it depends on the coexisting acid anhydride, 50% or more of hydrogenated trimellitic acid anhydride should be used in order to substantially suppress the resin viquet (resin volume decrease due to volatilization of the acid anhydride) associated with thermosetting. It is desirable to contain. The resin composition of the present invention having such a hydrogenated trimellitic anhydride content can also be applied to sealing of surface-mounted light emitting diodes.
水素添加トリメリット酸無水物と共に使用する酸無水物としては、本発明の所望の効果が得られる限り特に限定されず、脂肪族酸無水物、例えば、ポリアゼライン酸無水物、ドデセニル無水コハク酸など、脂環族酸無水物、例えば、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、エンドメチレンテトラヒドロフタル酸（メタノテトラヒドロフタル酸）、無水メチルナジック酸、ビシクロ［２．２．１］ヘプタン−２，３−ジカルボン酸無水物、ビシクロ［２．２．１］ヘプタン−２，３，５，６−テトラカルボン酸無水物など、芳香族酸無水物、例えば、無水トリメット酸、無水ピロメリット酸など、ハロゲン系酸無水物、例えば、無水ヘット酸、テトラブロモ無水フタル酸などが挙げられる。 The acid anhydride used together with the hydrogenated trimellitic anhydride is not particularly limited as long as the desired effect of the present invention is obtained, and aliphatic acid anhydrides such as polyazeline acid anhydride, dodecenyl succinic anhydride, etc. Alicyclic acid anhydrides such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic acid (methanotetrahydrophthalic acid), methyl nadic anhydride, Aromatic acid anhydrides such as bicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid anhydride, For example, halogenated acid anhydrides such as trimetic anhydride, pyromellitic anhydride, etc. Such as phthalic anhydride and the like.
耐紫外線性を考慮すると炭素−炭素二重結合を含まないものが好ましく、好適な酸無水物として下記式（３）〜式（６）で表されるヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸などの化合物が挙げられる。ただし、封止樹脂として要求される耐久性を損なわない範囲において、少量の炭素−炭素二重結合を有する酸無水物を補うことが好ましい場合もある。例えば、水素添加トリメリット酸無水物を低粘度の液状酸無水物である程度希釈することにより、本発明の樹脂組成物の粘度を下げ、水素添加トリメリット酸無水物由来の取り扱いにくさを著しく改善することができる。 In view of UV resistance, those containing no carbon-carbon double bond are preferred, and preferred acid anhydrides include hexahydrophthalic anhydride and methylhexahydrophthalic anhydride represented by the following formulas (3) to (6). And the like. However, it may be preferable to supplement a small amount of an acid anhydride having a carbon-carbon double bond as long as the durability required as a sealing resin is not impaired. For example, by diluting the hydrogenated trimellitic anhydride to some extent with a low-viscosity liquid acid anhydride, the viscosity of the resin composition of the present invention is lowered and the handling difficulty derived from the hydrogenated trimellitic anhydride is remarkably improved. can do.
これらの酸無水物はそれぞれ単独で使用することができ、また２種以上混合して用いてもよい。
本発明の熱硬化性樹脂組成物は、エポキシ樹脂成分として上記式（１）で表される1,4-シクロヘキサンジメタノールと3,4-エポキシシクロヘキサンカルボン酸とのジエステル化合物を必須成分として含む。
酸無水物硬化型エポキシ樹脂の耐紫外線性は、酸無水物のみならずエポキシ樹脂成分にも依存する。耐紫外線性に優れるエポキシ樹脂としては、各種脂環式エポキシ樹脂、水素添加ビスフェノールＡジグリシジルエーテル、ヘキサヒドロフタル酸ジグリシジルエステル、エポキシ変性テトラメチルジシロキサン、1,4-シクロヘキサンジメタノールと3,4-エポキシシクロヘキサンカルボン酸とのジエステル化合物などが例示できる。そこで本発明者らは、これらのエポキシ樹脂のそれぞれと水素添加トリメリット酸無水物との化学量論的混合物の樹脂物性を鋭意検討した。その結果、水素添加トリメリット酸無水物を硬化剤として用いることで、それぞれのエポキシ樹脂の耐紫外線性および耐熱安定性が改善されることが確認されたが、1,4-シクロヘキサンジメタノールと3,4-エポキシシクロヘキサンカルボン酸とのジエステル化合物と水素添加トリメリット酸無水物を含む組成物から得られた硬化物の耐熱衝撃性が著しく高いことを見出したものである。The thermosetting resin composition of the present invention contains a diester compound of 1,4-cyclohexanedimethanol represented by the above formula (1) and 3,4-epoxycyclohexanecarboxylic acid as an essential component as an epoxy resin component.
The ultraviolet resistance of the acid anhydride curable epoxy resin depends not only on the acid anhydride but also on the epoxy resin component. Epoxy resins with excellent UV resistance include various alicyclic epoxy resins, hydrogenated bisphenol A diglycidyl ether, hexahydrophthalic acid diglycidyl ester, epoxy-modified tetramethyldisiloxane, 1,4-cyclohexanedimethanol and 3,4 Examples include diester compounds with 4-epoxycyclohexanecarboxylic acid. Therefore, the present inventors have intensively studied the resin physical properties of a stoichiometric mixture of each of these epoxy resins and hydrogenated trimellitic anhydride. As a result, it was confirmed that by using hydrogenated trimellitic anhydride as a curing agent, the ultraviolet resistance and heat stability of each epoxy resin were improved, but 1,4-cyclohexanedimethanol and 3 It has been found that the thermal shock resistance of a cured product obtained from a composition containing a diester compound with 4-epoxycyclohexanecarboxylic acid and a hydrogenated trimellitic anhydride is extremely high.
本発明の熱硬化性樹脂組成物が含有するエポキシ樹脂成分中の1,4-シクロヘキサンジメタノールと3,4-エポキシシクロヘキサンカルボン酸とのジエステル化合物の含有量は、発光ダイオードの封止樹脂に求められる要求特性（可撓性・靭性など）を満たすために適宜設定されるが、エポキシ樹脂成分全体に対する1,4-シクロヘキサンジメタノールと3,4-エポキシシクロヘキサンカルボン酸とのジエステル化合物含量は重量パーセントで好ましくは３３〜１００％、より好ましくは５０〜１００％、さらに好ましくは６７〜１００％である。エポキシ樹脂成分に占める1,4-シクロヘキサンジメタノールと3,4-エポキシシクロヘキサンカルボン酸とのジエステル化合物含量が３３％未満では、水素添加トリメリット酸無水物を硬化剤としたことによる耐熱安定性の改善効果が得られにくい。ただし、発光ダイオードの封止樹脂に求められる他の要求特性（可撓性、靭性など）を満たすために異種のエポキシ樹脂成分や樹脂改質剤などで希釈することが好ましい場合もあり、本発明の所望の効果が得られる限り、異種のエポキシ樹脂成分を加えることができる。 The content of the diester compound of 1,4-cyclohexanedimethanol and 3,4-epoxycyclohexanecarboxylic acid in the epoxy resin component contained in the thermosetting resin composition of the present invention is determined for the sealing resin of the light emitting diode. However, the content of diester compounds of 1,4-cyclohexanedimethanol and 3,4-epoxycyclohexanecarboxylic acid in the total epoxy resin component is weight percent. And preferably 33 to 100%, more preferably 50 to 100%, still more preferably 67 to 100%. When the diester compound content of 1,4-cyclohexanedimethanol and 3,4-epoxycyclohexanecarboxylic acid in the epoxy resin component is less than 33%, the heat stability due to the use of hydrogenated trimellitic anhydride as a curing agent Improvement effect is difficult to obtain. However, in order to satisfy other required characteristics (flexibility, toughness, etc.) required for the sealing resin of the light emitting diode, it may be preferable to dilute with a different kind of epoxy resin component or resin modifier. As long as the desired effect is obtained, different types of epoxy resin components can be added.
1,4-シクロヘキサンジメタノールと3,4-エポキシシクロヘキサンカルボン酸とのジエステル化合物とともに使用することができる好ましいエポキシ樹脂成分としては、耐紫外線性に優れる各種エポキシ樹脂、例えば、脂環式エポキシ樹脂、脂肪族エポキシ樹脂、水素添加ビスフェノールＡジグリシジルエーテル、ヘキサヒドロフタル酸ジグリシジルエステル、エポキシ変性テトラメチルジシロキサンなどが挙げられるが、これらに限定されるものではない。
また、封止樹脂として要求される耐久性を損なわない範囲において、少量の炭素−炭素二重結合を有するエポキシ樹脂を含有してもよい。これらのエポキシ樹脂成分はそれぞれ単独で使用することができ、また２種以上混合して用いてもよい。さらには、エポキシ樹脂と共重合可能なオキセタン樹脂や各種変性樹脂などを使用してもよい。As a preferable epoxy resin component that can be used together with a diester compound of 1,4-cyclohexanedimethanol and 3,4-epoxycyclohexanecarboxylic acid, various epoxy resins excellent in ultraviolet resistance, for example, alicyclic epoxy resins, Examples include, but are not limited to, aliphatic epoxy resins, hydrogenated bisphenol A diglycidyl ether, hexahydrophthalic acid diglycidyl ester, and epoxy-modified tetramethyldisiloxane.
Moreover, you may contain the epoxy resin which has a small amount of carbon-carbon double bonds in the range which does not impair the durability requested | required as sealing resin. These epoxy resin components can be used alone or in combination of two or more. Furthermore, an oxetane resin copolymerizable with an epoxy resin or various modified resins may be used.
本発明の熱硬化樹脂組成物における上記酸無水物硬化剤は、エポキシ樹脂成分に対して化学量論量程度含まれればよいが、エポキシ樹脂成分１当量に対して好ましくは０.４〜１.２当量、好ましくは０.５〜１.０当量程度である。さらに酸無水物硬化剤およびエポキシ樹脂成分中の1,4-シクロヘキサンジメタノールと3,4-エポキシシクロヘキサンカルボン酸とのジエステル化合物と水素添加トリメリット酸無水物の含量はそれぞれ上記の範囲から任意に選択することによりそれぞれの成分の添加による効果の程度を調節することができ、両者の含量を調節することにより両者の含量に応じた種々の特性を有する樹脂硬化物が得られる。 Although the said acid anhydride hardening | curing agent in the thermosetting resin composition of this invention should just be contained about the stoichiometric amount with respect to an epoxy resin component, Preferably it is 0.4-1 with respect to 1 equivalent of epoxy resin components. It is about 2 equivalents, preferably about 0.5 to 1.0 equivalents. Further, the content of the diester compound of 1,4-cyclohexanedimethanol and 3,4-epoxycyclohexanecarboxylic acid and the hydrogenated trimellitic anhydride in the acid anhydride curing agent and the epoxy resin component are arbitrarily selected from the above ranges. By selecting, the degree of the effect by addition of each component can be adjusted, and by adjusting the contents of both, a cured resin product having various characteristics according to the contents of both can be obtained.
本発明の目的は、優れた耐紫外線性および耐熱衝撃性を有しかつ発光ダイオードの封止樹脂に求められる機械的特性を満足する熱硬化性樹脂組成物と該組成物を封止材とした発光ダイオードを提供することである。したがって、本発明の目的が達成される限り、本発明の熱硬化性樹脂組成物は、色変換用蛍光体、無機フィラー、酸化防止剤、光安定化剤、樹脂改質剤、シランカップリング剤などの各種添加剤の1種以上を含んでもよい。 An object of the present invention is to provide a thermosetting resin composition having excellent ultraviolet resistance and thermal shock resistance and satisfying mechanical properties required for a sealing resin for light-emitting diodes, and the composition as a sealing material. It is to provide a light emitting diode. Therefore, as long as the object of the present invention is achieved, the thermosetting resin composition of the present invention includes a phosphor for color conversion, an inorganic filler, an antioxidant, a light stabilizer, a resin modifier, and a silane coupling agent. One or more of various additives such as
本発明の熱硬化性樹脂組成物により得られる硬化物の耐熱安定性をさらに向上させるために、該組成物に酸化防止剤を添加剤として含有させることが好ましい。酸化防止剤としては、例えば、フェノール系酸化防止剤（ＢＨＴなど）、イオウ系酸化防止剤（メルカプトプロピオン酸誘導体など）、リン系酸化防止剤（ＨＣＡなど）などが挙げられる。これらの中で、フェノール系酸化防止剤を好適に用いることができ、さらに好ましくはフェノール系酸化防止剤と相対的に少量のイオウ系酸化防止剤を併用することができる。 In order to further improve the heat stability of the cured product obtained from the thermosetting resin composition of the present invention, it is preferable to contain an antioxidant as an additive in the composition. Examples of the antioxidant include phenolic antioxidants (such as BHT), sulfur-based antioxidants (such as mercaptopropionic acid derivatives), and phosphorus-based antioxidants (such as HCA). Among these, a phenolic antioxidant can be suitably used, and more preferably, a phenolic antioxidant and a relatively small amount of a sulfur-based antioxidant can be used in combination.
本発明の樹脂組成物におけるフェノール系酸化防止剤の含有量としては、通常、組成物成分の合計１００重量部に対して０．１〜４重量部程度であり、好ましくは０．２〜２重量部程度、より好ましくは０．５〜１重量部程度である。イオウ系酸化防止剤を併用する際は、その含有量を組成物成分の合計１００重量部に対して０．１重量部程度以下とすることが好ましい。 As content of the phenolic antioxidant in the resin composition of this invention, it is about 0.1-4 weight part normally with respect to a total of 100 weight part of a composition component, Preferably it is 0.2-2 weight About 1 part, more preferably about 0.5 to 1 part by weight. When using a sulfur type antioxidant together, it is preferable to make the content into about 0.1 weight part or less with respect to a total of 100 weight part of a composition component.
本発明は、本発明の熱硬化性樹脂組成物を硬化して得られる透光性樹脂硬化物も提供する。本発明の熱硬化性樹脂組成物は、酸無水物硬化型エポキシ樹脂に通常用いられる方法により硬化させ、樹脂硬化物とすることができる。本発明の透光性樹脂硬化物は、特定のエポキシ樹脂成分と特定の酸無水物との組み合わせた上記本発明の熱硬化性樹脂組成物の構成により、耐紫外線性および耐熱衝撃性に極めて優れた樹脂硬化物となり、また十分な硬化速度により硬化し得ることから、表面実装型発光ダイオードに好適に使用できる。 The present invention also provides a translucent resin cured product obtained by curing the thermosetting resin composition of the present invention. The thermosetting resin composition of the present invention can be cured by a method usually used for acid anhydride curable epoxy resins to obtain a cured resin. The translucent resin cured product of the present invention is extremely excellent in UV resistance and thermal shock resistance due to the constitution of the thermosetting resin composition of the present invention in combination with a specific epoxy resin component and a specific acid anhydride. Therefore, it can be suitably used for a surface-mount type light emitting diode.
本発明はさらに、本発明の透光性樹脂硬化物により発光素子を封止した発光ダイオードを提供する。本発明の透光性樹脂硬化物は耐紫外線性および耐熱衝撃性に優れ、着色などが少なく、極めて優れた透光性を有していることから、発光波長が５５０ｎｍ以下の青色発光、紫外線発光などの短波長発光ダイオードの封止樹脂として好適に使用することができる。
特に、プリント基板等の表面上に直接ハンダ接合などにより実装するタイプの表面実装型発光ダイオードの場合には、発光素子を封止する透光性樹脂硬化物の量が、２本の接続用端子が透光性樹脂硬化物から延びるいわゆる砲弾型（またはThrough-hole type）に比べて少なく、かつ発光素子表面から透光性樹脂硬化物の表面までの距離が短い。したがって、透光性樹脂硬化物を薄く形成する場合であっても十分な封止を得ることができ好適に使用することができる。The present invention further provides a light-emitting diode in which the light-emitting element is sealed with the light-transmitting resin cured product of the present invention. The light-transmitting resin cured product of the present invention is excellent in ultraviolet resistance and thermal shock resistance, has little coloring, etc., and has extremely excellent light-transmitting properties. Therefore, blue light emission and ultraviolet light emission with an emission wavelength of 550 nm or less. It can be suitably used as a sealing resin for short wavelength light emitting diodes.
In particular, in the case of a surface mount type light emitting diode of a type that is directly mounted on the surface of a printed circuit board by solder bonding or the like, the amount of the light-transmitting resin cured material that seals the light emitting element is two connection terminals. Is smaller than the so-called shell-hole type (or Through-hole type) extending from the light-transmitting resin cured product, and the distance from the light emitting element surface to the surface of the light-transmitting resin cured material is short. Therefore, even when the transparent resin cured product is formed thinly, sufficient sealing can be obtained and it can be used preferably.
また、熱硬化性樹脂組成物に、発光素子、特に好ましくは主発光ピーク波長が５５０ｎｍ以下である発光素子から発光される光の少なくとも一部を吸収して蛍光を発光することが可能な蛍光物質を添加して該発光素子の封止材として使用することにより、該発光素子を含む色変換型発光ダイオードを得ることができる。 In addition, the thermosetting resin composition can be a fluorescent substance capable of emitting fluorescence by absorbing at least a part of light emitted from a light emitting element, particularly preferably a light emitting element having a main emission peak wavelength of 550 nm or less. Is added as a sealing material for the light emitting element, whereby a color conversion type light emitting diode including the light emitting element can be obtained.
以下、本発明を実施例により説明するが、本発明は以下に示す実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to the Example shown below.
［実施例１］
三菱ガス化学（株）の水素添加トリメリット酸無水物（ＨＴＭＡｎ；１．５官能として混合）とダウ・ケミカル社のＥＲＬＸ−４３６０（式（１）の1,4-シクロヘキサンジメタノールと3,4-エポキシシクロヘキサンカルボン酸とのジエステル化合物；２官能）とを化学量論比がほぼ０．５となるように秤量し、８０℃に予備加熱したものをよく攪拌混合して流動性の樹脂組成物を得た。ついで、２ ｍｍ厚の樹脂プレートを作製するための樹脂整形型に樹脂組成物を流しこみ、１２０℃×１時間および１５０℃×３時間の熱硬化処理を施し、硬化物として２ ｍｍ厚の無色透明の樹脂プレートを得た。また、リードフレーム上に配置された表面実装型発光ダイオードのパッケージに当該樹脂組成物を流しこみ、１２０℃×１時間および１５０℃×３時間の熱硬化処理を施し、無色透明の硬化物を得、リードフレームサンプル（表面実装ＬＥＤ）を得た。[Example 1]
Mitsubishi Gas Chemical Co., Ltd. hydrogenated trimellitic anhydride (HTAn; mixed as 1.5 functional) and Dow Chemical's ERLX-4360 (formula (1) 1,4-cyclohexanedimethanol and 3,4 -A diester compound with epoxycyclohexanecarboxylic acid; bifunctional) was weighed so that the stoichiometric ratio was approximately 0.5, and preheated to 80 ° C. and mixed well. Got. Next, the resin composition was poured into a resin shaping mold for producing a 2 mm thick resin plate and subjected to heat curing treatment at 120 ° C. for 1 hour and 150 ° C. for 3 hours to obtain a colorless 2 mm thick product as a cured product. A transparent resin plate was obtained. In addition, the resin composition is poured into a package of surface-mounted light-emitting diodes arranged on a lead frame, and subjected to thermosetting treatment at 120 ° C. for 1 hour and 150 ° C. for 3 hours to obtain a colorless and transparent cured product. A lead frame sample (surface mounted LED) was obtained.
［実施例２］
実施例１に記載の樹脂組成物１００重量部に０．５重量部のＢＨＴを加え、実施例１と同様の手順で、硬化物として２ ｍｍ厚の無色透明の樹脂プレートおよびリードフレームサンプル（表面実装ＬＥＤ）を得た。[Example 2]
0.5 parts by weight of BHT was added to 100 parts by weight of the resin composition described in Example 1, and a 2 mm-thick colorless and transparent resin plate and a lead frame sample (surface) were used in the same procedure as in Example 1. Mounting LED) was obtained.
［比較例１］
実施例１に記載の1,4-シクロヘキサンジメタノールと3,4-エポキシシクロヘキサンカルボン酸とのジエステル化合物に代えて、ジャパンエポキシレジン（株）の水素添加ビスフェノールＡジグリシジルエーテル（ＹＸ８０００；２官能）を用い、実施例１と同様の手順で、硬化物として２ ｍｍ厚のごくわずかに黄色を呈した樹脂プレートおよびリードフレームサンプル（表面実装ＬＥＤ）を得た。[Comparative Example 1]
Instead of the diester compound of 1,4-cyclohexanedimethanol and 3,4-epoxycyclohexanecarboxylic acid described in Example 1, hydrogenated bisphenol A diglycidyl ether (YX8000; bifunctional) of Japan Epoxy Resin Co., Ltd. In the same procedure as in Example 1, a resin plate and a lead frame sample (surface mounted LED) having a very slightly yellow color with a thickness of 2 mm were obtained as a cured product.
［比較例２］
実施例１に記載の1,4-シクロヘキサンジメタノールと3,4-エポキシシクロヘキサンカルボン酸とのジエステル化合物に代えて、ダイセル化学工業（株）の脂環式エポキシ樹脂、セロキサイド２０２１Ｐ（３，４−エポキシシクロヘキセニルメチル−３’，４’−エポシキシクロヘキセンカルボキシレート；２官能）を用い、実施例１と同様の手順で、硬化物として２ ｍｍ厚の無色透明の樹脂プレートおよびリードフレームサンプル（表面実装ＬＥＤ）を得た。[Comparative Example 2]
Instead of the diester compound of 1,4-cyclohexanedimethanol and 3,4-epoxycyclohexanecarboxylic acid described in Example 1, Daicel Chemical Industries, Ltd. alicyclic epoxy resin, Celoxide 2021P (3,4- Using epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate; bifunctional), a colorless transparent resin plate having a thickness of 2 mm as a cured product and a lead frame sample (surface mount) in the same procedure as in Example 1. LED).
［比較例３］
実施例１に記載の1,4-シクロヘキサンジメタノールと3,4-エポキシシクロヘキサンカルボン酸とのジエステル化合物に代えて、阪本薬品工業のヘキサヒドロフタル酸ジグリシジルエステル（ＳＲ−ＨＨＰＡ；２官能）を用い、実施例１と同様の手順で、硬化物として２ ｍｍ厚の無色透明の樹脂プレートおよびリードフレームサンプル（表面実装ＬＥＤ）を得た。[Comparative Example 3]
Instead of the diester compound of 1,4-cyclohexanedimethanol and 3,4-epoxycyclohexanecarboxylic acid described in Example 1, Sakamoto Pharmaceutical's hexahydrophthalic acid diglycidyl ester (SR-HHPA; bifunctional) was used. Using the same procedure as in Example 1, a colorless transparent resin plate having a thickness of 2 mm and a lead frame sample (surface mount LED) were obtained as a cured product.
［比較例４］
実施例１に記載の1,4-シクロヘキサンジメタノールと3,4-エポキシシクロヘキサンカルボン酸とのジエステル化合物に代えて、東亞合成(株)の脂環式エポキシ変性テトラメチルジシロキサン（式（７）、ＢＥＰ−ＳＩ２；２官能）を用い、実施例１と同様の手順で硬化物として２ ｍｍ厚の無色透明の樹脂プレートおよびリードフレームサンプル（表面実装ＬＥＤ）を得た。
Instead of the diester compound of 1,4-cyclohexanedimethanol and 3,4-epoxycyclohexanecarboxylic acid described in Example 1, an alicyclic epoxy-modified tetramethyldisiloxane (formula (7)) manufactured by Toagosei Co., Ltd. , BEP-SI2; bifunctional) and a 2 mm thick colorless and transparent resin plate and lead frame sample (surface mount LED) were obtained as a cured product in the same procedure as in Example 1.
［比較例５］
新日本理化（株）のメチルヘキサヒドロフタル酸無水物（ＭＨ−７００；１官能）とダウ・ケミカル社のＥＲＬＸ−４３６０（式（１）の1,4-シクロヘキサンジメタノールと3,4-エポキシシクロヘキサンカルボン酸とのジエステル化合物；２官能）とを化学量論比がほぼ０．５となるように秤量し、さらに全体１００重量部に対して有機ホスホニウム塩化合物エポキシ硬化触媒、日本化学工業（株）製 ヒシコーリンＰＸ−４ＥＴ ０．２重量部を硬化促進剤として加えたものをよく攪拌混合して、流動性の樹脂組成物を得た。以降は実施例１と同じ手順で硬化物として２ ｍｍ厚のごくわずかに黄色を呈した樹脂プレートおよびリードフレームサンプル（表面実装ＬＥＤ）を得た。[Comparative Example 5]
Methylhexahydrophthalic anhydride (MH-700; monofunctional) from Shin Nippon Rika Co., Ltd. and ERLX-4360 from Dow Chemical Company (1,4-cyclohexanedimethanol and 3,4-epoxy of formula (1)) Diester compound with cyclohexanecarboxylic acid; bifunctional) was weighed so that the stoichiometric ratio was about 0.5, and further, an organic phosphonium salt compound epoxy curing catalyst for 100 parts by weight as a whole, Nippon Chemical Industry Co., Ltd. ) Hishicolin PX-4ET 0.2 parts by weight added as a curing accelerator was thoroughly stirred and mixed to obtain a fluid resin composition. Thereafter, a resin plate and a lead frame sample (surface mounted LED) having a very slightly yellow color with a thickness of 2 mm were obtained as a cured product in the same procedure as in Example 1.
［比較例６］
比較例５に記載の1,4-シクロヘキサンジメタノールと3,4-エポキシシクロヘキサンカルボン酸とのジエステル化合物に代えて、ジャパンエポキシレジン（株）の水素添加ビスフェノールＡジグリシジルエーテル（ＹＸ８０００）を用い、比較例５と同様の手順で硬化物として２ ｍｍ厚のごくわずかに黄色を呈した樹脂プレートおよびリードフレームサンプル（表面実装ＬＥＤ）を得た。[Comparative Example 6]
Instead of the diester compound of 1,4-cyclohexanedimethanol and 3,4-epoxycyclohexanecarboxylic acid described in Comparative Example 5, hydrogenated bisphenol A diglycidyl ether (YX8000) from Japan Epoxy Resin Co., Ltd. was used. A resin plate and a lead frame sample (surface mounted LED) having a very slight yellow color of 2 mm thickness were obtained as a cured product by the same procedure as in Comparative Example 5.
［比較例７］
比較例５に記載の1,4-シクロヘキサンジメタノールと3,4-エポキシシクロヘキサンカルボン酸とのジエステル化合物に代えて、ダイセル化学工業（株）の脂環式エポキシ樹脂、セロキサイド２０２１Ｐを用い、比較例５と同様の手順で硬化物として２ ｍｍ厚のごくわずかに黄色を呈した樹脂プレートおよびリードフレームサンプル（表面実装ＬＥＤ）を得た。[Comparative Example 7]
In place of the diester compound of 1,4-cyclohexanedimethanol and 3,4-epoxycyclohexanecarboxylic acid described in Comparative Example 5, an alicyclic epoxy resin, Celoxide 2021P from Daicel Chemical Industries, Ltd. was used as a comparative example. A resin plate and a lead frame sample (surface mount LED) having a very slightly yellow color with a thickness of 2 mm were obtained by the same procedure as in No. 5.
上記実施例１、２および比較例１〜７で得られた樹脂プレートサンプルおよびリードフレームサンプル（表面実装ＬＥＤ）を使用して、下記（１）〜（４）に示す耐紫外線性試験、耐熱安定性試験、耐熱衝撃性試験および体積減少度評価試験を行った。 Using the resin plate samples and lead frame samples (surface mounted LEDs) obtained in Examples 1 and 2 and Comparative Examples 1 to 7, UV resistance tests and heat stability shown in the following (1) to (4) Property test, thermal shock resistance test and volume reduction degree evaluation test were conducted.
（１）耐紫外線性試験
ウシオ電機製SP-V超高圧水銀ランプからの光をカットオフフィルターに通し、350 nm以下の紫外光成分を除去したものを樹脂プレートに集光照射し、目視により黄変が認められるまでの時間でサンプルの耐紫外線性を評価した。サンプル照射面での光照度は5000 mW/cm２、スポット径は 5 mmとした。評価時の雰囲気温度は60℃に設定した。
評価基準
◎:>100時間
○:50〜100時間
△:5〜50時間
×:<5時間(1) Ultraviolet resistance test Light from the SP-V ultra-high pressure mercury lamp manufactured by USHIO ELECTRIC CO., LTD. The UV resistance of the sample was evaluated by the time until the change was recognized. The light illuminance on the sample irradiation surface was 5000 mW / cm2 and the spot diameter was 5 mm. The atmospheric temperature at the time of evaluation was set to 60 ° C.
Evaluation criteria ◎:> 100 hours ○: 50-100 hours △: 5-50 hours ×: <5 hours
（２）耐熱安定性試験
180℃の電気乾燥炉内に樹脂プレートサンプルを48時間放置した後の黄変の程度を目視で評価し、サンプルの耐熱安定性を評価した。
評価基準
◎:変化なし
○:わずかな着色
△: 黄変
×:強い黄変（褐色変）(2) Heat stability test
The degree of yellowing after the resin plate sample was left in an electric drying oven at 180 ° C. for 48 hours was visually evaluated to evaluate the heat stability of the sample.
Evaluation criteria ◎: No change ○: Slight coloration △: Yellowing ×: Strong yellowing (browning)
（３）耐熱衝撃性試験
-40℃および120℃に各15分暴露の熱ショックサイクルを繰り返し、リードフレームサンプルにおいて樹脂のクラックあるいは樹脂−基材間の剥離が初めて認められるサイクル数でサンプルの耐熱衝撃性を評価した。
評価基準
◎:>1000回
○:200〜1000回
△:50〜200回
×:<50回(3) Thermal shock resistance test
The thermal shock cycle was repeated at -40 ° C and 120 ° C for 15 minutes each, and the thermal shock resistance of the sample was evaluated by the number of cycles in which lead cracking was first observed in a lead frame sample.
Evaluation criteria ◎:> 1000 times ○: 200-1000 times △: 50-200 times ×: <50 times
（４）体積減少度評価試験
リードフレームサンプルに硬化前樹脂組成物を開口部が平面となるまで満たし、それを硬化させた時の体積減少に伴う樹脂表面の凹化の有無を目視で評価した。
評価基準
○:体積減少・凹化なし
×:体積減少・凹化あり(4) Volume reduction degree evaluation test The lead frame sample was filled with the pre-curing resin composition until the opening became a flat surface, and the presence or absence of depression of the resin surface due to the volume reduction when it was cured was visually evaluated. .
Evaluation criteria ○: Volume reduction / no depression ×: Volume reduction / concave
下記表に実施例１から比較例７までの評価結果を示す。
上記表に示した結果から明らかなように、本発明の熱硬化性樹脂組成物が与える硬化物は耐紫外線性および耐熱安定性のいずれにも優れているのみならず、優れた耐熱衝撃性を有している。特に最適量のフェノール系酸化防止剤を配合した硬化物（実施例２）はエポキシ樹脂としては特筆すべき耐紫外線性および耐熱衝撃性を有している。
As is clear from the results shown in the above table, the cured product provided by the thermosetting resin composition of the present invention is not only excellent in both UV resistance and heat stability, but also has excellent thermal shock resistance. Have. In particular, a cured product (Example 2) containing an optimal amount of a phenolic antioxidant has UV resistance and thermal shock resistance, which are notable as an epoxy resin.
Claims (13)
Translated fromJapanese11. A light emitting diode, wherein the light emitting element has a main emission peak wavelength of 550 nm or less, and the light emitting element is sealed with the light-transmitting resin cured product according to claim 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005223852AJP2007039521A (en) | 2005-08-02 | 2005-08-02 | Thermosetting resin composition, translucent cured product obtained by thermosetting said composition, and light emitting diode sealed with said cured product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005223852AJP2007039521A (en) | 2005-08-02 | 2005-08-02 | Thermosetting resin composition, translucent cured product obtained by thermosetting said composition, and light emitting diode sealed with said cured product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2007039521Atrue JP2007039521A (en) | 2007-02-15 |
Family
ID=37797811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005223852APendingJP2007039521A (en) | 2005-08-02 | 2005-08-02 | Thermosetting resin composition, translucent cured product obtained by thermosetting said composition, and light emitting diode sealed with said cured product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2007039521A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009041389A1 (en) | 2007-09-27 | 2009-04-02 | Mitsubishi Gas Chemical Company, Inc. | Epoxy resin composition, cured object obtained therefrom, and light-emitting diode |
| JP2010241942A (en)* | 2009-04-03 | 2010-10-28 | Nippon Kayaku Co Ltd | Diolefin compound, epoxy resin, curable resin composition and cured product thereof |
| WO2011019003A1 (en)* | 2009-08-10 | 2011-02-17 | 三菱瓦斯化学株式会社 | Thermosetting resin composition for surface protection layers |
| WO2011043474A1 (en)* | 2009-10-09 | 2011-04-14 | 日本化薬株式会社 | Curable resin composition and cured products thereof |
| KR20150084824A (en) | 2012-11-09 | 2015-07-22 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Epoxy resin composition, cured product of same, and light emitting diode |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003176334A (en)* | 2001-01-24 | 2003-06-24 | Nichia Chem Ind Ltd | Epoxy resin composition, method for producing the same, and optical semiconductor device using the same |
| JP2005036218A (en)* | 2003-06-30 | 2005-02-10 | Mitsubishi Gas Chem Co Inc | Thermosetting resin composition and use thereof |
| WO2005044890A1 (en)* | 2003-11-03 | 2005-05-19 | Union Carbide Chemicals & Plastics Technology Corporation | Tougher cycloaliphatic epoxide resins |
- 2005
- 2005-08-02JPJP2005223852Apatent/JP2007039521A/enactivePending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003176334A (en)* | 2001-01-24 | 2003-06-24 | Nichia Chem Ind Ltd | Epoxy resin composition, method for producing the same, and optical semiconductor device using the same |
| JP2005036218A (en)* | 2003-06-30 | 2005-02-10 | Mitsubishi Gas Chem Co Inc | Thermosetting resin composition and use thereof |
| WO2005044890A1 (en)* | 2003-11-03 | 2005-05-19 | Union Carbide Chemicals & Plastics Technology Corporation | Tougher cycloaliphatic epoxide resins |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009041389A1 (en) | 2007-09-27 | 2009-04-02 | Mitsubishi Gas Chemical Company, Inc. | Epoxy resin composition, cured object obtained therefrom, and light-emitting diode |
| US9102786B2 (en) | 2007-09-27 | 2015-08-11 | Mitsubishi Gas Chemical Company, Inc. | Epoxy resin composition, cured object obtained therefrom, and light-emitting diode |
| JP2010241942A (en)* | 2009-04-03 | 2010-10-28 | Nippon Kayaku Co Ltd | Diolefin compound, epoxy resin, curable resin composition and cured product thereof |
| WO2011019003A1 (en)* | 2009-08-10 | 2011-02-17 | 三菱瓦斯化学株式会社 | Thermosetting resin composition for surface protection layers |
| US20120142822A1 (en)* | 2009-08-10 | 2012-06-07 | Mitsubishi Gas Chemical Company, Inc. | Thermosetting resin composition for surface protection layers |
| US9028911B2 (en)* | 2009-08-10 | 2015-05-12 | Mitsubishi Gas Chemical Company, Inc. | Thermosetting resin composition for surface protection layers |
| WO2011043474A1 (en)* | 2009-10-09 | 2011-04-14 | 日本化薬株式会社 | Curable resin composition and cured products thereof |
| JP5519685B2 (en)* | 2009-10-09 | 2014-06-11 | 日本化薬株式会社 | Curable resin composition and cured product thereof |
| KR20150084824A (en) | 2012-11-09 | 2015-07-22 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Epoxy resin composition, cured product of same, and light emitting diode |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4808056B2 (en) | Thermosetting resin composition, translucent cured product obtained by thermosetting said composition, and light emitting diode sealed with said cured product | |
| JP4250949B2 (en) | Light emitting device and manufacturing method thereof | |
| WO2006109768A1 (en) | Light-transmitting resin composition | |
| KR20150047448A (en) | LED encapsulant | |
| JP2003176333A (en) | Epoxy resin composition, solid state device encapsulated with the composition, and encapsulation method | |
| JP2003192765A (en) | Epoxy resin composition, solid state device encapsulated with the composition, and encapsulation method | |
| JP4421192B2 (en) | Sealing resin composition for light emitting diode and surface mount light emitting diode using the same | |
| JP2008163260A (en) | Light emitting device sealing resin composition and lamp | |
| JP4301905B2 (en) | Thermosetting resin composition, light emitting diode having light emitting element sealed with the thermosetting resin composition, and color conversion type light emitting diode | |
| JP2003073452A (en) | Epoxy resin and epoxy resin material for ultraviolet light emitting device | |
| JP2012041403A (en) | Thermosetting epoxy resin composition and semiconductor device | |
| JP2006193570A (en) | Thermosetting resin composition, translucent cured product obtained by thermosetting said composition, and light emitting diode sealed with said cured product | |
| JP2006182961A (en) | Thermosetting transparent resin composition, translucent cured product obtained by thermosetting the composition, and light emitting diode sealed with the cured product | |
| JP3876251B2 (en) | Thermosetting resin composition and light emitting diode using the composition as sealant | |
| JP2007039521A (en) | Thermosetting resin composition, translucent cured product obtained by thermosetting said composition, and light emitting diode sealed with said cured product | |
| TW201833167A (en) | Curing resin composition for light reflection and cured product thereof, and optical semiconductor device | |
| JP2006093716A (en) | White light emitting device and manufacturing method thereof | |
| JP4433876B2 (en) | Epoxy resin composition and adhesive for optical semiconductor using the same | |
| JP2003012896A (en) | UV-resistant epoxy resin and light emitting diode or wavelength conversion element for light emitting diode sealed using the epoxy resin | |
| JP2007039522A (en) | Thermosetting resin composition, translucent cured product obtained by thermosetting said composition, and light emitting diode sealed with said cured product | |
| KR20130134942A (en) | Epoxy resin composition and light emitting apparatus | |
| US20100213490A1 (en) | Sealing composition for light emitting device and light emitting device including the same | |
| TW201233724A (en) | Resin composition | |
| WO2015083576A1 (en) | Heat-curable resin composition for optical semiconductor device, lead frame for optical semiconductor device and obtained using same, and optical semiconductor device | |
| JP5544819B2 (en) | Epoxy group-containing adhesive resin composition and optical semiconductor adhesive using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination | Free format text:JAPANESE INTERMEDIATE CODE: A621 Effective date:20080714 | |
| A977 | Report on retrieval | Free format text:JAPANESE INTERMEDIATE CODE: A971007 Effective date:20101207 | |
| A131 | Notification of reasons for refusal | Free format text:JAPANESE INTERMEDIATE CODE: A131 Effective date:20101214 | |
| A02 | Decision of refusal | Free format text:JAPANESE INTERMEDIATE CODE: A02 Effective date:20110412 |