JP2011001418A - Resin composition for sealing optical semiconductor - Google Patents
Resin composition for sealing optical semiconductor Download PDFInfo
- Publication number
- JP2011001418A JP2011001418A JP2009144119A JP2009144119A JP2011001418A JP 2011001418 A JP2011001418 A JP 2011001418A JP 2009144119 A JP2009144119 A JP 2009144119A JP 2009144119 A JP2009144119 A JP 2009144119A JP 2011001418 A JP2011001418 A JP 2011001418A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- optical semiconductor
- viscosity
- resin
- meth
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3236—Heterocylic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/06—Triglycidylisocyanurates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Abstract
Description
本発明は、無色透明な光半導体封止用樹脂組成物に関する。 The present invention relates to a colorless and transparent resin composition for encapsulating an optical semiconductor.
一般に、ＬＥＤ（発光ダイオード素子）、フォトトランジスタ、フォトダイオード、ＣＣＤ（電荷結合素子）、ＥＰＲＯＭ（消去・書込可能ＲＯＭ）等の受光あるいは発光するための光半導体チップ分野で利用されているパッケージ封止の代表的態様の一つとして、半導体封止用樹脂組成物をシリンジに充填し、シリンジの細いノズル（約１０μｍ経）から光半導体チップを収容したパッケージ容器に供給したり、実装基板に実装された光半導体チップにポッティングしたりするというディスペンス方式が広く利用されている。 In general, package packages used in the field of optical semiconductor chips for receiving or emitting light such as LEDs (light emitting diode elements), phototransistors, photodiodes, CCDs (charge coupled devices), EPROMs (erasable / writable ROM), etc. As one of the typical forms of stopping, a resin composition for semiconductor sealing is filled in a syringe and supplied to a package container containing an optical semiconductor chip from a thin nozzle (approximately 10 μm) of the syringe or mounted on a mounting substrate. A dispensing method in which potting is performed on the manufactured optical semiconductor chip is widely used.
このようなディスペンス方式に適用される光半導体封止用樹脂組成物に対しては、封止作業、特にポッティングの作業の際に、ディスペンサーから吐出させるときには低粘度を示し、ポッティング後には高粘度を示して流動しにくくなるように、高チクソ性を示すことが求められている。また、光半導体封止用樹脂組成物の硬化物に対しては、経時的に変化しない透明性が求められている。更に、硬化物と封止すべき光半導体チップを搭載する基材との間の線膨張係数の差に起因して硬化物に反りやクラックが生ずることがあるが、硬化物に対してはそのような反りやクラックの発生がないという性質、即ち、良好な耐クラック性を示すこと等が求められている。さらに、硬化した封止樹脂材料の紫外線による変色の抑制が急務の問題となっている。 The optical semiconductor sealing resin composition applied to such a dispensing method exhibits a low viscosity when discharged from a dispenser during sealing, particularly potting, and has a high viscosity after potting. It is required to exhibit high thixotropy so that it is difficult to flow. Moreover, the transparency which does not change with time is calculated | required with respect to the hardened | cured material of the resin composition for optical semiconductor sealing. Furthermore, the cured product may be warped or cracked due to the difference in linear expansion coefficient between the cured product and the substrate on which the optical semiconductor chip to be sealed is mounted. There is a demand for the property that such warpage and cracks do not occur, that is, good crack resistance. Furthermore, suppression of discoloration of the cured encapsulating resin material by ultraviolet rays is an urgent issue.
このような様々な要求を満たすべく、ディスペンス方式に適用される従来の光半導体封止用樹脂組成物は、光透過性、接着性、コストの観点から、液状のビスフェノールＡ型エポキシ主剤あるいは脂環式エポキシ主剤に、ヘキサヒドロフタル酸無水物等の酸無水物系硬化剤と、硬化促進剤と、必要に応じて老化防止剤とを配合した比較的高粘度の樹脂組成物から構成されている。 In order to satisfy such various requirements, the conventional resin composition for encapsulating an optical semiconductor applied to the dispensing system is a liquid bisphenol A type epoxy main agent or alicyclic ring from the viewpoint of light transmittance, adhesiveness, and cost. It is composed of a relatively high viscosity resin composition in which an acid anhydride-based curing agent such as hexahydrophthalic anhydride, a curing accelerator, and an anti-aging agent as necessary is blended with a basic epoxy compound. .
ところが、近年、光半導体チップにおいては、使用する光源の短波長化や高出力化が大きく進行しており、光半導体封止用樹脂組成物に対しても今まで以上の耐熱光耐久性が求められるようになっている。このため、液状のエポキシ主剤の一部を、より良好な耐熱光耐久性を示す室温で粉末固体のトリス−（２，３−エポキシプロピル）−イソシアヌレートアヌレートに換えることが提案されている（特許文献１の実施例１）。この半導体封止樹脂組成物の硬化物は、エポキシ主剤の一部にトリス−（２，３−エポキシプロピル）−イソシアヌレートを使用しているために、経時的に良好な透明性と、良好な耐クラック性と、良好な耐熱光耐久性とを示すと期待できる。 However, in recent years, in optical semiconductor chips, there has been a great progress in shortening the wavelength and increasing the output of the light source to be used. It is supposed to be. For this reason, it has been proposed to replace a part of the liquid epoxy base material with tris- (2,3-epoxypropyl) -isocyanurate annulate which is a powdered solid at room temperature which exhibits better heat and light durability ( Example 1 of Patent Document 1). The cured product of this semiconductor encapsulating resin composition uses tris- (2,3-epoxypropyl) -isocyanurate as a part of the epoxy main agent, so that it has good transparency over time and good It can be expected to exhibit crack resistance and good heat-resistant light durability.
しかしながら、特許文献１の光半導体封止用樹脂組成物の場合、トリス−（２，３−エポキシプロピル）−イソシアヌレートが液状のビスフェノールＡ型エポキシ主剤あるいは脂環式エポキシ主剤に溶解しにくく、いったん加熱溶解させたとしても冷却により析出してしまう場合があるという問題があった。このため、エポキシ主剤に高濃度でトリス−（２，３−エポキシプロピル）−イソシアヌレートを配合した光半導体封止用樹脂組成物あるいはエポキシ主剤としてトリス−（２，３−エポキシプロピル）−イソシアヌレートのみを使用した光半導体封止用樹脂組成物の場合、ディスペンサーノズルに目詰まりが生じるおそれがあるため、ディスペンス方式への適用が難しいという問題があった。しかも、析出したトリス−（２，３−エポキシプロピル）−イソシアヌレートが樹脂組成物中で沈降してしまい、均一な組成で樹脂封止することができないという問題もあった。しかも、特許文献１の光半導体封止用樹脂組成物の場合、ディスペンス方式に適した高チクソ性を実現するための考慮は全くなされていない。 However, in the case of the resin composition for optical semiconductor encapsulation of Patent Document 1, tris- (2,3-epoxypropyl) -isocyanurate is difficult to dissolve in the liquid bisphenol A type epoxy main agent or alicyclic epoxy main agent. There is a problem that even if heated and dissolved, it may precipitate due to cooling. For this reason, the resin composition for optical semiconductor sealing which mix | blended tris- (2,3-epoxypropyl) -isocyanurate with high concentration in the epoxy main ingredient, or tris- (2,3-epoxypropyl) -isocyanurate as the epoxy main ingredient In the case of the resin composition for encapsulating an optical semiconductor using only the liquid, there is a possibility that the dispenser nozzle may be clogged, which makes it difficult to apply to the dispensing method. In addition, the precipitated tris- (2,3-epoxypropyl) -isocyanurate settles in the resin composition, and there is a problem that the resin cannot be sealed with a uniform composition. In addition, in the case of the resin composition for sealing an optical semiconductor of Patent Document 1, no consideration has been made to realize high thixotropy suitable for the dispensing method.
本発明の目的は、上述したような従来の問題点を解決しようとするものであり、トリス−（２，３−エポキシプロピル）−イソシアヌレートなどのトリグリシジルイソシアヌレート類をエポキシ主剤として使用する光半導体封止用樹脂組成物に高チクソ性を付与し、しかもその硬化物に経時的に良好な透明性と良好な耐クラック性と良好な耐熱光耐久性とを同時に付与することである。 An object of the present invention is to solve the conventional problems as described above, and is a light using triglycidyl isocyanurates such as tris- (2,3-epoxypropyl) -isocyanurate as an epoxy main agent. It is to impart high thixotropy to the resin composition for semiconductor encapsulation, and to simultaneously impart good transparency, good crack resistance and good heat-resistant durability to the cured product over time.
本発明者は、エポキシ主剤であるトリグリシジルイソシアヌレート類を、特定の重量平均分子量と特定の粘度とを示す高チクソ性のグリシジル基含有（メタ）アクリル酸エステル系樹脂に分散させ、光半導体封止用樹脂組成物自体の粘度を特定範囲に調整すると共に、チクソトロピックインデックスも特定範囲に調整することにより、上述の目的を達成できることを見出し、本発明を完成させた。 The present inventor has dispersed triglycidyl isocyanurates, which are epoxy base materials, in a highly thixotropic glycidyl group-containing (meth) acrylic acid ester-based resin exhibiting a specific weight average molecular weight and a specific viscosity, thereby encapsulating an optical semiconductor. The inventors have found that the above-mentioned object can be achieved by adjusting the viscosity of the stopping resin composition itself to a specific range and adjusting the thixotropic index to a specific range, and completed the present invention.
即ち、本発明は、トリグリシジルイソシアヌレート類を含有するエポキシ成分と、酸無水物系硬化剤と、重量平均分子量が２００００〜６５０００、粘度が１０００〜１００００Ｐａ・ｓであるグリシジル基含有（メタ）アクリル酸エステル系樹脂と、硬化促進剤とを含有する光半導体封止用樹脂組成物であって、粘度が１０〜２００Ｐａ・ｓであり、且つチクソトロピックインデックスが３〜１５であることを特徴とする光半導体封止用樹脂組成物を提供する。 That is, the present invention relates to an epoxy component containing triglycidyl isocyanurates, an acid anhydride curing agent, a glycidyl group-containing (meth) acrylic having a weight average molecular weight of 20,000 to 65,000 and a viscosity of 1,000 to 10,000 Pa · s. An optical semiconductor encapsulating resin composition comprising an acid ester resin and a curing accelerator, wherein the viscosity is 10 to 200 Pa · s and the thixotropic index is 3 to 15. A resin composition for optical semiconductor encapsulation is provided.
また、本発明は、光半導体チップが、上述の光半導体封止用樹脂組成物で半導体パッケージに封止されてなる光半導体装置を提供する。 The present invention also provides an optical semiconductor device in which an optical semiconductor chip is sealed in a semiconductor package with the above-described resin composition for sealing an optical semiconductor.
本発明の光半導体封止用樹脂組成物は、エポキシ主剤となるエポキシ成分にトリグリシジルイソシアヌレート類を配合し、且つエポキシ成分の分散媒体として特定の重量平均分子量と特定の粘度とを示す高チクソ性のグリシジル基含有（メタ）アクリル酸エステル系樹脂を使用する。このため、光半導体封止用樹脂組成物は、高チクソ性を示し、しかもトリグリシジルイソシアヌレート類は沈降せずに良好な分散状態となっている。従って、本発明の光半導体封止用樹脂組成物は、ディスペンス方式に適したものとなっている。また、その硬化物は、エポキシ主剤となるエポキシ化合物にトリグリシジルイソシアヌレート類を配合しているために、経時的に良好な透明性と良好な耐クラック性と良好な耐熱光耐久性とを同時に示す。 The resin composition for encapsulating an optical semiconductor according to the present invention is a high thixotrope having a specific weight average molecular weight and a specific viscosity as a dispersion medium of an epoxy component by blending triglycidyl isocyanurates with an epoxy component as an epoxy main component. Glycidyl group-containing (meth) acrylic ester resin is used. For this reason, the resin composition for optical semiconductor sealing shows high thixotropy, and the triglycidyl isocyanurates are in a well dispersed state without being settled. Therefore, the resin composition for sealing an optical semiconductor of the present invention is suitable for a dispensing method. Moreover, since the cured product contains triglycidyl isocyanurates in an epoxy compound as an epoxy main agent, it has good transparency over time, good crack resistance, and good heat-resistant durability at the same time. Show.
本発明の光半導体封止用樹脂組成物は、光半導体チップを半導体パッケージに封止するためのものであり、基本的にエポキシ主剤となるエポキシ成分とグリシジル基含有（メタ）アクリル酸エステル系樹脂と硬化促進剤とを含有する。ここで、光半導体チップとしては、発光または受光する機能を有する半導体チップが挙げられ、具体的にはＬＥＤ（発光ダイオード素子）、フォトトランジスタ、フォトダイオード、ＣＣＤ（電荷結合素子）、ＥＰＲＯＭ（消去・書込可能ＲＯＭ）等が挙げられる。また、従来の光半導体パッケージに使用されているものと同様のものを使用することができる。 The resin composition for encapsulating an optical semiconductor of the present invention is for encapsulating an optical semiconductor chip in a semiconductor package, and basically comprises an epoxy component which is an epoxy main component and a glycidyl group-containing (meth) acrylic ester resin. And a curing accelerator. Here, examples of the optical semiconductor chip include a semiconductor chip having a function of emitting or receiving light. Specifically, an LED (light emitting diode element), a phototransistor, a photodiode, a CCD (charge coupled device), an EPROM (erasing / erasing device). And a writable ROM). Moreover, the thing similar to what is used for the conventional optical semiconductor package can be used.
本発明の光半導体封止用樹脂組成物は、レオメーター（例えば、レオストレスＲＳ−１５０、ＨＡＡＫＥ社製、パラレルプレート使用、ギャップ０．０５２ｍｍ、周波数０．６〜６００ｓ−１）を用いて２５℃、１０ｓ−１で測定した粘度が１０〜２００Ｐａ・ｓ、好ましくは１２〜２０Ｐａ・ｓであり、且つ１ｓ−１で測定した粘度値を１０ｓ−１で測定した粘度値で除して得たチクソトロピックインデックスが３〜１５、好ましくは４〜７であることを特徴とする。粘度が１０Ｐａ・ｓ未満であるとトリグリシジルイソシアヌレート類が沈降し、２００Ｐａ・ｓを超えるとディスペンサーノズルからの吐出が困難となる。また、チクソトロピックインデックスが３未満であると、粉末のエポキシ成分の樹脂組成物中の含有量が少なすぎることを意味し、このことは、架橋相手の酸無水物系硬化剤の官能基が１００％架橋できず、換言すれば官能基の一部が架橋反応に寄与しないこととなり、耐熱光特性に悪影響を与える。また、１５を超えると粉末成分に対する液状成分の割合が高いことを意味し、樹脂組成物の吐出時及び吐出後に相分離が生じることが懸念される。ここで、レオメーター測定において「１０ｓ−１」という条件は、ディスペンサーノズルから吐出されるときのような強い剪断力が付加された状態を想定しており、「１ｓ−１」という条件は、シリンジ中で保存あるいは移送されているような弱い剪断力が付加された状態を想定している。 The resin composition for optical semiconductor encapsulation of the present invention is 25 using a rheometer (for example, rheostress RS-150, manufactured by HAAKE, using a parallel plate, gap 0.052 mm, frequency 0.6 to 600 s −1 ). The viscosity measured at 10 ° C. and 10 s −1 is 10 to 200 Pa · s, preferably 12 to 20 Pa · s, and the viscosity value measured at 1 s −1 is divided by the viscosity value measured at 10 s −1 . The thixotropic index is 3 to 15, preferably 4 to 7. When the viscosity is less than 10 Pa · s, triglycidyl isocyanurates precipitate, and when it exceeds 200 Pa · s, it becomes difficult to discharge from the dispenser nozzle. Further, if the thixotropic index is less than 3, it means that the content of the powdered epoxy component in the resin composition is too small, and this means that the functional group of the acid anhydride curing agent as the crosslinking partner is 100. % Cannot be cross-linked, in other words, a part of the functional group does not contribute to the cross-linking reaction, which adversely affects the heat resistant light characteristics. Moreover, when it exceeds 15, it means that the ratio of the liquid component with respect to a powder component is high, and we are anxious about phase separation arising at the time of discharge of a resin composition and after discharge. Here, in the rheometer measurement, the condition of “10 s −1 ” assumes a state in which a strong shearing force is applied as when discharged from the dispenser nozzle, and the condition of “1 s −1 ” It is assumed that a weak shear force such as stored or transported is applied.
本発明において使用するエポキシ成分は、トリグリシジルイソシアヌレート類を含有する。トリグリシジルイソシアヌレート類としては、トリス−（２，３−エポキシプロピル）イソシアヌレート、低級アルキル基、低級アルコキシ基または低級アシルオキシ基置換トリグリシジルイソシアヌレート（特開２００８−４５０１４号公報、段落００２１〜００２３）、脂肪族または脂環式カルボン酸変性トリグリシジルイソシアヌレート（特開２００８−４５０１４号公報、段落００２５〜００３２）を挙げることができる。特に好ましいトリグリシジルイソシアヌレート類としては、前述のトリス−（２，３−エポキシプロピル）イソシアヌレートを挙げることができる。 The epoxy component used in the present invention contains triglycidyl isocyanurates. Examples of triglycidyl isocyanurates include tris- (2,3-epoxypropyl) isocyanurate, lower alkyl group, lower alkoxy group or lower acyloxy group-substituted triglycidyl isocyanurate (Japanese Patent Laid-Open No. 2008-45014, paragraphs 0021 to 0023). ), Aliphatic or alicyclic carboxylic acid-modified triglycidyl isocyanurate (Japanese Patent Laid-Open No. 2008-45014, paragraphs 0025 to 0032). Particularly preferable triglycidyl isocyanurates include the aforementioned tris- (2,3-epoxypropyl) isocyanurates.
エポキシ成分中のトリグリシジルイソシアヌレート類の含有量は、少なすぎると耐熱光耐久性が不十分となるので、少なくとも６０質量％、好ましくは８０質量％以上である。エポキシ化合物の全量がトリグリシジルイソシアヌレート類でもよい。 If the content of triglycidyl isocyanurates in the epoxy component is too small, the heat and light durability becomes insufficient, so that it is at least 60% by mass, preferably 80% by mass or more. The total amount of the epoxy compound may be triglycidyl isocyanurates.
エポキシ成分は、必要に応じて、トリグリシジルイソシアヌレート類以外の公知のエポキシ化合物を含有してもよい。この場合、透明性（特に無色透明性）を確保する観点から分子内に二重結合が存在しない液状のものが好ましく、特に脂環式エポキシ化合物および／または水添芳香族エポキシ化合物を使用することが好ましい。脂環式エポキシ化合物としては、３，４−エポキシシクロヘキセニルメチル−３´，４´−エポキシシクロヘキセンカルボキシレートあるいは２，２−ビス（ヒドロキシメチル）−１−ブタノール、１，２−エポキシ−４−２（オキシラニル）シクロヘキサン付加物等が挙げられる。水添芳香族エポキシ化合物としては、水添ビスフェノールＡ型エポキシ化合物、水添ビスフェノールＦ型エポキシ化合物等が挙げられる。中でも、耐熱光透過性の点から３，４−エポキシシクロヘキセニルメチル−３´，４´−エポキシシクロヘキセンカルボキシレート又は水添ビスフェノールＡ型エポキシ化合物を好ましく使用することができる。また、液状の１，３，５−トリ−２−プロペニル−１，３，５−トリアジン−２，４，５（１Ｈ，Ｈ，５Ｈ）−トリオン、モノアリルジグリシジルイソシアヌレート、ジアリルグリシジルイソシアヌレートも併用できる。 The epoxy component may contain a known epoxy compound other than triglycidyl isocyanurates as necessary. In this case, from the viewpoint of ensuring transparency (especially colorless transparency), a liquid compound having no double bond in the molecule is preferable, and in particular, an alicyclic epoxy compound and / or a hydrogenated aromatic epoxy compound should be used. Is preferred. Examples of alicyclic epoxy compounds include 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, 2,2-bis (hydroxymethyl) -1-butanol, and 1,2-epoxy-4- Examples include 2 (oxiranyl) cyclohexane adducts. Examples of the hydrogenated aromatic epoxy compound include a hydrogenated bisphenol A type epoxy compound and a hydrogenated bisphenol F type epoxy compound. Among these, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate or hydrogenated bisphenol A type epoxy compound can be preferably used from the viewpoint of heat-resistant light transmittance. Liquid 1,3,5-tri-2-propenyl-1,3,5-triazine-2,4,5 (1H, H, 5H) -trione, monoallyl diglycidyl isocyanurate, diallyl glycidyl isocyanurate Can also be used together.
エポキシ成分の光半導体封止用樹脂組成物の配合量は、少なすぎても多すぎても耐熱光特性を低下させるので、エポキシ成分と酸無水物系硬化剤とグリシジル基含有（メタ）アクリル酸エステル系樹脂との合計に対し、好ましくは３０〜７０質量％、より好ましくは４０ 〜６０質量％である。特に、トリグリシジルイソシアヌレート類の含有量は、エポキシ成分と酸無水物系硬化剤とグリシジル基含有（メタ）アクリル酸エステル系樹脂との合計に対し、好ましくは３０〜５０質量％、より好ましくは３５〜４５質量％である。 If the amount of the epoxy component resin composition for encapsulating an optical semiconductor is too small or too large, the heat resistant light characteristics are deteriorated. Therefore, the epoxy component, the acid anhydride curing agent, and the glycidyl group-containing (meth) acrylic acid Preferably it is 30-70 mass% with respect to the sum total with ester resin, More preferably, it is 40-60 mass%. In particular, the content of triglycidyl isocyanurates is preferably 30 to 50% by mass, more preferably based on the total of the epoxy component, the acid anhydride curing agent, and the glycidyl group-containing (meth) acrylic ester resin. It is 35-45 mass%.
本発明の光半導体封止用樹脂組成物は、エポキシ成分の硬化剤として酸無水物系硬化剤を使用する。この場合、硬化物の透明性を確保する観点から分子内に二重結合が存在しないものが好ましく、特に脂環式または脂肪族酸無水物が好ましい。脂環式酸無水物としては、ヘキサヒドロフタル酸無水物、メチルヘキサヒドロフタル酸無水物等が挙げられる。脂肪族酸無水物としては、ドデセニル無水コハク酸が挙げられる。中でも、耐熱光透過性の点からメチルヘキサヒドロフタル酸無水物を好ましく使用することができる。 The resin composition for optical semiconductor encapsulation of the present invention uses an acid anhydride curing agent as a curing agent for the epoxy component. In this case, from the viewpoint of ensuring the transparency of the cured product, those having no double bond in the molecule are preferable, and alicyclic or aliphatic acid anhydrides are particularly preferable. Examples of the alicyclic acid anhydride include hexahydrophthalic acid anhydride and methylhexahydrophthalic acid anhydride. Examples of the aliphatic acid anhydride include dodecenyl succinic anhydride. Among these, methylhexahydrophthalic anhydride can be preferably used from the viewpoint of heat resistance and light transmittance.
酸無水物系硬化剤の光半導体封止用樹脂組成物中の配合量は、少なすぎても多すぎても耐熱光特性を低下させるので、エポキシ成分と酸無水物硬化剤とグリシジル基含有（メタ）アクリル酸エステル系樹脂との合計に対し、好ましくは４０〜６０質量％、より好ましくは４５〜５５質量％である。なお、官能基濃度という観点から見た場合には、酸無水物系硬化剤の酸無水物当量を、エポキシ成分並びにグリシジル基含有（メタ）アクリル酸エステル系樹脂の合算エポキシ当量で除した当量比が、小さすぎると吸湿性が低下し、多すぎると耐熱光透過性及び吸湿性が低下するので、当量比が好ましくは０．８５〜１．１５、より好ましくは０．９５〜１．０５となるように酸無水物系硬化剤を配合する。 If the amount of the acid anhydride curing agent in the resin composition for encapsulating an optical semiconductor is too small or too large, the heat resistant light characteristics are deteriorated. Therefore, an epoxy component, an acid anhydride curing agent, and a glycidyl group-containing ( Preferably it is 40-60 mass% with respect to the sum total with a meth) acrylic-ester resin, More preferably, it is 45-55 mass%. In addition, when viewed from the viewpoint of functional group concentration, the equivalent ratio obtained by dividing the acid anhydride equivalent of the acid anhydride curing agent by the total epoxy equivalent of the epoxy component and the glycidyl group-containing (meth) acrylic ester resin. However, if it is too small, the hygroscopicity is lowered, and if it is too much, the heat resistant light transmittance and the hygroscopicity are lowered, so that the equivalent ratio is preferably 0.85 to 1.15, more preferably 0.95 to 1.05. An acid anhydride curing agent is blended so as to be.
本発明の光半導体封止用樹脂組成物においては、トリグリシジルイソシアヌレート類を安定的に分散させ、且つ樹脂組成物全体に高チクソ性を付与する分散樹脂として、グリシジル基含有（メタ）アクリル酸エステル系樹脂を使用する。ここで、“（メタ）アクリル”なる用語は、“アクリル”と“メタクリル”とを包含する。また、この（メタ）アクリル酸エステル系樹脂がグリシジル基を含有しなければならない理由は、エポキシ成分と相溶し、架橋反応することで硬化物に優れた耐熱性と適度な表面硬度とを与えるためである。 In the resin composition for optical semiconductor encapsulation of the present invention, a glycidyl group-containing (meth) acrylic acid is used as a dispersion resin that stably disperses triglycidyl isocyanurates and imparts high thixotropy to the entire resin composition. Use ester resin. Here, the term “(meth) acryl” includes “acryl” and “methacryl”. The reason why this (meth) acrylic acid ester resin must contain a glycidyl group is that it is compatible with the epoxy component and crosslinks to give the cured product excellent heat resistance and appropriate surface hardness. Because.
このグリシジル基含有（メタ）アクリル酸エステル系樹脂の重量平均分子量は、十分な構造粘性を示すために２００００〜６５０００、好ましくは３００００〜５５０００という範囲である。 The weight average molecular weight of the glycidyl group-containing (meth) acrylic acid ester-based resin is in the range of 20000 to 65000, preferably 30000 to 55000 in order to exhibit sufficient structural viscosity.
また、このグリシジル基含有（メタ）アクリル酸エステル系樹脂の、レオメーターを用いて２５℃、１０Ｓ−１で測定した粘度は、１００〜１００００Ｐａ・ｓ、好ましくは２００〜５０００Ｐａ・ｓである。粘度が１００Ｐａ・ｓ未満であることは、当該樹脂が過度に低分子量であることを意味し、このため硬化物の接着力の低下をもたらす結果となり、他方、１００００Ｐａ・ｓを超えることは、当該樹脂が過度に高分子量であることを意味し、このため樹脂組成物の粘度が過度に高いものとなり、酸無水物系硬化剤に対する相溶性の低下をもたらす。 Moreover, the viscosity of this glycidyl group-containing (meth) acrylic acid ester resin measured with a rheometer at 25 ° C. and 10S −1 is 100 to 10,000 Pa · s, preferably 200 to 5000 Pa · s. A viscosity of less than 100 Pa · s means that the resin has an excessively low molecular weight, which results in a decrease in the adhesive strength of the cured product, while exceeding 10000 Pa · s This means that the resin has an excessively high molecular weight, and thus the viscosity of the resin composition becomes excessively high, resulting in a decrease in compatibility with the acid anhydride curing agent.
また、このグリシジル基含有（メタ）アクリル酸エステル系樹脂について、レオメーターを用いて２５℃、１ｓ−１で測定したその粘度値を、１０ｓ−１で測定したその粘度値で除して得たグリシジル基含有（メタ）アクリル酸エステル系樹脂のチクソトロピックインデックスは、小さすぎると分散樹脂として十分に機能せず、粉末状のエポキシ成分が沈降してしまい、高粘度すぎてディスペンサーノズルから吐出できなくなりことが懸念されるので、好ましくは２〜５０、より好ましくは４〜３０である。 Moreover, about this glycidyl group containing (meth) acrylic acid ester-type resin, it obtained by dividing | segmenting the viscosity value measured at 25 degreeC and 1 s- 1 using the rheometer by the viscosity value measured at 10 s- 1 . If the thixotropic index of the glycidyl group-containing (meth) acrylic acid ester resin is too small, it will not function sufficiently as a dispersion resin, and the powdered epoxy component will settle out, making it too viscous to be discharged from the dispenser nozzle. Therefore, it is preferably 2 to 50, more preferably 4 to 30.
グリシジル基含有（メタ）アクリル酸エステル系樹脂の光半導体封止用樹脂組成物中の配合量は、少なすぎると分散樹脂として十分な機能を発現することができず、粉末状のエポキシ成分が沈殿し、相分離が生じ、封止用樹脂組成物の接着性が低下する。他方、多すぎると硬化物の耐熱光特性が低下するので、エポキシ成分と酸無水物系硬化剤とグリシジル基含有（メタ）アクリル酸エステル系樹脂との合計に対し、好ましくは５〜３０質量％、より好ましくは７〜１５質量％である。 If the amount of the glycidyl group-containing (meth) acrylic acid ester-based resin in the resin composition for encapsulating an optical semiconductor is too small, sufficient function as a dispersion resin cannot be expressed, and a powdery epoxy component is precipitated. Then, phase separation occurs, and the adhesiveness of the sealing resin composition decreases. On the other hand, if the amount is too large, the heat-resistant light characteristics of the cured product will decrease, so the total amount of the epoxy component, the acid anhydride-based curing agent, and the glycidyl group-containing (meth) acrylic ester-based resin is preferably 5 to 30% by mass. More preferably, it is 7-15 mass%.
なお、グリシジル基含有（メタ）アクリル酸エステル系樹脂は、グリシジル基（メタ）アクリレート３０質量部に対し、エチル、プロピルまたはブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート等のアルキル（メタ）アクリレート７０質量部とを、アゾビスブチロニトリル等のラジカル重合開始剤の存在下で、ラジカル重合させることにより調製することができる。 The glycidyl group-containing (meth) acrylic ester resin is an alkyl (meth) such as ethyl, propyl or butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate with respect to 30 parts by mass of glycidyl group (meth) acrylate. It can be prepared by radical polymerization of 70 parts by mass of acrylate in the presence of a radical polymerization initiator such as azobisbutyronitrile.
本発明の光半導体封止用樹脂組成物は、樹脂組成物の硬化物の透明性を損なわない硬化促進剤を含有する。このような硬化促進剤としては、第四級アンモニウム塩、１，８−ジアザビシクロ［５．４．０］ウンデカ−７−エン（ＤＢＵ）−ｐ−トルエンスルホン酸塩、有機ホスフィン等を使用することができる。中でも、耐熱光特性の点からテトラフェニルホスホニウムテトラフェニルボレートを使用することが好ましい。 The resin composition for encapsulating an optical semiconductor of the present invention contains a curing accelerator that does not impair the transparency of the cured product of the resin composition. As such a curing accelerator, a quaternary ammonium salt, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) -p-toluenesulfonate, organic phosphine, etc. should be used. Can do. Among them, it is preferable to use tetraphenylphosphonium tetraphenylborate from the viewpoint of heat-resistant light characteristics.
硬化促進剤の光半導体封止用樹脂組成物中の配合量は、少なすぎると硬化反応が著しく遅くなり、多すぎると硬化反応が著しく早くなり、耐熱光特性が低下するので、エポキシ成分と酸無水物系硬化剤とグリシジル基含有（メタ）アクリル酸エステル系樹脂との合計１００質量部に対し、好ましくは０．１〜５質量部、より好ましくは０．１５〜３質量部である。 If the blending amount of the curing accelerator in the resin composition for encapsulating an optical semiconductor is too small, the curing reaction is remarkably slow, and if it is too large, the curing reaction is remarkably accelerated and the heat resistant light characteristics are deteriorated. Preferably it is 0.1-5 mass parts with respect to a total of 100 mass parts of an anhydride type hardening | curing agent and glycidyl group containing (meth) acrylic acid ester-type resin, More preferably, it is 0.15-3 mass parts.
本発明の光半導体封止用樹脂組成物は、必要に応じて、老化防止剤を含有することができる。老化防止剤としては、硬化物の劣化過程で生成するラジカル（ＲＯＯ・）を捕捉するラジカル連鎖禁止剤等の一次酸化防止剤、例えば、フェノール系酸化防止剤、アミン系酸化防止剤等を使用することができる。また、不安定な過酸化物（ＲＯＯＨ）を捕捉して積極的に分解して安定な化合物に変化させる過酸化物分解剤等の二次酸化防止剤、例えば、イオン系酸化防止剤、リン系酸化防止剤等を使用することもできる。このような老化防止剤は、光半導体封止用樹脂組成物の硬化温度で樹脂組成物中に溶解することが好ましく、例えば、融点が１５０℃以下のものが好ましい。 The resin composition for optical semiconductor sealing of this invention can contain an anti-aging agent as needed. As an anti-aging agent, a primary antioxidant such as a radical chain inhibitor that captures radicals (ROO.) Generated during the deterioration process of the cured product, for example, a phenol-based antioxidant, an amine-based antioxidant, or the like is used. be able to. In addition, secondary antioxidants such as peroxide decomposers that trap unstable peroxides (ROOH) and actively decompose them into stable compounds, such as ionic antioxidants, phosphorus-based compounds Antioxidants and the like can also be used. Such an anti-aging agent is preferably dissolved in the resin composition at the curing temperature of the optical semiconductor sealing resin composition, and for example, those having a melting point of 150 ° C. or lower are preferable.
老化防止剤の光半導体封止用樹脂組成物中の配合量は、少なすぎても多すぎても耐熱光特性が低下するので、エポキシ成分と酸無水物系硬化剤とグリシジル基含有（メタ）アクリル酸エステル系樹脂との合計１００質量部に対し、好ましくは０．１〜５質量部、より好ましくは０．５〜３質量部である。 If the amount of the anti-aging agent in the resin composition for encapsulating an optical semiconductor is too small or too large, the heat-resistant light characteristics will deteriorate, so an epoxy component, an acid anhydride curing agent, and a glycidyl group-containing (meth) Preferably it is 0.1-5 mass parts with respect to a total of 100 mass parts with acrylic ester resin, More preferably, it is 0.5-3 mass parts.
更に、本発明の光半導体封止樹脂組成物には、硬化物の用途などに応じて、公知の紫外線吸収剤、カップリング剤、難燃剤等を配合することができる。 Furthermore, in the optical semiconductor encapsulating resin composition of the present invention, known ultraviolet absorbers, coupling agents, flame retardants and the like can be blended depending on the use of the cured product.
本発明の光半導体封止樹脂組成物は、エポキシ成分、酸無水物系硬化剤、グリシジル基含有（メタ）アクリル酸エステル系樹脂、硬化促進剤、及び必要に応じて他の成分、例えば老化防止剤を均一に混合することにより調製することができる。 The optical semiconductor encapsulating resin composition of the present invention comprises an epoxy component, an acid anhydride-based curing agent, a glycidyl group-containing (meth) acrylic acid ester-based resin, a curing accelerator, and other components as necessary, such as anti-aging. It can be prepared by mixing the agent uniformly.
本発明の光半導体封止用樹脂組成物は、光半導体装置に好ましく適用できる。かかる光半導体装置も本発明の一部である。このような光半導体装置は、具体的には、光学用半導体チップが、光半導体パッケージ封止樹脂材料で半導体パッケージに封止されてなるものであり、封止樹脂として本発明の光半導体封止用樹脂組成物を使用する以外は、従来の光半導体装置と同様の構成とすることができる。 The resin composition for optical semiconductor encapsulation of the present invention can be preferably applied to an optical semiconductor device. Such an optical semiconductor device is also a part of the present invention. Specifically, such an optical semiconductor device is an optical semiconductor chip in which an optical semiconductor chip is sealed in a semiconductor package with an optical semiconductor package sealing resin material. Except for the use of the resin composition for use, the same structure as that of the conventional optical semiconductor device can be adopted.
以下、本発明を実施例により具体的に説明する。なお、グリシジル基含有（メタ）アクリル酸エステル系樹脂（分散樹脂）として使用したアクリル樹脂Ａ、Ｂ及びＣの製造例を以下に説明する。また、その後に使用した他の成分を説明する。 Hereinafter, the present invention will be specifically described by way of examples. In addition, the manufacture example of acrylic resin A, B, and C used as glycidyl group containing (meth) acrylic-ester resin (dispersion resin) is demonstrated below. Moreover, the other component used after that is demonstrated.
＜アクリル樹脂Ａの製造例＞
撹拌棒と冷却管とを備えた四つ口フラスコに、ブチルアクリレートと、ブチルメタクリレートと、グリシジルメタクリレートと、２−エチルヘキシルメタクリレートと、ラジカル重合開始剤（２，２′−アゾビス（２−メチルプロピオニトリル）とを合計で１００ｇ（但し、３０：３０：３０：２：０．０５の質量比）、ＭＥＫ３００ｇ、及びアセトン１０ｇを投入し、８０℃で４時間撹拌し、重量平均分子量３５８００、粘度３００Ｐａ・ｓ（レオメーター（レオストレスＲＳ−１５０、ＨＡＡＫＥ社製；パラレルプレート使用、ギャップ０．０５２ｍｍ、周波数０．６〜６００ｓ−１）用いて２５℃、１０ｓ−１で測定した粘度）、チクソトロピックインデックス（ＴＩ）５．０（１ｓ−１で測定した粘度を１０ｓ−１で測定した粘度値で除した数値）のグリシジル基を含有するアクリル樹脂Ａを得た。
<Example of production of acrylic resin A>
Into a four-necked flask equipped with a stir bar and a cooling tube, butyl acrylate, butyl methacrylate, glycidyl methacrylate, 2-ethylhexyl methacrylate, radical polymerization initiator (2,2′-azobis (2-methylpropio Nitrile) in total 100 g (however, 30: 30: 30: 2: 0.05 mass ratio), MEK 300 g, and acetone 10 g were added, stirred at 80 ° C. for 4 hours, weight average molecular weight 35800, viscosity 300 Pa. S (rheometer (Rheostress RS-150, manufactured by HAAKE; parallel plate used, gap 0.052 mm, frequency 0.6 to 600 s −1 ), viscosity measured at 25 ° C. and 10 s −1 ), thixotropic index (TI) 5.0 (viscosity measured at 1s -1 viscosity measured at 10s -1 To obtain an acrylic resin A containing glycidyl groups value a value obtained by dividing by).
＜アクリル樹脂Ｂの製造例＞
撹拌棒と冷却管とを備えた四つ口フラスコに、ブチルアクリレートと、ブチルメタクリレートと、グリシジルメタクリレートと、ラジカル重合開始剤（２，２′−アゾビス（２−メチルプロピオニトリル）とを合計で１００ｇ（但し、３０：５０：２０：０．０５の質量比）、ＭＥＫ３００ｇ、及びアセトン１０ｇを投入し、８０℃で４時間撹拌し、重量平均分子量３１５００、粘度２５０Ｐａ・ｓ（レオメーター（レオストレスＲＳ−１５０、ＨＡＡＫＥ社製；パラレルプレート使用、ギャップ０．０５２ｍｍ、周波数０．６〜６００ｓ−１）用いて２５℃、１０ｓ−１で測定した粘度）、チクソトロピックインデックス４．８（１ｓ−１で測定した粘度を１０ｓ−１で測定した粘度値で除した数値）のグリシジル基を含有するアクリル樹脂Ｂを得た。
<Production example of acrylic resin B>
In a four-necked flask equipped with a stir bar and a condenser tube, butyl acrylate, butyl methacrylate, glycidyl methacrylate, and a radical polymerization initiator (2,2′-azobis (2-methylpropionitrile) are combined. 100 g (however, a mass ratio of 30: 50: 20: 0.05), 300 g of MEK and 10 g of acetone were added, stirred at 80 ° C. for 4 hours, weight average molecular weight 31500, viscosity 250 Pa · s (rheometer (rheostress) RS-150, manufactured by HAAKE; parallel plate used, gap 0.052 mm, frequency measured at 25 ° C. and 10 s −1 using a frequency of 0.6 to 600 s −1 ), thixotropic index 4.8 (1 s −1) acrylate containing glycidyl groups divisor value which is) in in viscosity values were measured the viscosity measured at 10s -1 To obtain a resin B.
＜アクリル樹脂Ｃの製造例＞
撹拌棒と冷却管とを備えた四つ口フラスコに、ブチルアクリレートと、ブチルメタクリレートと、グリシジルメタクリレートと、２−エチルヘキシルメタクリレートと、ラジカル重合開始剤（２，２′−アゾビス（２−メチルプロピオニトリル）とを合計で１００ｇ（但し、３０：３０：３０：２：０．０５の質量比）、ＭＥＫ３００ｇ、及びアセトン１０ｇを投入し、８０℃で２時間撹拌し、重量平均分子量１００００、粘度１０５Ｐａ・ｓ（レオメーター（レオストレスＲＳ−１５０、ＨＡＡＫＥ社製；パラレルプレート使用、ギャップ０．０５２ｍｍ、周波数０．６〜６００ｓ−１）用いて２５℃、１０ｓ−１で測定した粘度）、チクソトロピックインデックス４．５（１ｓ−１で測定した粘度を１０ｓ−１で測定した粘度値で除した数値）のグリシジル基を含有するアクリル樹脂Ｃを得た。
<Production example of acrylic resin C>
Into a four-necked flask equipped with a stir bar and a cooling tube, butyl acrylate, butyl methacrylate, glycidyl methacrylate, 2-ethylhexyl methacrylate, radical polymerization initiator (2,2′-azobis (2-methylpropio Nitrile) in total 100 g (however, 30: 30: 30: 2: 0.05 mass ratio), MEK 300 g, and acetone 10 g were added, stirred at 80 ° C. for 2 hours, weight average molecular weight 10,000, viscosity 105 Pa S (rheometer (Rheostress RS-150, manufactured by HAAKE; parallel plate used, gap 0.052 mm, frequency 0.6 to 600 s −1 ), viscosity measured at 25 ° C. and 10 s −1 ), thixotropic divided by the viscosity value measured at index 4.5 (10s -1 the viscosity measured at 1s -1 To obtain an acrylic resin C containing a glycidyl group of numerical value).
＜その他の成分＞
エポキシ化合物：トリス−（２，３−エポキシプロピル）−イソシアヌレート（ＴＥＰＩＣ−Ｐ、日産化学工業（株）：粉末 融点９０℃）；３，４−エポキシシクロヘキセニルメチル−３′，４′−エポキシシクロヘキセンカルボキシレート（ＣＥＬ２０２１Ｐ、ダイセル化学工業（株））
酸無水物系硬化剤：メチルヘキサヒドロフタル酸無水物（ＭＨ−７００（新日本理化（株））
硬化促進剤：テトラフェニルホスホニウムテトラフェニルボレート（ＴＰＰ−Ｋ、北興化学工業（株））
老化防止剤：オクタデシル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（Ｉｒｇａｎｏｘ １０７６、チバ・スペシャリティ・ケミカルズ：粉末 融点 ５５℃）
<Other ingredients>
Epoxy compound: Tris- (2,3-epoxypropyl) -isocyanurate (TEPIC-P, Nissan Chemical Industries, Ltd .: powder, melting point 90 ° C.); 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxy Cyclohexene carboxylate (CEL2021P, Daicel Chemical Industries, Ltd.)
Acid anhydride curing agent: Methylhexahydrophthalic anhydride (MH-700 (Shin Nihon Rika Co., Ltd.))
Curing accelerator: Tetraphenylphosphonium tetraphenylborate (TPP-K, Hokuko Chemical Co., Ltd.)
Anti-aging agent: octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Irganox 1076, Ciba Specialty Chemicals: powder melting point 55 ° C.)
実施例１〜２及び比較例１〜７
表１に示した配合の成分を均一に混合することにより、１５０℃で２時間加熱することで透明な硬化物を与える光半導体封止樹脂組成物を得た。得られた封止樹脂組成物に関し、以下の評価試験(ａ)〜（ｇ）を行った。得られた結果を表１に示す。
Examples 1-2 and Comparative Examples 1-7
By uniformly mixing the components shown in Table 1, an optical semiconductor encapsulating resin composition giving a transparent cured product by heating at 150 ° C. for 2 hours was obtained. The following evaluation tests (a) to (g) were performed on the obtained sealing resin composition. The obtained results are shown in Table 1.
（(a)樹脂組成物の初期粘度評価試験）
封止用樹脂組成物のチクソ性を評価するために、レオメーター（レトストレスＲＳ−１５０、ＨＡＡＫＥ社（測定環境条件：２５℃、パラレルプレート使用、ギャップ０．０５２ｍｍ、周波数０．６〜６００ｓ-1））を用いて１０ｓ−１で封止用樹脂組成物の初期粘度を測定し、また、チクソトロピックインデックス値を求めた。チクソトロピックインデックス値（ＴＩ値）は、１ｓ-1で測定した粘度値を、１０ｓ-1で測定した粘度値で除した値である。ディスペンス方式に望ましい粘度は１０〜２００Ｐａ・ｓである。
((A) Resin composition initial viscosity evaluation test)
In order to evaluate the thixotropy of the sealing resin composition, a rheometer (Letostress RS-150, HAAKE Corporation (measuring environmental conditions: 25 ° C., parallel plate used, gap 0.052 mm, frequency 0.6 to 600 s − 1 )) was used to measure the initial viscosity of the encapsulating resin composition at 10 s −1 and the thixotropic index value was determined. Thixotropic index value (TI value), the viscosity value measured at 1s -1, a value obtained by dividing the viscosity value measured at 10s -1. The desirable viscosity for the dispensing method is 10 to 200 Pa · s.
（(b)樹脂組成物の粘度経時変化評価試験）
封止用樹脂組成物を、内径２０ｍｍ、長さ２００ｍｍのガラスシリンジに充填し、２５℃、５０％ＲＨ環境下に１００時間、２００時間、３００時間放置した後に、シリンジから封止用樹脂組成物を取り出し、上述の(a) 樹脂組成物の初期粘度評価試験と同様に、１０ｓ−１で粘度を測定した。粘度変化がないことは、ポットライフが良好であることを示している。また、ディスペンス方式に望ましい粘度は長期保存後でも１０〜２００Ｐａ・ｓである。
((B) Viscosity change evaluation test of resin composition)
A sealing resin composition is filled in a glass syringe having an inner diameter of 20 mm and a length of 200 mm, and left in a 25 ° C., 50% RH environment for 100 hours, 200 hours, and 300 hours, and then the sealing resin composition is discharged from the syringe. The viscosity was measured at 10 s −1 in the same manner as in the initial viscosity evaluation test of (a) resin composition described above. The absence of viscosity change indicates that the pot life is good. The desirable viscosity for the dispensing method is 10 to 200 Pa · s even after long-term storage.
（(c)耐クラック性評価試験）
０．２ｍｍ厚のガラスエポキシ基板（６０ｍｍ角）上に、Ｓｉチップ（０．５ｍｍ厚、２ｍｍ角）を貼り付け、そのＳｉチップに封止用樹脂組成物を適用し硬化させ、Ｓｉチップを１０ｍｍ×１０ｍｍ×０．５ｍｍ厚の封止用樹脂組成物の硬化物で封止したパッケージサンプルを作成した。このサンプルを−４０℃（３０分）〜１００℃（３０分）の冷熱サイクル試験等に４８時間投入した。４８時間後にＳｉチップのエッジ周辺におけるクラック発生の有無を目視にて観察した。クラックがされないことが望ましい。
((C) Crack resistance evaluation test)
An Si chip (0.5 mm thickness, 2 mm square) is pasted on a 0.2 mm thick glass epoxy substrate (60 mm square), a sealing resin composition is applied to the Si chip and cured, and the Si chip is 10 mm thick. A package sample sealed with a cured product of a sealing resin composition having a thickness of × 10 mm × 0.5 mm was prepared. This sample was put into a cold cycle test at −40 ° C. (30 minutes) to 100 ° C. (30 minutes) for 48 hours. After 48 hours, the presence or absence of cracks around the edge of the Si chip was visually observed. It is desirable that no cracks occur.
（(ｄ)）初期光透過率評価試験）
封止樹脂材料を、１０ｍｍ角で１ｍｍ厚のプレート状に硬化させ、硬化物の４００ｎｍの光に対する初期光透過率を分光光度計（Ｕ−３３００ Ｓｐｅｃｔｒｏ Ｐｈｏｔｏｍｅｔｅｒ、日立ハイテクノロジーズ社）を用いて測定した。初期光透過率は９２％以上であることが望まれる。
((D) Initial light transmittance evaluation test)
The encapsulating resin material was cured into a 10 mm square plate with a thickness of 1 mm, and the initial light transmittance of the cured product with respect to 400 nm light was measured using a spectrophotometer (U-3300 Spectro Photometer, Hitachi High-Technologies Corporation). . The initial light transmittance is desirably 92% or more.
（(ｅ)初期へーズ評価試験）
初期光透過率評価試験に用いたプレート状の硬化物の濁度を、へーズメータ（Σ８０ Ｃｏｌｏｒ Ｍｅａｓｕｒｉｎｇ Ｓｙｓｔｅｍ、日本電色工業社）を用いて測定した。具体的には、この測定で得られた散乱光透過率の値を、全光線透過率の値で除することにより算出した。初期へーズは０．５以下であることが望まれる。
((E) Initial haze evaluation test)
The turbidity of the plate-like cured product used in the initial light transmittance evaluation test was measured using a haze meter (Σ80 Color Measuring System, Nippon Denshoku Industries Co., Ltd.). Specifically, it was calculated by dividing the scattered light transmittance value obtained by this measurement by the total light transmittance value. The initial haze is desirably 0.5 or less.
（(ｆ)耐熱光透過率評価試験）
封止樹脂材料を硬化させて得られた硬化物を、リフロー槽に投入し、最高２６０℃となる温度プロファイルの熱処理を３度（それぞれ１０秒）繰り返した後、熱処理した硬化物を１８０℃に保たれたオーブンへ投入した。そして１００時間経過後にサンプルを取り出し、再度光透過率を分光光度計（Ｕ−３３００ Ｓｐｅｃｔｒｏ Ｐｈｏｔｏｍｅｔｅｒ、日立ハイテクノロジーズ社）を用いて測定した。耐熱光透過率は７０％以上であることが望まれる。
((F) Heat-resistant light transmittance evaluation test)
The cured product obtained by curing the encapsulating resin material is put into a reflow tank, and heat treatment with a temperature profile of 260 ° C. at maximum is repeated 3 times (10 seconds each), and then the heat treated cured product is heated to 180 ° C. It was put into a kept oven. The sample was taken out after 100 hours, and the light transmittance was measured again using a spectrophotometer (U-3300 Spectro Photometer, Hitachi High-Technologies Corporation). The heat resistant light transmittance is desirably 70% or more.
（(ｇ)耐熱耐光光透過率評価試験）
封止樹脂材料を硬化させて得られた硬化物を、リフロー槽に投入し、最高２６０℃となる温度プロファイルの熱処理を３度（それぞれ１０秒）繰り返した後、熱処理した硬化物を、フェードメーター（スガ試験機社）を用いて、紫外線フェード試験（３０Ｗ／ｍ２、３８０ｎｍピーク波長光源、６０℃）を１００時間行い、再度光透過率を分光光度計（Ｕ−３３００ Ｓｐｅｃｔｒｏ Ｐｈｏｔｏｍｅｔｅｒ、日立ハイテクノロジーズ社）を用いて測定した。耐熱耐光光透過率は、８０％以上であることが望まれる。
((G) Heat-resistant and light-resistant transmittance evaluation test)
The cured product obtained by curing the encapsulating resin material is put into a reflow tank, and heat treatment with a temperature profile of 260 ° C. at maximum is repeated three times (10 seconds each). (Suga Test Instruments Co., Ltd.), ultraviolet fading test (30 W / m 2 , 380 nm peak wavelength light source, 60 ° C.) was conducted for 100 hours, and light transmittance was again measured with a spectrophotometer (U-3300 Spectro Photometer, Hitachi High-Technologies) ). The heat and light resistance and light transmittance are desired to be 80% or more.
表１の結果から、実施例１及び２の封止用樹脂組成物の初期粘度は、いずれもディスペンス方式に適した粘度（１０〜２００Ｐａ・ｓ）を示しており、しかも３００時間という長期保存後もディスペンス方式に適した粘度範囲にあることがわかる。しかもチクソトロピックインデックスが４．８又は４．９であり、粉末のエポキシ化合物の良好な分散性を確保していることがわかる。また、耐クラック性、初期光透過率、初期ヘーズ、耐熱光透過率、耐熱耐光光透過率のいずれの評価項目についても、望ましい結果を示していたことがわかった。 From the results shown in Table 1, the initial viscosities of the sealing resin compositions of Examples 1 and 2 all indicate viscosities (10 to 200 Pa · s) suitable for the dispensing method, and after long-term storage of 300 hours. It can also be seen that the viscosity range is suitable for the dispensing method. In addition, the thixotropic index is 4.8 or 4.9, and it can be seen that good dispersibility of the powdered epoxy compound is secured. It was also found that desirable results were shown for all evaluation items of crack resistance, initial light transmittance, initial haze, heat-resistant light transmittance, and heat-resistant light-resistant light transmittance.
なお、実施例２の封止用樹脂組成物は、昇温とともに低粘度化し、１００℃付近で粘度が０．１Ｐａ・ｓ以下となった。この段階では、エポキシ化合物（ＴＥＰＩＣ―Ｐ）は溶融しており、均一な溶融相となっていた。１５０℃付近で急激な粘度上昇が観察され、封止用樹脂組成物の硬化が確認できた。 In addition, the resin composition for sealing of Example 2 decreased in viscosity with increasing temperature, and the viscosity became 0.1 Pa · s or less near 100 ° C. At this stage, the epoxy compound (TEPIC-P) was melted and became a uniform molten phase. A sudden increase in viscosity was observed at around 150 ° C., and curing of the encapsulating resin composition could be confirmed.
また、表１の実施例１及び２の結果から、封止用樹脂組成物に老化防止剤を添加することにより、耐熱光透過率と耐熱耐光光透過率とを向上させ得ることがわかった。 Moreover, from the results of Examples 1 and 2 in Table 1, it was found that the heat resistant light transmittance and the heat resistant light resistant light transmittance can be improved by adding an anti-aging agent to the sealing resin composition.
他方、分散樹脂を含有していない比較例１の封止用樹脂組成物の場合、昇温とともに低粘度化し、７５℃付近で粘度が０．１Ｐａ・ｓ以下となった。エポキシ化合物（ＴＥＰＩＣ―Ｐ）の融点が９０℃であるから、封止用樹脂組成物中で、粉末のエポキシ化合物が溶解しきれておらず、しかも樹脂組成物の粘度が低いものであるから、エポキシ化合物の粉末が沈降し、樹脂組成物中のエポキシ化合物と硬化剤との存在比が不均一になっていることがわかった。この点については、後述の試験例にて詳細に説明する。 On the other hand, in the case of the sealing resin composition of Comparative Example 1 containing no dispersion resin, the viscosity decreased with increasing temperature, and the viscosity became 0.1 Pa · s or less near 75 ° C. Since the melting point of the epoxy compound (TEPIC-P) is 90 ° C., the powdered epoxy compound is not completely dissolved in the sealing resin composition, and the viscosity of the resin composition is low. It turned out that the powder of an epoxy compound settled and the abundance ratio of the epoxy compound and hardening | curing agent in a resin composition became non-uniform | heterogenous. This point will be described in detail in a test example described later.
エポキシ成分として、トリス−（２，３−エポキシプロピル）−イソシアヌレートに代えて液状の脂環式エポキシ化合物を使用した比較例２の封止用樹脂組成物の場合、チクソ性を有するアクリル樹脂Ａを使用しているにも関わらず、封止用樹脂組成物としてチクソ性を示さず、ディスペンス方式に適用できないものであった。しかも、脂環式エポキシ化合物が液状であるため硬化剤と反応し易く、ポットライフが１００時間も持たないものであった。 In the case of the sealing resin composition of Comparative Example 2 using a liquid alicyclic epoxy compound in place of tris- (2,3-epoxypropyl) -isocyanurate as the epoxy component, acrylic resin A having thixotropy In spite of being used, the resin composition for sealing does not exhibit thixotropy and cannot be applied to the dispensing method. Moreover, since the alicyclic epoxy compound is in a liquid state, it easily reacts with the curing agent, and the pot life does not have 100 hours.
分散樹脂においてグリシジルメタクリレートの量が比較的少ないアクリル樹脂Ｂを使用した比較例３の封止用樹脂組成物の場合、エポキシ化合物とアクリル樹脂Ｂとの相溶性及び反応性が十分ではないため、硬化物が白濁してしまった。 In the case of the sealing resin composition of Comparative Example 3 using the acrylic resin B having a relatively small amount of glycidyl methacrylate in the dispersion resin, the compatibility and reactivity between the epoxy compound and the acrylic resin B are not sufficient, and thus the curing. Things have become cloudy.
アクリル樹脂Ａとエポキシ化合物との混合比が実施例２と異なる比較例４〜６の封止用樹脂組成物の場合、チクソトロピックインデックスが１５を超えていた比較例４及び６の封止用樹脂組成物は、ディスペンサーノズルから吐出させる際に粘度が低すぎ、吐出後に相分離してしまった。また、チクソトロピックインデックスが３未満の比較例５の封止用樹脂組成物は、相対的にアクリル樹脂の割合がエポキシ成分に対し過剰となるため、耐熱光透過率及び耐熱耐光光透過率の結果が、実施例２の封止用樹脂組成物に比べ劣っていた。 In the case of the sealing resin compositions of Comparative Examples 4 to 6 in which the mixing ratio of the acrylic resin A and the epoxy compound is different from that of Example 2, the sealing resins of Comparative Examples 4 and 6 having a thixotropic index exceeding 15 The composition was too low in viscosity when ejected from a dispenser nozzle, and phase separated after ejection. In addition, the sealing resin composition of Comparative Example 5 having a thixotropic index of less than 3 has a relatively high acrylic resin ratio relative to the epoxy component, so that the heat resistance light transmittance and heat resistance light resistance transmittance results. However, it was inferior to the sealing resin composition of Example 2.
分散樹脂として重量平均分子量１００００のアクリル樹脂Ｃを使用した比較例７の封止用樹脂組成物の場合、耐クラック性が低下してしまった。 In the case of the sealing resin composition of Comparative Example 7 using the acrylic resin C having a weight average molecular weight of 10000 as the dispersion resin, the crack resistance was lowered.
試験例
分散樹脂を使用した場合（実施例２）と分散樹脂を使用しない場合（比較例１）とで、粉末のトリス−（２，３−エポキシプロピル）−イソシアヌレートの樹脂組成物中の沈降現象を以下のように確認した。
Test Example Precipitation in a resin composition of tris- (2,3-epoxypropyl) -isocyanurate in powder when a dispersion resin is used (Example 2) and when a dispersion resin is not used (Comparative Example 1) The phenomenon was confirmed as follows.
実施例２及び比較例１の封止用樹脂組成物を、ディスペンサーのシリンジ（内径２０ｍｍ、長さ２００ｍｍ）に充填した。このシリンジから以下の（ａ）〜（ｄ）に従って得た硬化物の４００ｎｍの光に対する光透過率を分光光度計（Ｕ−３３００ Ｓｐｅｃｔｒｏ Ｐｈｏｔｏｍｅｔｅｒ、日立ハイテクノロジーズ社）を用いて測定した。
（ａ）シリンジ充填直後に採取した樹脂組成物を１５０℃で硬化させた硬化物
（ｂ）（ａ）の硬化物を、リフロー槽に投入し、最高２６０℃となる温度プロファイルの熱処理を３度（それぞれ１０秒）繰り返した後、熱処理した硬化物を、フェードメーター（スガ試験機社）を用いて、紫外線フェード試験（３０Ｗ／ｍ２、３８０ｎｍピーク波長光源、６０℃）を１００時間行った硬化物
（ｃ）シリンジ充填後３００時間経過後に採取した樹脂組成物を１５０℃で硬化させた硬化物
（ｄ）（ｃ）の硬化物を、リフロー槽に投入し、最高２６０℃となる温度プロファイルの熱処理を３度（それぞれ１０秒）繰り返した後、熱処理した硬化物を、フェードメーター（スガ試験機社）を用いて、紫外線フェード試験（３０Ｗ／ｍ２、３８０ｎｍピーク波長光源、６０℃）を１００時間行った硬化物
The sealing resin compositions of Example 2 and Comparative Example 1 were filled in a dispenser syringe (inner diameter 20 mm, length 200 mm). The light transmittance of the cured product obtained from the syringe according to the following (a) to (d) with respect to 400 nm light was measured using a spectrophotometer (U-3300 Spectro Photometer, Hitachi High-Technologies Corporation).
(A) Cured product obtained by curing resin composition collected immediately after syringe filling at 150 ° C. (b) Cured product of (a) is put into a reflow tank, and heat treatment with a temperature profile of 260 ° C. at maximum is performed three times. (10 seconds each) After repeating the heat treatment, the cured product was subjected to an ultraviolet fade test (30 W / m 2 , 380 nm peak wavelength light source, 60 ° C.) for 100 hours using a fade meter (Suga Test Instruments Co., Ltd.). Product (c) Cured product obtained by curing resin composition collected at 300 hours after syringe filling at 150 ° C. (d) Cured product of (c) is put into a reflow tank, and a temperature profile of maximum 260 ° C. is obtained. After repeating the heat treatment three times (10 seconds each), the heat-treated cured product was subjected to an ultraviolet fade test (30 W / m 2 , 380 nm peak) using a fade meter (Suga Test Instruments Co., Ltd.). Cured product obtained by performing a 100-hour long wavelength light source, 60 ° C.)
上述の（ａ）〜（ｄ）の硬化物の光透過率を図１に示す。図１は、比較例１の場合には、明らかにシリンジの上部でのエポキシ化合物濃度が低下していることを示している。 FIG. 1 shows the light transmittance of the cured products (a) to (d) described above. FIG. 1 clearly shows that in the case of Comparative Example 1, the concentration of the epoxy compound at the upper portion of the syringe is lowered.
本発明の光半導体封止用樹脂組成物は、エポキシ主剤となるエポキシ成分にトリグリシジルイソシアヌレート類を配合し、且つエポキシ成分の分散媒体として特定の重量平均分子量と特定の粘度とを示す高チクソ性のグリシジル基含有（メタ）アクリル酸エステル系樹脂を使用する。このため、光半導体封止用樹脂組成物は、高チクソ性を示し、しかもトリグリシジルイソシアヌレート類は沈降せずに良好な分散状態となっている。従って、本発明の光半導体封止用樹脂組成物は、ディスペンス方式で光半導体を封止する際に有用である。 The resin composition for encapsulating an optical semiconductor according to the present invention is a high thixotrope having a specific weight average molecular weight and a specific viscosity as a dispersion medium of an epoxy component by blending triglycidyl isocyanurates with an epoxy component as an epoxy main component. Glycidyl group-containing (meth) acrylic ester resin is used. For this reason, the resin composition for optical semiconductor sealing shows high thixotropy, and the triglycidyl isocyanurates are in a well dispersed state without being settled. Therefore, the resin composition for encapsulating an optical semiconductor of the present invention is useful when encapsulating an optical semiconductor by a dispense method.
Claims (9)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009144119A JP5564835B2 (en) | 2009-06-17 | 2009-06-17 | Resin composition for optical semiconductor encapsulation |
| KR1020117020900A KR20120036795A (en) | 2009-06-17 | 2010-05-28 | Resin composition for encapsulation of photosemiconductors |
| PCT/JP2010/059064 WO2010146979A1 (en) | 2009-06-17 | 2010-05-28 | Resin composition for encapsulation of photosemiconductors |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009144119A JP5564835B2 (en) | 2009-06-17 | 2009-06-17 | Resin composition for optical semiconductor encapsulation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2011001418A true JP2011001418A (en) | 2011-01-06 |
| JP5564835B2 JP5564835B2 (en) | 2014-08-06 |
Family
ID=43356299
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009144119A Expired - Fee Related JP5564835B2 (en) | 2009-06-17 | 2009-06-17 | Resin composition for optical semiconductor encapsulation |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5564835B2 (en) |
| KR (1) | KR20120036795A (en) |
| WO (1) | WO2010146979A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012147611A1 (en) * | 2011-04-26 | 2012-11-01 | サンユレック株式会社 | Method and apparatus for manufacturing optical device |
| WO2013051280A1 (en) * | 2011-10-07 | 2013-04-11 | コニカミノルタアドバンストレイヤー株式会社 | Phosphor dispersion liquid, and production method for led device using same |
| JP2015054965A (en) * | 2013-09-13 | 2015-03-23 | 株式会社東芝 | Encapsulation resin, semiconductor device, and optical coupling device |
| JP2015101633A (en) * | 2013-11-25 | 2015-06-04 | スリーボンドファインケミカル株式会社 | Epoxy resin composition |
| JP2015227390A (en) * | 2014-05-30 | 2015-12-17 | 京セラケミカル株式会社 | Resin composition for encapsulating optical semiconductor and optical semiconductor device |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113365680B (en) * | 2019-03-29 | 2023-12-01 | 纳美仕有限公司 | Syringe filled with resin composition, method for producing same, and method for storing same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003160640A (en) * | 2001-09-14 | 2003-06-03 | Sumitomo Chem Co Ltd | Resin composition for sealing optical semiconductor |
| WO2004034148A1 (en) * | 2002-10-09 | 2004-04-22 | Nissan Chemical Industries, Ltd. | Composition for forming antireflection film for lithography |
| JP2005036218A (en) * | 2003-06-30 | 2005-02-10 | Mitsubishi Gas Chem Co Inc | Thermosetting resin composition and its application |
| JP2005306952A (en) * | 2004-04-20 | 2005-11-04 | Japan Epoxy Resin Kk | Epoxy resin composition as sealing material for light-emitting element |
| JP2008045014A (en) * | 2006-08-14 | 2008-02-28 | Mitsubishi Chemicals Corp | Epoxy resin composition and its use |
-
2009
- 2009-06-17 JP JP2009144119A patent/JP5564835B2/en not_active Expired - Fee Related
-
2010
- 2010-05-28 KR KR1020117020900A patent/KR20120036795A/en not_active Application Discontinuation
- 2010-05-28 WO PCT/JP2010/059064 patent/WO2010146979A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003160640A (en) * | 2001-09-14 | 2003-06-03 | Sumitomo Chem Co Ltd | Resin composition for sealing optical semiconductor |
| WO2004034148A1 (en) * | 2002-10-09 | 2004-04-22 | Nissan Chemical Industries, Ltd. | Composition for forming antireflection film for lithography |
| JP2005036218A (en) * | 2003-06-30 | 2005-02-10 | Mitsubishi Gas Chem Co Inc | Thermosetting resin composition and its application |
| JP2005306952A (en) * | 2004-04-20 | 2005-11-04 | Japan Epoxy Resin Kk | Epoxy resin composition as sealing material for light-emitting element |
| JP2008045014A (en) * | 2006-08-14 | 2008-02-28 | Mitsubishi Chemicals Corp | Epoxy resin composition and its use |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012147611A1 (en) * | 2011-04-26 | 2012-11-01 | サンユレック株式会社 | Method and apparatus for manufacturing optical device |
| JPWO2012147611A1 (en) * | 2011-04-26 | 2014-07-28 | サンユレック株式会社 | Opto device manufacturing method and manufacturing apparatus |
| US9373730B2 (en) | 2011-04-26 | 2016-06-21 | Sanyu Rec Co., Ltd. | Method and apparatus for manufacturing optical device |
| US10050158B2 (en) | 2011-04-26 | 2018-08-14 | Sanyu Rec Co., Ltd. | Method and apparatus for manufacturing optical device |
| WO2013051280A1 (en) * | 2011-10-07 | 2013-04-11 | コニカミノルタアドバンストレイヤー株式会社 | Phosphor dispersion liquid, and production method for led device using same |
| JPWO2013051280A1 (en) * | 2011-10-07 | 2015-03-30 | コニカミノルタ株式会社 | Phosphor dispersion liquid and method for manufacturing LED device using the same |
| US9184352B2 (en) | 2011-10-07 | 2015-11-10 | Konica Minolta, Inc. | Phosphor dispersion liquid, and production method for LED device using same |
| JP2015054965A (en) * | 2013-09-13 | 2015-03-23 | 株式会社東芝 | Encapsulation resin, semiconductor device, and optical coupling device |
| JP2015101633A (en) * | 2013-11-25 | 2015-06-04 | スリーボンドファインケミカル株式会社 | Epoxy resin composition |
| JP2015227390A (en) * | 2014-05-30 | 2015-12-17 | 京セラケミカル株式会社 | Resin composition for encapsulating optical semiconductor and optical semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20120036795A (en) | 2012-04-18 |
| WO2010146979A1 (en) | 2010-12-23 |
| JP5564835B2 (en) | 2014-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5564835B2 (en) | Resin composition for optical semiconductor encapsulation | |
| EP2584015B1 (en) | Light-reflecting anisotropically conductive adhesive and light emitting device | |
| EP2500932B1 (en) | Adhesive composition | |
| JP2007308683A (en) | Epoxy resin curing agent, epoxy resin composition, epoxy resin cured product and optical member using the same | |
| TW201631044A (en) | Curable silicone resin composition, and cured product thereof | |
| JP5119364B1 (en) | White curable composition for optical semiconductor device and molded article for optical semiconductor device | |
| JP5253260B2 (en) | Fluorescent resin composition for LED, sealing material using the same, and phosphorescent material | |
| JP2009227849A (en) | Epoxy resin composition for use in sealing optical semiconductor element | |
| KR102340593B1 (en) | Transparent resin composition, adhesive comprising composition, die bond material comprising composition, conductive connection method using composition, and optical semiconductor device obtained using method | |
| KR101657528B1 (en) | Heat-curable conductive silicone composition, conductive adhesive comprising the composition, conductive die-bonding material comprising the composition, and optical semiconductor device having cured product of the die-bonding material | |
| KR101947621B1 (en) | Heat-curable silicone composition, die bond material comprising composition, and optical semiconductor device using cured article of die bond material | |
| JP5556671B2 (en) | Curable composition, cured film, and semiconductor light emitting device | |
| KR101915341B1 (en) | Curable epoxy resin composition | |
| TWI579312B (en) | Curable epoxy resin composition | |
| JP6061471B2 (en) | Optical semiconductor device and method for manufacturing optical semiconductor device | |
| JP2016153447A (en) | White thermosetting epoxy resin composition for led reflector | |
| JP4433876B2 (en) | Epoxy resin composition and adhesive for optical semiconductor using the same | |
| JP6142782B2 (en) | Epoxy resin composition and optical semiconductor device | |
| KR20170084028A (en) | Adhesive, die bond material comprising adhesive, conductive connection method using adhesive, and optical semiconductor device obtained using method | |
| JP2011088947A (en) | Epoxy group-containing adhesive resin composition and adhesive for optical semiconductor prepared by using the same | |
| JP2019108457A (en) | Light-reflecting thermosetting resin tablet, optical semiconductor element mounting board, method for manufacture thereof, and optical semiconductor device | |
| JP6884192B2 (en) | Epoxy resin curing agent composition, epoxy resin composition containing it, cured product thereof | |
| JP2011042762A (en) | Composition for transparent sealing material | |
| JP2006328188A (en) | Resin composition for optical semiconductor, and optical semiconductor device | |
| WO2023090317A1 (en) | Curable resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120214 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20131001 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20131202 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140121 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140324 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140520 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140602 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5564835 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |