JPH07109361A - Cured material of thermosetting resin composition - Google Patents
Cured material of thermosetting resin compositionInfo
- Publication number
- JPH07109361A JPH07109361A JP25819393A JP25819393A JPH07109361A JP H07109361 A JPH07109361 A JP H07109361A JP 25819393 A JP25819393 A JP 25819393A JP 25819393 A JP25819393 A JP 25819393A JP H07109361 A JPH07109361 A JP H07109361A
- Authority
- JP
- Japan
- Prior art keywords
- cured product
- resin composition
- component
- thermosetting resin
- release agent
- 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
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、成型時の離型性が優
れ、金型汚れが少なく、優れたマ−キング特性を有する
熱硬化性樹脂組成物硬化体、およびその硬化体により封
止されてなる半導体装置に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cured product of a thermosetting resin composition having excellent releasability at the time of molding, little stains on the mold, and excellent marking properties, and sealing with the cured product. The present invention relates to a semiconductor device that is manufactured.
【０００２】[0002]
【従来の技術】ＩＣやＬＳＩなどの半導体装置は、通常
セラミックパッケ−ジあるいはプラスチックパッケ−ジ
により封止されている。セラミックパッケ−ジは、耐熱
性、耐湿性に優れ、かつパッケ−ジ内部の半導体素子へ
の損傷もなく信頼性の高い封止が可能であるが、構成材
料が比較的高価なものであること、量産性に劣る欠点が
あるために、最近では、プラスチックパッケ−ジを用い
た樹脂封止が主流になっている。なかでもエポキシ樹脂
組成物によるトランスファ−モ−ルドで行われた樹脂封
止は、モ−ルド時の作業性、量産性やモ−ルド後の信頼
性の点において良好な成績を収めている。2. Description of the Related Art Semiconductor devices such as ICs and LSIs are usually sealed with a ceramic package or a plastic package. The ceramic package has excellent heat resistance and moisture resistance, and enables highly reliable sealing without damaging the semiconductor elements inside the package, but the constituent material is relatively expensive. However, because of the drawback of being inferior in mass productivity, resin sealing using a plastic package has become the mainstream these days. In particular, the resin encapsulation performed by transfer molding with an epoxy resin composition has a good result in terms of workability in molding, mass productivity and reliability after molding.
【０００３】通常、このエポキシ樹脂組成物を用いて、
半導体素子をトランスファ−成型で封止する際には、金
型からの離型性を良くするためにエポキシ樹脂組成物に
カルナバワックスやポリエチレンワックスなどの離型剤
が内部添加される。Usually, using this epoxy resin composition,
When the semiconductor element is sealed by transfer molding, a release agent such as carnauba wax or polyethylene wax is internally added to the epoxy resin composition in order to improve the releasability from the mold.
【０００４】[0004]
【発明が解決しようとする課題】これらの離型剤を成型
時に樹脂組成物中から金型表面にブル−ミングさせるこ
とにより離型性が発現するため、離型剤としては、樹脂
と相溶しない材料が用いられる。The mold release property is exhibited by blooming these mold release agents from the resin composition onto the surface of the mold at the time of molding. Therefore, the mold release agent is compatible with the resin. Not used material is used.
【０００５】また、エポキシ樹脂組成物をトランスファ
−成型する際には、金型からの離型性を良くするため、
比較的多量の離型剤を必要とする場合が多い。しかし、
多量の離型剤を配合すると、成型物表面での離型剤のブ
ル−ミングが激しくなり、離型性は良好になるものの、
これらを除去する工程を経ないと印刷あるいは捺印（マ
−キング性）などを行うことが困難になるといった不都
合が生じる。また離型剤の配合量が増加するにしたがっ
て、金型の微小間隔からの樹脂もれも多くなり、金型汚
れなど他の成型性をも悪くしてしまうといった欠点が生
じる。Further, when transfer molding an epoxy resin composition, in order to improve the releasability from the mold,
Often a relatively large amount of release agent is required. But,
When a large amount of a release agent is blended, blooming of the release agent on the surface of the molded product becomes severe and the releasability is improved, but
If a step of removing these is not performed, it is difficult to perform printing or marking (marking property). Further, as the compounding amount of the release agent increases, the resin leaks from the minute gaps of the mold, and other moldability such as stain of the mold deteriorates.
【０００６】この発明は、このような事情に鑑みなされ
たもので、優れた離型性および金型汚れが少なく、優れ
たマ−キング特性を備えた熱硬化性樹脂組成物硬化体、
およびそれにより包被されてなる半導体装置の提供を目
的とする。The present invention has been made in view of the above circumstances, and is a cured product of a thermosetting resin composition having excellent releasability and less mold stain, and excellent marking characteristics,
It is also an object of the present invention to provide a semiconductor device covered with the semiconductor device.
【０００７】[0007]
【課題を解決するための手段】上記目的を達成するため
に、この発明の熱硬化性樹脂組成物硬化体は、硬化体中
に成型時の離型性を附与する成分を含有する粒子（Ａ）
が、実質的に均一分散していると共に、上記粒子（Ａ）
中には、該粒子よりも親水性の成分を含有する微粒子
（Ｂ）が分散した構造をとる。In order to achieve the above object, the cured product of the thermosetting resin composition of the present invention comprises particles containing a component imparting releasability during molding to the cured product ( A)
Of the above particles (A)
A fine particle (B) containing a component more hydrophilic than the particle is dispersed therein.
【０００８】[0008]
【作用】すなわち、本発明者らは、離型性が良好で、か
つ金型汚れが少なくマ−キング特性に優れた熱硬化性樹
脂組成物硬化体を得るために、できるだけ少量の離型剤
を添加した際の、熱硬化性樹脂組成物硬化体の構造につ
いて研究を重ねた。その結果、先ず始めにＨＬＢ価の異
なる二種以上の離型剤を混合し、次いで熱硬化性樹脂組
成物に添加した。それによって、硬化体中に離型性を付
与する成分を含有する粒子（Ａ）（以下「離型剤
（Ａ）」と略す）および離型剤（Ａ）中に離型剤（Ａ）
よりも親水性の成分を含有する微粒子（Ｂ）（以下「離
型剤（Ｂ）」と略す）が分散した三相以上の相構造をと
る熱硬化性樹脂組成物硬化体は、離型性が良好で、かつ
マ−キング特性にも優れることを見出し、この発明に到
達した。That is, in order to obtain a cured product of a thermosetting resin composition which has good mold releasability, little mold stains, and excellent marking characteristics, the present inventors have used as little release agent as possible. Studies have been repeated on the structure of the cured product of the thermosetting resin composition when added with. As a result, first, two or more release agents having different HLB values were mixed, and then added to the thermosetting resin composition. Thereby, particles (A) containing a component imparting releasability to the cured product (hereinafter abbreviated as "release agent (A)") and release agent (A) in release agent (A)
A cured product of a thermosetting resin composition having a phase structure of three or more phases in which fine particles (B) containing a more hydrophilic component (hereinafter abbreviated as “release agent (B)”) are dispersed has releasability. The present invention has been achieved by discovering that the above characteristics are good and the marking characteristics are also excellent.
【０００９】つぎに、この発明を詳しく説明する。Next, the present invention will be described in detail.
【００１０】この発明に用いられる熱硬化性樹脂組成物
硬化体は、熱硬化性樹脂、硬化剤および特定の離型剤、
必要に応じて硬化促進剤を用いて硬化して得られるもの
である。その実例を図１により説明すると、（Ｘ）は組
成物硬化体、（Ａ）はＨＬＢ価が２以上であり２０未満
の離型剤であり、（Ｂ）は実際に使用する特定の（Ａ）
離型剤よりも大きいＨＬＢ価を有する離型剤である。そ
のＨＬＢ価の差は、０．５〜１０．０が好ましい。The cured product of the thermosetting resin composition used in the present invention comprises a thermosetting resin, a curing agent and a specific release agent,
It is obtained by curing with a curing accelerator if necessary. An example thereof will be described with reference to FIG. 1. (X) is a cured product of the composition, (A) is a release agent having an HLB value of 2 or more and less than 20, and (B) is a specific (A) actually used. )
It is a release agent having an HLB value higher than that of the release agent. The difference in HLB value is preferably 0.5 to 10.0.
【００１１】上記熱硬化性樹脂としては、エポキシ樹
脂、尿素樹脂、メラミン樹脂、フェノ−ル樹脂、ポリエ
ステル、ウレタン樹脂およびイミド樹脂等が用いられ
る。また、上記エポキシ樹脂は、シリコ−ン樹脂との反
応によって得られる変性エポキシ樹脂を用いることも可
能である。As the thermosetting resin, epoxy resin, urea resin, melamine resin, phenol resin, polyester, urethane resin, imide resin and the like are used. Further, as the epoxy resin, it is also possible to use a modified epoxy resin obtained by a reaction with a silicone resin.
【００１２】上記熱硬化性樹脂とともに用いられる硬化
剤としては、例えば、エポキシ樹脂では、アミン類、フ
ェノ−ル樹脂、酸無水物、ポリアミドおよびポリメルカ
プタン等が用いられる。また、尿素樹脂、メラミン樹脂
およびフェノ−ル樹脂では、ホルムアルデヒドやヘキサ
メチレンテトラミン等のアルデヒド類、ポリエステルや
ウレタン樹脂では、多価アルコ−ル、イミド樹脂では、
多価アミンおよび多価アミド等が用いられる。As the curing agent used together with the thermosetting resin, for example, in the case of epoxy resin, amines, phenol resin, acid anhydride, polyamide, polymercaptan and the like are used. Further, in urea resins, melamine resins and phenol resins, aldehydes such as formaldehyde and hexamethylenetetramine, in polyesters and urethane resins, polyhydric alcohols, in imide resins,
A polyvalent amine and a polyvalent amide are used.
【００１３】上記熱硬化性樹脂と硬化剤の配合比は、熱
硬化性樹脂１００重量部（以下「部」と略す）に対して
硬化剤を３０〜１５０部の範囲に設定することが好まし
い。特に、エポキシ樹脂においては、エポキシ樹脂のエ
ポキシ基に対する硬化剤中の反応性官能基の当量比（エ
ポキシ基／反応性官能基）が通常１／０．４〜１／１．
２、好ましくは１／０．８〜１／１．１の範囲が半導体
装置の耐熱性および耐湿性の観点から選ばれる。The blending ratio of the thermosetting resin to the curing agent is preferably set in the range of 30 to 150 parts of the curing agent to 100 parts by weight of the thermosetting resin (hereinafter abbreviated as "part"). Particularly, in an epoxy resin, the equivalent ratio of the reactive functional group in the curing agent to the epoxy group of the epoxy resin (epoxy group / reactive functional group) is usually 1 / 0.4 to 1/1.
2, preferably 1 / 0.8 to 1/1. 1 is selected from the viewpoint of heat resistance and moisture resistance of the semiconductor device.
【００１４】本発明に用いられる離型剤（Ａ）として
は、物質の親水性／親油性を表す尺度であるＨＬＢ価
が、２以上であり２０未満の界面活性剤であれば特定さ
れるものでない。例えば、脂肪族アルコ−ル、芳香族ア
ルコ−ル、脂肪酸、脂肪酸エステル、脂肪酸金属塩、脂
肪族スルホキシドポリエ−テル類、脂肪族アミンおよび
脂肪族アミド等が挙げられる。好ましくは、ＨＬＢ価が
２以上であり１５未満の界面活性剤がよく、脂肪酸およ
び脂肪族エステル等が挙げられる。このような離型剤
（Ａ）の硬化体中における粒子径は、０．０１〜１０μ
ｍになるように設定されているのが好ましく、さらに好
ましくは、０．０１〜１μｍである。The mold release agent (A) used in the present invention is specified if it is a surfactant having an HLB value of 2 or more and less than 20 which is a measure of hydrophilicity / lipophilicity of a substance. Not. Examples thereof include aliphatic alcohols, aromatic alcohols, fatty acids, fatty acid esters, fatty acid metal salts, aliphatic sulfoxide ethers, aliphatic amines and aliphatic amides. A surfactant having an HLB value of 2 or more and less than 15 is preferable, and examples thereof include fatty acids and aliphatic esters. The particle size of the release agent (A) in the cured product is 0.01 to 10 μm.
It is preferably set to be m, and more preferably 0.01 to 1 μm.
【００１５】離型剤（Ａ）中に形成される離型剤（Ｂ）
の成分としては、ＨＬＢ価が３以上であり２０以下の界
面活性剤がよく、さらに好ましくはＨＬＢ価が１０以上
であり２０以下の界面活性剤である。かつＨＬＢ価が
（Ａ）成分のそれよりも大きいものであれば特定される
ものでない。そのような界面活性剤としては、脂肪族の
金属塩、脂肪族スルホキシドおよび脂肪族アミド等が挙
げられる。このような離型剤（Ｂ）の硬化体中における
粒子径は、０．００５〜０．５μｍになるように設定さ
れているのが好ましく、さらに好ましくは、０．００５
〜０．１μｍである。Release agent (B) formed in release agent (A)
The component is preferably a surfactant having an HLB value of 3 or more and 20 or less, and more preferably a surfactant having an HLB value of 10 or more and 20 or less. Moreover, if the HLB value is larger than that of the component (A), it is not specified. Examples of such surfactants include aliphatic metal salts, aliphatic sulfoxides and aliphatic amides. The particle size of the release agent (B) in the cured product is preferably set to 0.005 to 0.5 μm, more preferably 0.005.
Is about 0.1 μm.
【００１６】上記離型剤（Ａ）を形成する成分に対し
て、離型剤（Ｂ）を形成する成分の配合量は、離型剤
（Ａ）成分１００部に対して、離型剤（Ｂ）成分が５〜
１００部が好ましく、さらに好ましくは５〜５０部に設
定することが望まれる。すなわち、離型剤（Ｂ）成分の
配合量が５部以下であるとマ−キング性や信頼性に問題
が生じる傾向があるためである。The compounding amount of the component forming the releasing agent (B) with respect to the component forming the releasing agent (A) is 100 parts by weight of the releasing agent (A) component. B) component is 5
The amount is preferably 100 parts, and more preferably 5 to 50 parts. That is, if the amount of the release agent (B) compounded is 5 parts or less, problems may occur in marking properties and reliability.
【００１７】さらに、これら離型剤全体、すなわち離型
剤（Ａ）と離型剤（Ｂ）の配合量は、熱硬化性樹脂組成
物硬化体全体の０．０１〜１０部の範囲になるように設
定することが好ましい。すなわち、離型剤の配合量が
０．０１部未満であると離型剤に問題が生じ易く、逆に
１０部を越えるとマ−キング性に劣る傾向があるからで
ある。Furthermore, the total amount of these release agents, that is, the amount of the release agent (A) and the release agent (B) blended, is in the range of 0.01 to 10 parts based on the total amount of the cured product of the thermosetting resin composition. It is preferable to set as follows. That is, if the compounding amount of the release agent is less than 0.01 part, a problem tends to occur in the release agent, and conversely, if it exceeds 10 parts, the marking property tends to be poor.
【００１８】必要に応じて本発明に用いられる硬化促進
剤は、通常の触媒であり、特に限定されない。具体例と
しては、例えば、エポキシ樹脂の場合、三級アミン、イ
ミダゾ−ル類、イミダゾリン類、ジアザビシクロアルケ
ン類、脂肪族アミン類および芳香族アミン類等の窒素原
子含有化合物、トリアリ−ルホスフィン、モノアルキル
ジアリ−ルホスフィンおよびテトラアリ−ルホスホニウ
ムテトラアリルボレ−ト等のホスホニウム塩、さらに
は、トリアリ−ルホスフィントリアリ−ルボロン錯体等
のリン化合物、アルミニウムトリアセタ−ルアセトナ−
ト等の金属錯体等が挙げられる。また、フェノ−ル樹脂
の場合は、トリエチルアミン、ホウ酸などの無機酸、有
機酸およびアルカリ等、ポリエステルの場合は、テトラ
ブチルジルコネ−トやテトラブチルチタネ−ト等の金属
有機化合物、ウレタン樹脂の場合は、有機すずや三級ア
ミン等が挙げられる。The curing accelerator used in the present invention, if necessary, is an ordinary catalyst and is not particularly limited. Specific examples include, in the case of epoxy resins, nitrogen atom-containing compounds such as tertiary amines, imidazoles, imidazolines, diazabicycloalkenes, aliphatic amines and aromatic amines, and triarylphosphine. Phosphonium salts such as monoalkyl diallyl phosphine and tetraaryl phosphonium tetraallylborate, phosphorus compounds such as triaryl phosphine triaryl boron complex, and aluminum triacetate acetonate.
And metal complexes such as G. In the case of a phenol resin, inorganic acids such as triethylamine and boric acid, organic acids and alkalis, and in the case of polyesters, metal organic compounds such as tetrabutyl zirconate and tetrabutyl titanate, urethanes. In the case of resin, organic tin, a tertiary amine, etc. are mentioned.
【００１９】さらに、この発明に用いられる熱硬化性樹
脂組成物硬化体は、上記各成分以外に、必要に応じて、
種々のものを配合した後、硬化して得られる。例えば、
充填剤や、充填剤の表面を処理するための表面処理剤や
難燃剤、着色剤および可撓性附与剤である。Further, the cured product of the thermosetting resin composition used in the present invention may contain, in addition to the above components, if necessary.
It is obtained by mixing various materials and then curing. For example,
It is a filler, a surface treatment agent for treating the surface of the filler, a flame retardant, a coloring agent, and a flexible additive.
【００２０】充填剤としては、特に限定はなく、例え
ば、結晶性シリカ粉、溶融性シリカ粉、石英ガラス粉、
タルク、ケイ酸カルシウム粉、ケイ酸ジルコニア粉およ
び炭酸カルシウム粉等が挙げられるが、シリカ系のもの
が好ましい。その充填剤の配合割合は、全樹脂組成物に
対して０〜９０重量％がよい。すなわち、充填剤の配合
量が９０重量％を超えると、樹脂組成物の流動性が低く
なり、成型が困難になるためである。The filler is not particularly limited, and examples thereof include crystalline silica powder, fusible silica powder, quartz glass powder,
Examples thereof include talc, calcium silicate powder, silicate zirconia powder, and calcium carbonate powder, with silica-based powders being preferred. The blending ratio of the filler is preferably 0 to 90% by weight based on the total resin composition. That is, if the compounding amount of the filler exceeds 90% by weight, the fluidity of the resin composition becomes low and molding becomes difficult.
【００２１】表面処理剤としては、公知のシランカップ
リング剤等が挙げられ、難燃剤としては、三酸化アンチ
モン、五酸化アンチモン、リン酸塩および臭化物が挙げ
られ、可撓性附与剤としては、シリコ−ン樹脂およびブ
タジエン−アクリロニトリルゴム等が用いられる。ただ
し、これらに限定されるものでない。Examples of the surface treating agent include known silane coupling agents and the like, flame retardants include antimony trioxide, antimony pentoxide, phosphates and bromides, and flexibility imparting agents. , Silicone resin, butadiene-acrylonitrile rubber and the like are used. However, it is not limited to these.
【００２２】このような熱硬化性樹脂組成物は、例え
ば、次のようにして製造することができる。すなわち、
上記熱硬化性樹脂および硬化剤に、あらかじめ離型剤
（Ａ）と離型剤（Ｂ）を配合しておいたものを加え、必
要に応じて硬化促進剤、それ以外の添加剤を適宜配合
し、予備混合した後、混練機により所定の温度で混練し
溶融混合する。そして、これを室温に冷却した後、固体
の場合は公知の手段により粉砕し、必要に応じてタブレ
ット状に打錠することにより熱硬化性樹脂組成物を製造
することができる。また、液状の場合は、混合するのみ
で熱硬化性樹脂組成物を得ることができる。Such a thermosetting resin composition can be manufactured, for example, as follows. That is,
To the above thermosetting resin and curing agent, a mixture of a release agent (A) and a release agent (B) is added in advance, and if necessary, a curing accelerator and other additives are appropriately added. Then, after premixing, they are kneaded and melt-mixed at a predetermined temperature by a kneader. Then, after being cooled to room temperature, in the case of a solid, it is pulverized by a known means, and if necessary, tableted into a tablet form to produce a thermosetting resin composition. In the case of a liquid, the thermosetting resin composition can be obtained only by mixing.
【００２３】このようにして得られた熱硬化性樹脂組成
物を、注型やトランスファ−成型など公知の成型法によ
り、本発明の目的とする熱硬化性樹脂組成物硬化体が得
られる。The thermosetting resin composition thus obtained is subjected to a known molding method such as casting or transfer molding to obtain a cured product of the thermosetting resin composition which is the object of the present invention.
【００２４】このようにして得られる熱硬化性樹脂組成
物硬化体は、組成物中に含まれる特定の離型剤が特定の
構造をとる作用により、成型時の離型性に優れ、かつマ
−キング性や信頼性にも極めて優れている。なお、特定
の構造、すなわち三相構造は透過型電子顕微鏡により観
察できる。The cured product of the thermosetting resin composition thus obtained has an excellent releasability at the time of molding due to the action of the specific release agent contained in the composition having a specific structure. -Excellent in king property and reliability. The specific structure, that is, the three-phase structure can be observed with a transmission electron microscope.
【００２５】[0025]
【発明の効果】以上のように、この発明の熱硬化性樹脂
硬化体は、特定の離型剤が硬化体中で特定の構造を有し
ている。すなわち、硬化体中に離型剤（Ａ）、離型剤
（Ａ）中に離型剤（Ｂ）の如く三相構造を有しているた
め、より少ない離型剤量で優れた離型性を備え、しかも
マ−キング特性が優れている。従って、従来に比較し、
成型効率が格段に向上し、半導体装置用の封止材として
使用する際の信頼性も極めて高くなる。As described above, in the thermosetting resin cured product of the present invention, the specific release agent has a specific structure in the cured product. That is, since the cured product has a three-phase structure like the mold release agent (A) and the mold release agent (A) is the mold release agent (B), excellent mold release with a smaller mold release agent amount. And has excellent marking characteristics. Therefore, compared to the conventional
The molding efficiency is remarkably improved, and the reliability when used as a sealing material for semiconductor devices is also extremely high.
【００２６】[0026]
【実施例】次に実施例について比較例と併せて説明す
る。 〔実施例１〕エポキシ当量６５０のビスフェノ−ルＡ型
エポキシ樹脂（固形樹脂）１００部に、硬化剤としてテ
トラヒドロ無水フタル酸１００部、硬化触媒として２−
エチル−４−メチルイミダゾ−ル０．３部に、あらかじ
め、離型剤（Ａ）としてベヘン酸ｎ−ブチル（ＨＬＢ価
５．２）１．５部、離型剤（Ｂ）としてステアリン酸亜
鉛（ＨＬＢ価１３．０）０．５部配合しておいたものを
添加し、９０〜１２０℃で溶融混合して冷却した後、粉
砕し、粉末をタブレット状に打錠した後、１５０℃でト
ランスファ−成型により硬化体を作製した。EXAMPLES Next, examples will be described together with comparative examples. Example 1 100 parts of a bisphenol A type epoxy resin (solid resin) having an epoxy equivalent of 650, 100 parts of tetrahydrophthalic anhydride as a curing agent, and 2-part as a curing catalyst.
To 0.3 parts of ethyl-4-methylimidazole, 1.5 parts of n-butyl behenate (HLB value 5.2) as a release agent (A) and zinc stearate as a release agent (B) were previously prepared. (HLB number 13.0) 0.5 parts of the compounded ingredients were added, melt-mixed at 90 to 120 ° C, cooled, crushed, and the powder was tabletted into tablets at 150 ° C. A cured product was produced by transfer molding.
【００２７】〔実施例２〜８〕および〔比較例１〜８〕
後記の表１、表２、表３、表４および表５に示された離
型剤（Ａ）と離型剤（Ｂ）の種類および配合量で、それ
以外は実施例１と同様にして目的とする硬化体を得た。[Examples 2-8] and [Comparative Examples 1-8]
The types and blending amounts of the release agent (A) and the release agent (B) shown in Tables 1, 2, 3, 4, and 5 below are the same as in Example 1 except for the above. A desired cured product was obtained.
【００２８】〔実施例９〕エポキシ当量１８０のビスフ
ェノ−ルＡ型エポキシ樹脂（液状樹脂）１００部にメチ
ルヘキサヒドロ無水フタル酸１００部、硬化触媒として
２−エチル−４−メチルイミダゾ−ル０．３部に、あら
かじめ、離型剤（Ａ）としてベヘン酸ｎ−ブチル１．５
部、離型剤（Ｂ）としてステアリン酸亜鉛０．５部配合
しておいたものを添加混合し、十分離型剤を樹脂中に分
散させた後、その樹脂組成物を注型後、１２０℃で１６
時間硬化させて硬化体を作製した。Example 9 100 parts of bisphenol A type epoxy resin (liquid resin) having an epoxy equivalent of 180, 100 parts of methylhexahydrophthalic anhydride, and 2-ethyl-4-methylimidazole as a curing catalyst were used. To 3 parts, in advance, n-butyl behenate 1.5 was used as a release agent (A).
Parts, 0.5 parts of zinc stearate as a release agent (B) was added and mixed, and the ten-separation agent was dispersed in the resin. After casting the resin composition, 120 16 at ℃
It was cured for a time to prepare a cured product.
【００２９】〔実施例１０〕エポキシ当量１９５のｏ−
クレゾ−ルノボラック型エポキシ樹脂（固形樹脂）１０
０部に、ノボラック型フェノ−ル樹脂（フェノ−ル当量
１０６）６０部、硬化触媒として２−エチルイミダゾ−
ル０．３部に、あらかじめ、離型剤（Ａ）としてベヘン
酸ｎ−ブチル１．５部、離型剤（Ｂ）としてステアリン
酸亜鉛０．５部配合しておいたものを添加し、９０〜１
２０℃で溶融混合して冷却した後、粉砕し、粉末をタブ
レット状に打錠した後、１５０℃でトランスファ−成型
により硬化体を作製した。[Example 10] Epoxy equivalent of 195 o-
Cresol Novolak Epoxy Resin (Solid Resin) 10
To 0 part, 60 parts of novolac type phenol resin (phenol equivalent 106), and 2-ethylimidazole as a curing catalyst.
To 0.3 part of the resin, 1.5 parts of n-butyl behenate as a release agent (A) and 0.5 part of zinc stearate as a release agent (B) were added in advance. 90-1
After melt-mixing at 20 ° C. and cooling, the mixture was crushed, the powder was tabletted, and then a cured product was produced by transfer molding at 150 ° C.
【００３０】〔実施例１１〕エポキシ当量１９５のｏ−
クレゾ−ルノボラック型エポキシ樹脂（固形樹脂）１０
０部に、あらかじめ両末端アミノ基ジメチルシリコ−ン
（分子量４０００）を１２部配合し、１００℃で５時間
反応させた樹脂に、ノボラック型フェノ−ル樹脂（フェ
ノ−ル当量１０６）６０部、硬化触媒として２−メチル
イミダゾ−ル０．３部に、あらかじめ、離型剤（Ａ）と
してベヘン酸ｎ−ブチル１．５部、離型剤（Ｂ）として
ステアリン酸亜鉛０．５部配合しておいたものを添加
し、９０〜１２０℃で溶融混合して冷却した後、粉砕
し、粉末をタブレット状に打錠した後、１５０℃でトラ
ンスファ−成型により硬化体を作製した。Example 11 Epoxy equivalent of 195 o-
Cresol Novolak Epoxy Resin (Solid Resin) 10
To 0 part, 12 parts of both terminal amino group dimethyl silicone (molecular weight 4000) was blended in advance, and the resin was reacted at 100 ° C. for 5 hours, and 60 parts of novolak type phenol resin (phenol equivalent 106), To 0.3 part of 2-methylimidazole as a curing catalyst, 1.5 parts of n-butyl behenate as a release agent (A) and 0.5 part of zinc stearate as a release agent (B) were previously mixed. The above-mentioned materials were added, melt-mixed at 90 to 120 ° C., cooled, pulverized, and the powder was tabletted into tablets. Then, a cured product was prepared by transfer molding at 150 ° C.
【００３１】[0031]
【表１】 [Table 1]
【表２】 [Table 2]
【表３】 [Table 3]
【表４】 [Table 4]
【表５】 [Table 5]
【００３２】次に、上記実施例および比較例によって得
られた硬化体の成型時の金型からの離型性、硬化体表面
へのマ−キング特性および硬化体中での離型剤の相構造
について評価した。これらの結果を下記の表４、表５お
よび表６に示した。Next, the releasability of the cured products obtained in the above Examples and Comparative Examples from the mold at the time of molding, the marking property on the surface of the cured product, and the phase of the release agent in the cured product. The structure was evaluated. The results are shown in Tables 4, 5 and 6 below.
【００３３】〔離型性〕離型性は、離型性評価用金型を
用いて、成型直後の離型荷重を測定し５段階で評価し
た。離型性の良い方から順番に５、４、３、２、１とし
た。 〔マ−キング特性〕マ−キング特性は、ＹＡＧレ−ザ−
（エネルギ−密度０．３ジュ−ル／ｃｍ2）を用いて、
硬化体に照射し、比較的暗い雰囲気下でのマ−キングの
鮮明度で評価した。これも、鮮明度の度合いを視覚的に
５段階に分けて評価した。良い方から順番に５、４、
３、２、１とした。 〔離型剤の相構造〕離型剤の相構造は、ＴＥＭ観察（透
過型電子顕微鏡による観察）により行った。ＴＥＭ観察
するために超薄切片法を用い、硬化体試料をミクロト−
ムで０．１μｍに薄く削り、上記顕微鏡にて観察を行っ
た。硬化体試料が、硬化体も含んで三相構造の場合を
○、二相構造の場合を△、相構造がない場合を×とし
た。[Releasability] The releasability was evaluated in five levels by measuring the release load immediately after molding using a mold for evaluating releasability. It was set to 5, 4, 3, 2, 1 in order from the one having good releasability. [Marking characteristics] The marking characteristics are those of the YAG laser.
(Energy-density 0.3 joule / cm 2 )
The cured product was irradiated and evaluated by the sharpness of marking in a relatively dark atmosphere. This was also evaluated by visually categorizing the degree of sharpness into 5 levels. 5, 4 in order from the best
It was set to 3, 2, 1. [Phase Structure of Release Agent] The phase structure of the release agent was determined by TEM observation (observation with a transmission electron microscope). The ultrathin section method was used for TEM observation, and the cured sample was microtoped.
It was thinly ground to 0.1 μm and observed with the above microscope. The case of the cured body sample including the cured body has a three-phase structure, the case of a two-phase structure is rated as Δ, and the case of no phase structure is rated as ×.
【００３４】[0034]
【表６】 [Table 6]
【表７】 [Table 7]
【００３５】表６および表７の結果から、比較例１は、
離型剤（Ａ）および離型剤（Ｂ）をまったく配合してい
ないため、離型性が非常に悪く、硬化体の表面平滑性も
悪いためにマ−キング特性も悪い。比較例２は、離型剤
（Ａ）のみであり、その離型剤（Ａ）だけでは樹脂組成
物と相溶するために離型性がほとんど発現しない。比較
例３は、離型剤（Ｂ）だけで、その極性が高いため離型
性は良好であるが、離型剤のブリ−ドが多いためマ−キ
ング特性が非常に悪い。比較例４および比較例５は、三
相構造を有していて分散性も良好であるが、極性の離型
剤（Ｂ）が少ないため離型性が悪い。また、比較例６は
三相構造を有するものの、離型剤（Ｂ）が離型剤（Ａ）
に比べて、その量が多いため、離型剤のブリ−ドが多
く、離型性は良好であるもののマ−キング特性が悪い。
比較例７も、三相構造を有するものの、離型剤（Ａ）お
よび離型剤（Ｂ）の合計量が多いため、離型剤のブリ−
ドが多く、離型性は良好であるもののマ−キング特性が
悪い。さらに、比較例８は、いずれの離型剤も樹脂組成
物と相溶してしまうため離型性が悪い。これに対して、
実施例品は、いずれも三相構造を示し、成型時の金型か
らの離型性が良好で、マ−キング特性にも優れているこ
とがわかる。From the results of Table 6 and Table 7, Comparative Example 1
Since the release agent (A) and the release agent (B) are not blended at all, the releasability is extremely poor, and the surface smoothness of the cured product is also poor, so that the marking properties are also poor. In Comparative Example 2, only the release agent (A) is used, and the release agent (A) alone is compatible with the resin composition, and therefore hardly exhibits releasability. In Comparative Example 3, the release agent (B) alone has a high polarity and thus has a good releasability, but the marking property is very poor because the release agent has many bleeds. Comparative Examples 4 and 5 have a three-phase structure and have good dispersibility, but have poor polar releasability (B), resulting in poor releasability. Further, although Comparative Example 6 has a three-phase structure, the release agent (B) is the release agent (A).
Compared with the above, since the amount of the release agent is large, the release agent has a large amount of bleeding and the releasing property is good, but the marking characteristics are poor.
Comparative Example 7 also has a three-phase structure, but since the total amount of the release agent (A) and the release agent (B) is large, the release agent bridging occurs.
However, the marking characteristics are poor, but the marking characteristics are poor. Further, in Comparative Example 8, any mold release agent is compatible with the resin composition, and thus the mold release property is poor. On the contrary,
It can be seen that each of the example products has a three-phase structure, has good mold releasability from the mold during molding, and has excellent marking characteristics.
【００３６】[0036]
【図１】樹脂組成物硬化体が三相構造であることを示す
説明図である。FIG. 1 is an explanatory diagram showing that a cured resin composition has a three-phase structure.
（Ｘ） 組成物硬化体 （Ａ） 離型剤（Ａ） （Ｂ） 離型剤（Ｂ） (X) Cured composition (A) Release agent (A) (B) Release agent (B)
Claims (7)
成分を含有する粒子（Ａ）が、実質的に均一分散してい
ると共に、上記粒子（Ａ）中には、該粒子よりも親水性
の成分を含有する微粒子（Ｂ）が分散してなる熱硬化性
樹脂組成物硬化体。1. Particles (A) containing a component imparting releasability at the time of molding are substantially uniformly dispersed in the cured product, and the particles (A) have A cured product of a thermosetting resin composition in which fine particles (B) containing a component more hydrophilic than particles are dispersed.
２０未満である請求項１記載の熱硬化性樹脂組成物硬化
体。2. The cured product of the thermosetting resin composition according to claim 1, wherein the particle (A) has an HLB value of 2 or more and less than 20.
２０以下である請求項１記載の熱硬化性樹脂組成物硬化
体。3. The cured product of the thermosetting resin composition according to claim 1, wherein the particle (B) has an HLB value of 3 or more and 20 or less.
が、０．０１〜１０μｍである請求項１記載の熱硬化性
樹脂組成物硬化体。4. The thermosetting resin composition cured product according to claim 1, wherein the size of the particles (A) in the cured product is 0.01 to 10 μm.
量が硬化体１００重量部に対して、０．０１〜１０重量
部である請求項１記載の熱硬化性樹脂組成物硬化体。5. The cured product of the thermosetting resin composition according to claim 1, wherein the total content of the particles (A) and the particles (B) is 0.01 to 10 parts by weight with respect to 100 parts by weight of the cured product. .
エステルであり、粒子（Ｂ）成分が脂肪族金属塩である
請求項１記載の熱硬化性樹脂組成物硬化体。6. The cured product of the thermosetting resin composition according to claim 1, wherein the particle (A) component is a fatty acid or an aliphatic ester, and the particle (B) component is an aliphatic metal salt.
載の熱硬化性樹脂組成物硬化体により包被されてなる半
導体装置。7. A semiconductor device which is covered with the cured product of the thermosetting resin composition according to any one of claims 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25819393A JP3300134B2 (en) | 1993-10-15 | 1993-10-15 | Thermosetting resin composition cured product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25819393A JP3300134B2 (en) | 1993-10-15 | 1993-10-15 | Thermosetting resin composition cured product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07109361A true JPH07109361A (en) | 1995-04-25 |
| JP3300134B2 JP3300134B2 (en) | 2002-07-08 |
Family
ID=17316807
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25819393A Expired - Lifetime JP3300134B2 (en) | 1993-10-15 | 1993-10-15 | Thermosetting resin composition cured product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3300134B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001342323A (en) * | 2000-05-30 | 2001-12-14 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP5994023B2 (en) * | 2013-05-14 | 2016-09-21 | 株式会社日立製作所 | Composite insulating resin material for high voltage equipment and high voltage equipment using the same |
-
1993
- 1993-10-15 JP JP25819393A patent/JP3300134B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001342323A (en) * | 2000-05-30 | 2001-12-14 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| JP4608736B2 (en) * | 2000-05-30 | 2011-01-12 | 住友ベークライト株式会社 | Method for producing epoxy resin composition for semiconductor encapsulation |
| JP5994023B2 (en) * | 2013-05-14 | 2016-09-21 | 株式会社日立製作所 | Composite insulating resin material for high voltage equipment and high voltage equipment using the same |
| US9938405B2 (en) | 2013-05-14 | 2018-04-10 | Hitachi, Ltd. | Hybridized insulating resin material for high voltage equipment and high voltage equipment using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3300134B2 (en) | 2002-07-08 |
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