JP2577613B2 - Adhesive epoxy resin composition, molded article thereof, method of producing molded article, and method of bonding and sealing - Google Patents

Description

【発明の詳細な説明】 （産業上の利用分野） 本発明は接着剤、封止剤等に使用されるエポキシ樹脂
組成物、その成形体、その成形体の製造方法及びその成
形体を利用した接着、封止方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial application field) The present invention utilizes an epoxy resin composition used for an adhesive, a sealant, etc., a molded article thereof, a method for producing the molded article, and the molded article. It relates to a bonding and sealing method.

（従来の技術） 最近、例えば電子部品のような小型、微細な部品を接
着、封止するニーズが増加しているが、このような比較
的小面積の必要個所だけに適用することは、液状の接着
剤の場合、はみ出しや充填不足が起こり易い。又、電子
部品等では熱硬化性の接着剤が要求される場合が多く、
この場合は硬化反応進行による粘度変化や、ゲル化等の
ため、作業性や取扱いに難点が多い。このため、このよ
うな用途には固型の予備成形された接着剤が要求される
が、従来、固型の熱硬化性接着剤の場合、粉末状熱硬化
性樹脂と配合材、添加材、硬化剤等の粉末をドライブレ
ンドして粉末状の混合物を打錠機にて成形体を得る製造
方法がとられている。しかし、これによつて得られた成
形体は脆く欠け易いため、製造できる形状、大きさに対
する制約が大きく、前記した小型、微細な部品を接着す
るニーズに適さない場合がある。又従来の方法で製造し
た固型接着剤は脆いために製造されてから部品等の接着
に使用されるまでの間に、例えば搬送時の振動等により
破損し易く、又粉を発生し易いために、この粉が被着物
を汚す等の不具合を生じることもある。更に従来の方法
で製造された固型接着剤は、粉末状接着剤を突き固めた
ものであるため、溶融接着後の状態は内部に気泡を多く
含み、信頼性の高い接着剤とは言えない。(Prior Art) Recently, there has been an increasing need for bonding and sealing small and fine components such as electronic components. However, application to only a necessary portion having such a relatively small area requires a liquid. In the case of the adhesive, the protrusion or insufficient filling is likely to occur. In addition, thermosetting adhesives are often required for electronic components and the like,
In this case, there are many difficulties in workability and handling due to a change in viscosity due to the progress of the curing reaction and gelation. For this reason, solid pre-formed adhesives are required for such applications, but conventionally, in the case of solid thermosetting adhesives, powdered thermosetting resin and compounding materials, additives, A production method has been employed in which a powder such as a curing agent is dry-blended to obtain a powdery mixture by a tableting machine to obtain a molded body. However, since the molded body obtained by this method is brittle and easily chipped, the shape and size that can be manufactured are greatly restricted, and the molded body may not be suitable for the need for bonding the small and fine parts described above. In addition, since the solid adhesive manufactured by the conventional method is fragile, it is easily broken, for example, due to vibration during transportation, and is liable to generate powder during a period from being manufactured to being used for bonding parts and the like. In some cases, the powder may cause problems such as soiling the adherend. Furthermore, since the solid adhesive manufactured by the conventional method is obtained by squeezing the powdery adhesive, the state after fusion bonding contains many bubbles inside and cannot be said to be a highly reliable adhesive. .

（発明が解決しようとする課題） 本発明の目的は小型で微細な形状を有し、又、破損し
難く、摩擦等によつて粉を生じることが少なく、更に溶
融接着後、内部に気泡を含まない、実質状未硬化状態の
接着性エポキシ樹脂組成物、その成形体、その成形体の
製造方法及び該成形体を利用した接着、封止方法を提供
することにある。(Problems to be Solved by the Invention) An object of the present invention is to have a small and fine shape, to be hard to be broken, to generate little powder due to friction and the like, and to further form bubbles inside after fusion bonding. An object of the present invention is to provide a substantially uncured adhesive epoxy resin composition in a substantially uncured state, a molded article thereof, a method for producing the molded article, and a bonding and sealing method using the molded article.

（課題を解決するための手段） 本発明は数平均分子量200以上、5000未満のエポキシ
樹脂100重量部に数平均分子量5000以上の熱可塑性樹脂
３〜33重量部を、 硬化剤以外の配合材、添加材等と共に、或いは単独
で、溶融混合する第１混合工程と、 硬化剤単独或いはこれを配合材、添加材等と共に溶
融混合する第２混合工程 によつて得られたエポキシ樹脂組成物、該組成物を成形
して得られる接着性エポキシ樹脂成形体、該組成物を実
質上未硬化状態で0.01mmから10mm厚みのフイルムないし
シートに成形した後、該フイルムないしシートを15℃以
上70℃未満の温度範囲で打抜くことを特徴とする接着性
エポキシ樹脂成形体の製造方法及び該成形体を用いた接
着、封止方法に関する。(Means for Solving the Problems) The present invention relates to 100 parts by weight of an epoxy resin having a number average molecular weight of 200 or more and less than 5000, and 3 to 33 parts by weight of a thermoplastic resin having a number average molecular weight of 5,000 or more. An epoxy resin composition obtained by a first mixing step of melt-mixing with an additive or the like alone or a second mixing step of melt-mixing a curing agent alone or with a compounding material, an additive or the like; Adhesive epoxy resin molded article obtained by molding the composition, after forming the composition into a film or sheet having a thickness of 0.01 mm to 10 mm in a substantially uncured state, the film or sheet is heated to 15 ° C or more and less than 70 ° C. The present invention relates to a method for producing an adhesive epoxy resin molded article characterized by punching in the above temperature range, and a method for bonding and sealing using the molded article.

本発明で用いられる数平均分子量（以下、単に分子量
という）200以上、5000未満のエポキシ樹脂としては、
ビスフエノールＡ型エポキシ樹脂〔油化シエルエポキシ
（株）製、エピコート828,834,1001,1002,1003,1004,10
05,1007,1010,1100L等〕、臭素化ビスフエノールＡ型エ
ポキシ樹脂〔油化シエルエポキシ（株）製、エピコート
5050,5051,5051H等〕、ｏ−クレゾールノボラツク型エ
ポキシ樹脂〔住友化学（株）製、ESCN-220L,ESCN-220F,
ESCN-220H,ESCN-220HH等〕、臭素化ノボラツク型エポキ
シ樹脂〔日本化薬（株）製、BREN−Ｓ等〕、フエノール
ノボラツク型エポキシ樹脂〔住友化学（株）製、ESPN-1
80等〕及びこれらを変性したエポキシ樹脂が挙げられ
る。これらのエポキシ樹脂は併用することも可能であ
り、又、分子量が200未満のエポキシ樹脂であつても、
又、Ｂステージ状のエポキシ樹脂のように分子量5000以
上であつても、これらの混合物の分子量が200以上、500
0未満であれば本発明のエポキシ樹脂として使用可能で
あるが、好ましくは分子量を1000〜2000に調整するのが
良い。As the epoxy resin having a number average molecular weight (hereinafter, simply referred to as molecular weight) of 200 or more and less than 5000 used in the present invention,
Bisphenol A-type epoxy resin [Yuka Kasei Epoxy Co., Ltd., Epicoat 828,834,1001,1002,1003,1004,10
05,1007,1010,1100L etc.), brominated bisphenol A type epoxy resin [Yuika Ciel Epoxy Co., Ltd., Epicoat
5050, 5051, 5051H etc.), o-cresol novolak type epoxy resin [manufactured by Sumitomo Chemical Co., Ltd., ESCN-220L, ESCN-220F,
ESCN-220H, ESCN-220HH, etc.), brominated novolak type epoxy resin [manufactured by Nippon Kayaku Co., Ltd., BREN-S], phenol novolak type epoxy resin [Sumitomo Chemical Co., Ltd., ESPN-1]
80 etc.] and modified epoxy resins. These epoxy resins can be used in combination, and even if the epoxy resin has a molecular weight of less than 200,
Further, even when the molecular weight is 5,000 or more, such as a B-stage epoxy resin, the molecular weight of these mixtures is 200 or more, 500
If it is less than 0, it can be used as the epoxy resin of the present invention, but the molecular weight is preferably adjusted to 1,000 to 2,000.

エポキシ樹脂の分子量が200未満の場合、たとえ分子
量5000以上の熱可塑性樹脂を３〜33重量部混合したとし
ても、室温で成形品表面がベタつき、互いにブロツキン
グする問題が生じる。一方分子量が5000以上の場合、融
点が高く、また熔融粘度が大きくなる為、第２混合工程
において温度を高く設定する必要があり、これによつて
エポキシ樹脂と硬化剤とが反応してしまう危険がある。If the epoxy resin has a molecular weight of less than 200, even if 3 to 33 parts by weight of a thermoplastic resin having a molecular weight of 5,000 or more are mixed, the surface of the molded product becomes sticky at room temperature and causes a problem of mutual blocking. On the other hand, when the molecular weight is 5,000 or more, the melting point is high and the melt viscosity is high. Therefore, it is necessary to set the temperature high in the second mixing step, which may cause the epoxy resin and the curing agent to react. There is.

分子量5000以上の熱可塑性樹脂としては、ポリアミド
系樹脂、ポリカーボネート系樹脂、ポリウレタン系樹
脂、ポリエステル系樹脂、シリコン系樹脂、フエノキシ
樹脂、塩化ビニル系樹脂、ポリスチレン系樹脂、ABS系
樹脂、ポリビニルアルコール系樹脂、アイオノマー系樹
脂、メタクリル系樹脂、ポノフエニレンオキサイド系樹
脂、塩素化ポリエチレンなどの熱可塑性樹脂或いはエラ
ストマー、天然ゴム、イソプレンゴム、ブタジエンゴ
ム、スチレンブタジエンゴム、ニトリルゴム、クロロプ
レンゴム、シリコンゴム、ノルボルネンポリマーなどの
ゴムが例示できる。Examples of the thermoplastic resin having a molecular weight of 5,000 or more include a polyamide resin, a polycarbonate resin, a polyurethane resin, a polyester resin, a silicone resin, a phenoxy resin, a vinyl chloride resin, a polystyrene resin, an ABS resin, and a polyvinyl alcohol resin. , Ionomer resins, methacrylic resins, ponophenylene oxide resins, thermoplastic resins or elastomers such as chlorinated polyethylene, natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, nitrile rubber, chloroprene rubber, silicone rubber, A rubber such as a norbornene polymer can be exemplified.

第２混合工程完了時、実質上未硬化状態を保持できる
のであれば、これらの熱可塑性樹脂の分子中或いは末端
に、エポキシ樹脂と反応する官能基をもつていてもよ
い。When the second mixing step is completed, the thermoplastic resin may have a functional group that reacts with the epoxy resin in the molecule or at the terminal thereof, as long as the thermoplastic resin can maintain a substantially uncured state.

本発明で用いる熱可塑性樹脂は成形体の機械的強度を
改善するのが目的であり、分子量が5000未満ではその改
善効果が小さく、成形体は非常に脆いものとなる。一方
分子量が100000以上となると融点が高く、また溶融粘度
が大きくなる為、混合温度が高くエネルギーロスが大き
く、又成形体にしたものが加熱溶融しにくいので、分子
量は100000以下が望ましい。又添加量が３重量部未満で
あると成形体の機械的強度の改善効果が小さく33重量部
を越えるとエポキシ樹脂の特性を損なつてしまう。本発
明でいう溶融混合とは、互いに溶融して混合してもよい
し、どちらか一方が溶融し、他方を分散させる混合であ
つてもよい。The purpose of the thermoplastic resin used in the present invention is to improve the mechanical strength of the molded article. If the molecular weight is less than 5,000, the effect of the improvement is small, and the molded article becomes very brittle. On the other hand, if the molecular weight is 100,000 or more, the melting point is high, and the melt viscosity is high. Therefore, the mixing temperature is high, the energy loss is large, and the molded product is difficult to be heated and melted. If the amount is less than 3 parts by weight, the effect of improving the mechanical strength of the molded article is small, and if it exceeds 33 parts by weight, the properties of the epoxy resin are impaired. The term “melt mixing” as used in the present invention may be such that both are melted and mixed, or one in which one is melted and the other is dispersed.

本発明の第１工程において添加される配合材、添加材
の例として、充填材、難燃材、補強材、滑材、分散材、
界面活性剤、顔料、染料、カツプリング剤等が挙げられ
る。充填材としてはマイカ、シリカ、ガラス繊維、ガラ
スフレーク、ガラス粉、炭素繊維、タルク、炭酸カルシ
ウム等の無機充填材、アラミド繊維、ナイロン繊維等の
有機充填材など、難燃材としては三酸化アンチモン、水
酸化アルミニウム、赤リン、ハロゲン化合物など、滑
材、分散材、界面活性剤としてはワツクス、ステアリン
酸亜鉛、シリコンオイルなど、顔料及び染料としてはカ
ーボンブラツク、ベンガラ、チタン白、シアニンブルー
など、カツプリング剤としてはシランカツプリング剤、
チタンカツプリング剤などを例示できる。溶融混合する
手段としては、混練押出機、加熱撹拌槽、ニーダー、バ
ンバリーミキサー、ロール等が例示される。Examples of the compounding material added in the first step of the present invention and the additive material include a filler, a flame retardant, a reinforcing material, a lubricant, a dispersant,
Examples include surfactants, pigments, dyes, and coupling agents. Fillers include mica, silica, glass fiber, glass flake, glass powder, inorganic fillers such as carbon fiber, talc and calcium carbonate, organic fillers such as aramid fiber and nylon fiber, and antimony trioxide as a flame retardant. , Aluminum hydroxide, red phosphorus, halogen compounds, etc., lubricants, dispersants, surfactants such as wax, zinc stearate, silicon oil, etc., and pigments and dyes such as carbon black, red iron, titanium white, cyanine blue, etc. As a coupling agent, a silane coupling agent,
Titanium coupling agents and the like can be exemplified. Examples of the means for melting and mixing include a kneading extruder, a heating and stirring tank, a kneader, a Banbury mixer, and a roll.

次の硬化剤単独或いはこれと配合材、添加材等と共に
溶融混合する第２混合工程において、その硬化剤の例と
して、アミン系硬化剤、酸無水物系硬化剤、フエノール
樹脂系硬化剤、触媒系硬化剤等、エポキシ樹脂と硬化反
応可能な硬化剤であれば特に限定はないが、好ましくは
室温で固型の硬化剤が望ましい。In the second mixing step of melt-mixing the following curing agent alone or together with a compounding material, an additive and the like, examples of the curing agent include amine-based curing agents, acid anhydride-based curing agents, phenolic resin-based curing agents, and catalysts. There is no particular limitation as long as it is a curing agent that can undergo a curing reaction with the epoxy resin, such as a system curing agent, but preferably a solid curing agent at room temperature is desirable.

アミン類の具体例としては、ジエチレントリアミン、
トリエチレンテトラミン、ビス（ヘキサメチレン）トリ
アミン、トリメチルヘキサメチレンジアミン、メンセン
ジアミン、イソホロンジアミン、メタキシリレンジアミ
ン、3,9−ビス（３−アミノプロピル）−2,4,8−テトラ
スピロ〔5.5〕ウンデカン、メタフエニレンジアミン、
ジアミノジフエニルメタン、ジアミノジフエニルスルホ
ン、4,4′−メチレンビス（２−クロロアニリン）及び
これとエポキシ樹脂とのアダクト等を、酸無水物の具体
例としては、無水フタル酸、無水トリメツト酸、無水ピ
ロメリツト酸、無水ベンゾフエノンテトラカルボン酸、
無水マレイン酸、テトラヒドロ無水フタル酸、ヘキサヒ
ドロ無水フタル酸、無水メタルナジツク酸、無水メチル
シクロヘキセンテトラカルボン酸、テトラクロロ無水フ
タル酸、テトラブロモ無水フタル酸等を、フエノール類
の具体例としては、フエノール、ｏ−クレゾールノボラ
ツク、フエノールノボラツク、フエノールアラルキル等
を挙げることができる。触媒系硬化剤としては例えばベ
ンジルジメチルアミン、2,4,6−トリス（ジメチルアミ
ノメチル）フエノール、ピペリジン、ピリジン、ピコリ
ン等の３級アミンや、２−エチル−４−メチルイミダゾ
ールで代表されるイミダゾール類、その他1,8−ジアザ
ビシクロ〔5.4.0〕ウンデセン、BF₃等のルイス酸、ジシ
アンジアミド、アミンイミド、有機酸ヒドラジド等、ま
たこれらを組合せた混合物や、塩、錯体等に変性したも
の等を挙げることができる。硬化剤の配合量は通常触媒
系硬化剤の場合はエポキシ樹脂100に対し0.1〜20phr、
その他の場合はエポキシ基に対して当量比で0.5〜２の
範囲とするのが好ましい。Specific examples of amines include diethylenetriamine,
Triethylenetetramine, bis (hexamethylene) triamine, trimethylhexamethylenediamine, mensendiamine, isophoronediamine, metaxylylenediamine, 3,9-bis (3-aminopropyl) -2,4,8-tetraspiro [5.5] Undecane, metaphenylenediamine,
Specific examples of acid anhydrides include diaminodiphenylmethane, diaminodiphenylsulfone, 4,4'-methylenebis (2-chloroaniline) and an adduct thereof with an epoxy resin, and phthalic anhydride, trimetic anhydride, Pyromellitic anhydride, benzophenonetetracarboxylic anhydride,
Maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, metalnadic anhydride, methylcyclohexenetetracarboxylic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride and the like, specific examples of phenols, phenols, o- Cresol novolak, phenol novolak, phenol aralkyl and the like can be mentioned. Examples of the catalyst-based curing agent include tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, piperidine, pyridine and picoline, and imidazole represented by 2-ethyl-4-methylimidazole. mentioned kind, other 1,8-diazabicyclo [5.4.0] undecene, Lewis acids such as BF _3, dicyandiamide, amine imides, organic acid hydrazide, also mixtures combination thereof or, salts, such as those obtained by modifying the complexes be able to. The amount of the curing agent is usually 0.1 to 20 phr for the epoxy resin 100 in the case of the catalyst curing agent.
In other cases, the equivalent ratio to the epoxy group is preferably in the range of 0.5 to 2.

硬化剤以外の配合材、添加材等を溶融混合する第１混
合工程と、硬化剤単独或いはこれと配合材、添加材等と
共に溶融混合する第２混合工程を分離した理由は、エポ
キシ樹脂と配合材、添加材とを十分に混合するために
は、比較的高温で長時間の混合が必要であり、この時硬
化剤を添加すると、硬化反応が進行する恐れがあるため
である。しかし、この第１混合工程で、２種類以上の硬
化剤から成り立つような硬化系の場合、この硬化反応を
支配する硬化剤以外の硬化剤、つまり第１混合工程で反
応が進行する恐れのない硬化剤について添加可能であ
る。例えばエポキシ樹脂に硬化剤としてフエノールノボ
ラツク樹脂とイミダゾールを添加する場合、この硬化反
応を支配するのはイミダゾールであり、エポキシ樹脂と
フエノールノボラツク樹脂との反応は極めて緩慢であ
り、第１混合工程で混合することは可能であり、第２混
合工程でイミダゾールを混合することになる。The reason for separating the first mixing step of melt-mixing the compounding materials and additives other than the curing agent and the second mixing step of melt-mixing the curing agent alone or with the compounding materials and additives is as follows. In order to sufficiently mix the material and the additive, it is necessary to perform mixing at a relatively high temperature for a long time, and if a curing agent is added at this time, the curing reaction may proceed. However, in the case of a curing system that is composed of two or more types of curing agents in the first mixing step, there is no possibility that the curing agent other than the curing agent that governs the curing reaction, that is, the reaction proceeds in the first mixing step. A curing agent can be added. For example, when a phenol novolak resin and imidazole are added as a curing agent to an epoxy resin, imidazole governs this curing reaction, and the reaction between the epoxy resin and the phenol novolak resin is extremely slow. And imidazole will be mixed in the second mixing step.

第２混合工程において硬化剤以外に、配合材、添加材
等を併用して混合することは可能であるが、これらを混
合することによつて混合温度を引上げ或いは時間を長く
することが無いようなものであるべきである。この第２
混合工程での混合手段は、第１混合工程と同じものが使
用可能であるが、混合物への熱履歴を少なくする意図か
ら混練押出機が望ましい。In the second mixing step, it is possible to mix and use a compounding material, an additive and the like in addition to the curing agent, but by mixing these, it is necessary to increase the mixing temperature or to prolong the time. It should be something. This second
As the mixing means in the mixing step, the same means as in the first mixing step can be used, but a kneading extruder is desirable from the viewpoint of reducing the heat history of the mixture.

本発明において、エポキシ樹脂混合物を実質上未硬化
状態でフイルムないしシート（以後、単にシートとい
う）に成形する方法として、シートダイを装着した押出
機による押出成形、カレンダーロールにより材料を圧延
しシート化する方法の他に、コーテイング機を用いて溶
液コーテイング、熱溶融コーテイング等の方法により離
型性基材の上にシートを形成することも可能である。い
ずれの方法を用いても、適宜、ガラス繊維の不織布或い
はガラスクロス等の繊維状の基材を供給することによ
り、前記エポキシ樹脂混合物を基材に含浸或いはラミネ
ートした複合シートに成形することも可能である。前記
の方法で得た実質上未硬化状態のエポキシ樹脂混合物の
シートを更に打抜金型又はトムソン刃型又は彫刻刃型等
の抜型を用いて、打抜プレス等の打抜機で打抜き、所要
の形状を有するエポキシ樹脂成形体を得る。ここで実施
上未硬化状態とは架橋が一部進行しているが完結してい
ない状態を意味する。シートの厚みについては0.01mm未
満の場合、打抜時の衝撃に耐えられない。又、たとえ打
抜けたとしても成形品の強度は非常に小さく取扱い上困
難である。一方厚みが10mmを越えると精度良い打抜きが
困難となる。打抜においてシートを15℃以上、70℃未満
に保つことが肝要である。これは実質上未硬化状態でシ
ート状に成形された前記エポキシ樹脂混合物の材料強度
が、15℃未満ではシートが非常に脆くなり打抜加工に耐
えるに十分でなく、又70℃以上では材料の打型に粘着し
たり打抜後の形状保持が不可能である等、打抜加工に適
さないためである。このため本発明において用いられる
打抜機には、熱盤又は恒温槽などがエポキシ樹脂混合物
のシートを15℃以上、70℃未満の、打抜きに適した温度
に温調する装置が装備されていることが好ましい。又打
抜金型を用いて打抜く場合には、打抜金型も温調する必
要がある。尚、例えば押出機によつてシートを成形する
場合、押出されたシートが冷却引取ロール等により70℃
下に冷却された後、15℃以下に冷却される前に、押出成
形と連続して打抜加工を行うことも可能で、この場合は
特にシートの温調装置を打抜機に装備する必要はない。In the present invention, as a method of forming the epoxy resin mixture into a film or sheet (hereinafter simply referred to as a sheet) in a substantially uncured state, the material is rolled into a sheet by extruding with an extruder equipped with a sheet die and using a calender roll. In addition to the method, it is also possible to form a sheet on a releasable substrate by a method such as solution coating or hot melt coating using a coating machine. Regardless of the method used, it is also possible to form a composite sheet in which the epoxy resin mixture is impregnated or laminated on the substrate by appropriately supplying a fibrous substrate such as a glass fiber nonwoven fabric or glass cloth. It is. The sheet of the epoxy resin mixture in the substantially uncured state obtained by the above method is further punched by a punching machine such as a punching press using a punching die or a punching die such as a Thomson blade die or an engraving blade die. An epoxy resin molded article having a shape is obtained. Here, the practically uncured state means a state in which crosslinking is partially progressed but not completed. If the thickness of the sheet is less than 0.01 mm, it cannot withstand the impact at the time of punching. Also, even if punching is performed, the strength of the molded product is extremely small and it is difficult to handle. On the other hand, if the thickness exceeds 10 mm, it becomes difficult to perform accurate punching. It is important to keep the sheet at 15 ° C or higher and lower than 70 ° C during punching. This is because the material strength of the epoxy resin mixture molded into a sheet in a substantially uncured state is less than 15 ° C., the sheet becomes very brittle and is not enough to withstand punching. This is because it is not suitable for punching, for example, it is not possible to adhere to a die or retain its shape after punching. Therefore, the punching machine used in the present invention is equipped with a device for controlling the temperature of a sheet of the epoxy resin mixture to a temperature suitable for punching, such as a hot plate or a constant temperature bath, of 15 ° C or more and less than 70 ° C. Is preferred. In the case of punching using a punching die, it is necessary to control the temperature of the punching die. For example, when a sheet is formed by an extruder, the extruded sheet is cooled to 70 ° C. by a cooling take-off roll or the like.
After being cooled down, before being cooled to 15 ° C or less, it is possible to perform punching continuously with extrusion molding.In this case, it is not particularly necessary to equip the punching machine with a sheet temperature control device. Absent.

このようにして得られた接着性エポキシ樹脂成形体
（以下、単に「成形体」と呼ぶ）を非接着物或いは非封
止物に接触させた状態で成形体の融点以上に加熱するこ
とによつて、成形体は溶融し被接着物或いは被封止物に
濡れ、更に必要な部位へ流動した後、硬化反応が進行し
て、接着或いは封止硬化するのである。By heating the thus obtained adhesive epoxy resin molded article (hereinafter simply referred to as “molded article”) to a temperature higher than the melting point of the molded article while being in contact with a non-adhesive or non-sealed article. Then, the molded body melts and wets the object to be bonded or the object to be sealed, and after flowing to a necessary portion, the curing reaction proceeds, and the adhesive or the sealing is cured.

被接着物或いは被封止物への接着性或いは封止性を良
くするための成形体の形状があり、これらは例えば棒
状、平板状、リング状、枠状、フイルム状、ペレツト
状、短冊状、更にこれらに孔をあけた形状等が例示でき
る。There is a shape of a molded body for improving the adhesiveness or sealing property to an object to be sealed or an object to be sealed, such as a bar, a plate, a ring, a frame, a film, a pellet, and a strip. And further, a shape in which a hole is formed in these, and the like.

（発明の効果） 本発明の接着性エポキシ樹脂成形体の製造方法によれ
ば、より小型で微細な形状、寸法の接着性熱硬化性成形
体を割れ、欠けなく成形することができ、最近増加しつ
つある電子部品等のような小型、微細な部品の接着、封
止のニーズに十分応えることができる。又、本発明の方
法によつて得られた成形体は、パーツフイーダーやロボ
ツト等の自動化機器で取扱うのに十分な強度を持つてい
るため、工程の自動化、コスト低減に優れた効果を発揮
する。又本発明の方法によつて得られた成形体は、搬送
時の取扱いや振動に対しても強いため、破損することが
なく、摩耗による粉を発生することも少ないので、被着
体である部品等を汚損することが少ない。更に本発明の
方法によれば、より緻密な成形体を得ることができるた
め、溶融接着（又は封止）後、内部に気泡を生じること
がなく、より強固な接着が可能となる。(Effect of the Invention) According to the method for producing an adhesive epoxy resin molded article of the present invention, an adhesive thermosetting molded article having a smaller and finer shape and dimensions can be molded without cracking and chipping, and has recently increased. It is possible to sufficiently meet the needs for bonding and sealing of small and fine components such as electronic components and the like that are becoming increasingly compact. In addition, the molded article obtained by the method of the present invention has sufficient strength to be handled by automated equipment such as a part feeder or a robot, and thus has an excellent effect in automation of a process and cost reduction. I do. Also, the molded article obtained by the method of the present invention is resistant to handling and vibration during transportation, so that it is not damaged and hardly generates powder due to abrasion. There is little contamination of parts. Further, according to the method of the present invention, a denser molded body can be obtained, so that after fusion bonding (or sealing), bubbles are not generated inside, and stronger bonding is possible.

一方、本発明の接着性エポキシ樹脂成形体によれば、
接着剤、封止剤の量的管理（＝体積）、被接着物或いは
被封止物の位置決め（＝形状）、及びロボツト等の自動
化への適応（固型、高強度）が可能であり、接着、封止
による組立が非常に楽になる。又エポキシ系樹脂を主成
分とする為、耐熱性、耐薬品性、耐溶剤性、電気特性、
接着性、密着性等も優れたものとなる。On the other hand, according to the adhesive epoxy resin molded article of the present invention,
Quantitative management (= volume) of adhesives and sealants, positioning (= shape) of objects to be bonded or objects to be sealed, and adaptation to automation of robots (solid type, high strength) are possible. Assembly by bonding and sealing becomes very easy. In addition, since epoxy resin is the main component, heat resistance, chemical resistance, solvent resistance, electrical characteristics,
Adhesion, adhesion and the like are also excellent.

（実施例） 以下に実施例及び比較例を挙げて説明する。尚、単に
部とあるのは重量部を示す。(Example) Hereinafter, an example and a comparative example will be described. It should be noted that the term “parts” simply indicates parts by weight.

実施例１〜４ 〈第１混合工程〉 第１表に示す組成のうち、カーボンブラツク及び硬化
剤を除く組成物を165℃に加熱したニーダーで約１時間
混合した後、室温まで冷却し、約3mm以下の塊状に粗粉
砕した。Examples 1 to 4 <First mixing step> Of the compositions shown in Table 1, the compositions except for the carbon black and the curing agent were mixed for about 1 hour in a kneader heated to 165 ° C, and then cooled to room temperature. It was coarsely pulverized into a lump of 3 mm or less.

〈第２混合工程〉 第１混合工程で得られた混合物のエポキシ樹脂成分10
0部に対して第１表に示すカーボンブラツク及び硬化剤
を添加し、100℃のシリンダー温度に調節された混練押
出機にて溶融混合し、約3mm大のペレツト化したエポキ
シ樹脂混合物を得た。<Second mixing step> The epoxy resin component 10 of the mixture obtained in the first mixing step
To 0 parts, a carbon black and a curing agent shown in Table 1 were added and melt-mixed by a kneading extruder adjusted to a cylinder temperature of 100 ° C. to obtain a pelletized epoxy resin mixture having a size of about 3 mm. .

〈シート製造工程〉 第２混合工程で得られたエポキシ樹脂混合物ペレツト
をリツプ長200mmのＴダイを装着したシリンダー口径が5
0mmの押出機を用いて、まず厚み0.45mm、幅155mmの実質
上未硬化状態のシートを得た。<Sheet manufacturing process> The epoxy resin mixture pellet obtained in the second mixing process was prepared by mounting a T-die having a lip length of 200 mm on a cylinder with a diameter of 5 mm.
First, a substantially uncured sheet having a thickness of 0.45 mm and a width of 155 mm was obtained using a 0 mm extruder.

〈打抜工程〉 このシートを幅20mm、長さ500mmに裁断した後、打抜
プレスに供給し、打抜金型で打抜き、割れや変形を伴う
ことなく所要の接着性エポキシ樹脂成形体を得た。この
打抜プレスには、打抜金型を含む部分を囲む恒温槽が装
備されており、内部温度を40℃に設定し、打抜金型及び
材料シートを予熱した後、打抜いた。打抜かれた成形体
の寸法、形状は中央に1mm×3.2mmの穴を有する外寸3mm
×4.7mmの長方形で厚みは0.45mmである。<Punching process> After cutting this sheet into a width of 20 mm and a length of 500 mm, it is supplied to a punching press and punched with a punching die to obtain the required adhesive epoxy resin molded product without cracking or deformation. Was. The punching press was equipped with a thermostat surrounding the part including the punching die, the internal temperature was set to 40 ° C., and the punching die and the material sheet were preheated before punching. The size and shape of the punched molded body is 3 mm outside diameter with a 1 mm × 3.2 mm hole in the center
It is a rectangle of × 4.7mm and the thickness is 0.45mm.

得られた成形体は室温でベタつくこともなく互いにブ
ロツキングしないものであつた。又、この成形体の強度
を調べるため約10000ケをパーツフイーダーに掛け、１
時間振動を加えたところ、割れ、欠けを生じたものは皆
無で、摩耗によつて発生した粉は認められなかつた。又
得られた成形体を150℃で２時間加熱し、溶融状態を経
て硬化させた後、内部を調べたところ、気泡の発生は全
く見られなかつた。更に成形体を電子部品の端子封着用
途に用いたところ、メラミン樹脂製電子部品本体及び銀
メツキを施した銅製の端子と強固に接着することを確認
した。更に銅製の端子に350℃に熱したハンダゴテを５
秒間あてても何ら外観上変化が起こらず、ハンダ耐熱性
を有していることが確認できた。The obtained molded articles did not stick to each other without stickiness at room temperature. To check the strength of this compact, apply about 10,000 pieces to the parts feeder.
When vibration was applied for a time, there was no crack or chipping, and no powder generated by abrasion was observed. Further, the obtained molded body was heated at 150 ° C. for 2 hours and cured through a molten state. Then, when the inside was examined, no generation of air bubbles was observed at all. Further, when the molded article was used for sealing a terminal of an electronic component, it was confirmed that the molded article was firmly bonded to the melamine resin electronic component main body and the silver-plated copper terminal. Solder iron heated to 350 ° C on copper terminals 5
The appearance did not change at all even after exposure for 2 seconds, confirming that it had solder heat resistance.

比較例１ 実施例１と同じ組成であるが、硬化剤（ジアミノジフ
エニルメタン）を第１混合工程で添加し、実施例１と同
様の条件で混合し、約3mm以下の塊状に粗粉砕した。Comparative Example 1 The same composition as in Example 1, but a curing agent (diaminodiphenylmethane) was added in the first mixing step, mixed under the same conditions as in Example 1, and coarsely pulverized into a lump of about 3 mm or less. .

第２混合工程で残りのカーボンブラツク２部を添加し
100℃のシリンダー温度に調節された混練押出機にて溶
融混合し、約3mm大のペレツト化したエポキシ樹脂混合
物を得たが、ペレツト表面が荒く、硬化反応が進行して
いることが認められた。In the second mixing step, add 2 parts of the remaining carbon black
The mixture was melt-mixed with a kneading extruder adjusted to a cylinder temperature of 100 ° C. to obtain a pelletized epoxy resin mixture of about 3 mm in size, but the pellet surface was rough, and it was recognized that the curing reaction was in progress. .

〈シート製造工程〉 第２混合工程で得られたエポキシ樹脂混合物ペレツト
を実施例１と同様にしてシートを作つた所、シート表面
が荒く、又、シート押出が均一にできず、良好なシート
が得られなかった。<Sheet Manufacturing Process> When a sheet was made from the epoxy resin mixture pellet obtained in the second mixing process in the same manner as in Example 1, the sheet surface was rough, and the sheet extrusion could not be uniform, resulting in a good sheet. Could not be obtained.

〈打抜工程〉 このシートを実施例１と同様に打抜いたが、良好な成
形体が得られず、又この成形体を150℃に加熱したとこ
ろ、全く溶融することが無く、到底接着剤として利用で
きるものではなかつた。<Punching Step> The sheet was punched in the same manner as in Example 1, but no good molded product was obtained. When this molded product was heated to 150 ° C., it was not melted at all, and the adhesive It is not something that can be used as.

比較例２ 分子量174のエポキシ樹脂（ナガセ化成社製、デナコ
ール EX-810）を用いて成形したところ、成形体の表面
は非常にベタつき、互いの成形体が一旦付着すると、は
がれない状態であつた。又成形体の強度も無く、少しの
外力で容易に変形するものであつた。Comparative Example 2 When molded using an epoxy resin having a molecular weight of 174 (Denacol EX-810, manufactured by Nagase Kasei Co., Ltd.), the surfaces of the molded bodies were very sticky, and once the molded bodies adhered to each other, they were in a state where they could not be separated. . Further, the molded article had no strength and was easily deformed by a small external force.

比較例３ 分子量8000のエポキシ樹脂（特開昭60-92320号の実施
例１の樹脂）を用いた場合、第２混合工程での温度が15
0℃以上でないと良好な分散が得られず、150℃で混合し
た場合、硬化反応が混合中に進行し、とてもシートに成
形できるようなものでなかつた。Comparative Example 3 When an epoxy resin having a molecular weight of 8000 (the resin of Example 1 in JP-A-60-92320) was used, the temperature in the second mixing step was 15
If the temperature was not higher than 0 ° C., good dispersion could not be obtained, and when mixed at 150 ° C., the curing reaction proceeded during the mixing, so that the composition could not be formed into a sheet.

比較例４ 熱可塑性樹脂の分子量が3700のポリエステル樹脂（分
子量17000のポリエステル樹脂を加水分解させ分子量を
調整したもの）を用いて成形したところ、成形体の表面
は非常にベタつき、又強度もなく、少しの外力で容易に
変形した。Comparative Example 4 The thermoplastic resin was molded using a polyester resin having a molecular weight of 3700 (having a molecular weight adjusted by hydrolyzing a polyester resin having a molecular weight of 17000), and the surface of the molded article was very sticky and lacked strength. It was easily deformed by a little external force.

比較例５ 熱可塑性樹脂を２部用いた以外、実施例２と同様にし
た場合、得られた成形体はベタつきもなくハンダ耐熱性
も良好であつたが、成形体は脆く、打抜による割れ、カ
ケのない成形体を得ることは非常に困難であつた。Comparative Example 5 When the same procedures were performed as in Example 2 except that two parts of the thermoplastic resin were used, the obtained molded article was not sticky and had good soldering heat resistance, but the molded article was brittle and was cracked by punching. However, it was very difficult to obtain a molded product without chips.

比較例６ 熱可塑性樹脂50部用いた以外、実施例２と同様にした
場合、得られた成形体はベタつきもなく、強度も充分で
あつた。しかし150℃で２時間加熱し、硬化反応を進め
たものでも、ハンダ耐熱性は良くなく、熱によつて溶解
する部分もあつた。Comparative Example 6 When the same procedure as in Example 2 was carried out except that 50 parts of the thermoplastic resin was used, the obtained molded article was not sticky and had sufficient strength. However, even when the composition was heated at 150 ° C. for 2 hours and the curing reaction was advanced, the solder heat resistance was not good, and there were portions that were melted by heat.

比較例７ 実施例１の打抜工程において、打抜金型を含む部分を
囲む恒温槽の内部温度を12℃に設定し、打抜金型及び材
料シートを予熱した後、打抜いたところ、打抜かれた成
形体は全て割れており、本発明の目的とする成形体は得
られなかつた。Comparative Example 7 In the punching step of Example 1, the temperature inside the thermostat surrounding the portion including the punching die was set to 12 ° C., and after the punching die and the material sheet were preheated, punching was performed. All of the punched compacts were cracked, and the desired compact of the present invention could not be obtained.

比較例８ 比較例７は同様に温度を75℃に設定して打抜いたとこ
ろ、シートが金型面に粘着し、打抜かれた成形体を取り
出すことが難しく、又無理に取出しても変形が大きく、
期待する形状とは掛け離れたものであつた。Comparative Example 8 In Comparative Example 7, similarly, when the temperature was set to 75 ° C. and punching was performed, the sheet adhered to the mold surface, and it was difficult to remove the punched molded body. big,
It was far from the expected shape.

Claims (4)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】数平均分子量200以上、5000未満のエポキ
シ樹脂100重量部に数平均分子量5000以上の熱可塑性樹
脂３〜33重量部を、 硬化剤以外の配合材、添加材等と共に、或いは単独
で、溶融混合する第１混合工程と、 硬化剤単独或いはこれを配合材、添加材等と共に溶
融混合する第２混合工程 によつて得られたエポキシ樹脂組成物。An epoxy resin having a number average molecular weight of 200 or more and less than 5000 is mixed with 3 to 33 parts by weight of a thermoplastic resin having a number average molecular weight of 5000 or more together with a compounding material other than a curing agent, an additive, or the like. An epoxy resin composition obtained by a first mixing step of melt-mixing and a second mixing step of melt-mixing the curing agent alone or with a compounding material, an additive and the like. 【請求項２】請求項１のエポキシ樹脂組成物を成形して
得られる接着性エポキシ樹脂成形体。2. An adhesive epoxy resin molded article obtained by molding the epoxy resin composition according to claim 1. 【請求項３】請求項１のエポキシ樹脂組成物を実質上未
硬化状態で0.01mmから10mm厚みのフイルムないしシート
に成形した後、該フイルムないしシートを15℃以上70℃
未満の温度範囲で打抜くことを特徴とする接着性エポキ
シ樹脂成形体の製造方法。3. After molding the epoxy resin composition of claim 1 in a substantially uncured state into a film or sheet having a thickness of 0.01 mm to 10 mm, the film or sheet is heated to 15 ° C. or more and 70 ° C.
A method for producing an adhesive epoxy resin molded body, comprising punching in a temperature range of less than. 【請求項４】請求項２の接着性エポキシ樹脂成形体を、
被接着物或いは被封止物に接触させた状態で、該成形体
の融点以上の温度で加熱し、溶融させ、更に硬化させる
ことを特徴とする接着、封止方法。4. An adhesive epoxy resin molded article according to claim 2,
A method of bonding and sealing, wherein the molded body is heated at a temperature equal to or higher than the melting point of the molded body, melted, and further cured while being in contact with an object to be bonded or an object to be sealed.