JP4395505B2 - Adhesive composition and method of using the composition - Google Patents
Adhesive composition and method of using the composition Download PDFInfo
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Description
本発明は接着剤組成物及びその使用方法に関する。該組成物は、Ｂステージでの安定性に優れ、且つ、気密性及び耐湿性に優れた硬化物を与え、密閉容器を形成するのに好適に使用される。 The present invention relates to an adhesive composition and a method for using the same. The composition is suitable for forming a closed container by giving a cured product excellent in stability at the B stage and excellent in airtightness and moisture resistance.
周囲の環境から保護するために、センサー等を容器内に密閉して使用する場合がある。該容器は、容器本体内にセンサー等を配置した後、蓋を該容器本体に接着して作成される。その際使用する接着剤としては、液状エポキシ樹脂を主剤としたものが多く、例えば、熱硬化型のもの（特許文献１）、紫外線硬化タイプのもの（特許文献２、３）が知られている。 In order to protect from the surrounding environment, a sensor or the like may be used in a sealed state in a container. The container is created by arranging a sensor or the like in the container body and then bonding a lid to the container body. In many cases, the adhesive used at this time is mainly a liquid epoxy resin, for example, a thermosetting type (Patent Document 1) and an ultraviolet curing type (Patent Documents 2 and 3). .
液状エポキシ樹脂を主剤としたものは、粘度が低いために取り扱いが容易であり、作業性も良好である。
しかし、液状エポキシ樹脂を主剤とする接着剤硬化物は、内部に発光性又は発熱性の半導体素子を設置した密閉容器に使用した場合、光劣化して変色等を起こし、場合によっては内部の素子を汚染することが分かった。また、該劣化により、密閉性も低下することが見出された。そこで、本発明は、気密性に優れた硬化物を形成するだけでなく、密閉容器内部を汚染することがなく、且つ、取り扱いに優れた接着剤組成物を提供することを目的とする。 However, cured adhesives based on liquid epoxy resin, when used in a sealed container with a light-emitting or heat-generating semiconductor element inside, cause light deterioration and discoloration, and in some cases, internal elements. Found to contaminate. It has also been found that due to the deterioration, the sealing performance is also lowered. Therefore, an object of the present invention is to provide an adhesive composition that not only forms a cured product having excellent airtightness but also does not contaminate the inside of a sealed container and is excellent in handling.
即ち本発明は、下記のものである。
（Ａ）軟化点が５０℃〜１００℃の芳香族エポキシ樹脂及び該成分（Ａ）のエポキシ基モル量に対する、フェノール性水酸基のモル量の比が０．８〜１．２となる量の（Ｂ）軟化点が５０℃〜１００℃のフェノール樹脂を含む、接着剤組成物。
That is, the present invention is as follows.
(A) the amount of the molar ratio of the phenolic hydroxyl group to the molar amount of the epoxy group of the aromatic epoxy resin having a softening point of 50 ° C to 100 ° C and the component (A) is 0.8 to 1.2 ( B) An adhesive composition containing a phenol resin having a softening point of 50C to 100C.
本発明の接着剤組成物は、軟化点が所定温度範囲の樹脂を使用しており、Ｂステージ状態で保存が容易であり、気密性に優れた封止を形成する。また、硬化の際に、周囲に在る部品を汚染することが無い。 The adhesive composition of the present invention uses a resin having a softening point in a predetermined temperature range, can be easily stored in a B-stage state, and forms a seal having excellent airtightness. In addition, there is no contamination of surrounding parts during curing.
（Ａ）芳香族エポキシ樹脂
芳香族エポキシ樹脂としては、軟化点が５０℃〜１００℃、好ましくは６０℃〜９０℃の樹脂を使用する。ここで軟化点が前記下限値未満である場合は、上述の問題点、即ち、硬化物の変色、接着物周囲に在る素子の汚染等が起こり易い。また、組成物が、後述する成分（Ｆ）希釈剤を含む場合に、該希釈剤を除去した後の状態（以下「Ｂステージ」という場合がある）で、粘着性であるので、Ｂステージでの保存が困難となる。一方、軟化点が上記上限値を越えると、Ｂステージ状態での組成物が堅くなり、保存或いは搬送中に欠けを生じる恐れがある。なお、軟化点は、例えば、ＪＩＳ Ｋ７２３４、示差熱分析（ＤＳＣ）により測定することができる。
(A) Aromatic epoxy resin As the aromatic epoxy resin, a resin having a softening point of 50C to 100C, preferably 60C to 90C is used. Here, when the softening point is less than the lower limit value, the above-mentioned problems, that is, discoloration of the cured product, contamination of elements around the adhesive, and the like are likely to occur. Further, when the composition contains a component (F) diluent described later, the composition is adhesive in the state after the diluent is removed (hereinafter sometimes referred to as “B stage”). It will be difficult to preserve. On the other hand, if the softening point exceeds the above upper limit, the composition in the B-stage state becomes stiff and there is a risk of chipping during storage or transportation. The softening point can be measured by, for example, JIS K7234, differential thermal analysis (DSC).
好ましくは、式（２）のクレゾールノボラック型エポキシ樹脂、或いは式（３）のビスフェノール型エポキシ樹脂である。
上記クレゾールノボラック型エポキシ樹脂としては、例えば、ＥＯＣＮ１０２０（５５）、ＥＯＣＮ１０２０（６５）（いずれも商品名、日本化薬（株）製）が挙げられる。また、ビスフェノール型エポキシ樹脂としては、例えばＥＰＩＫＯＴＥ１００１（商品名、油化シェルエポキシ（株）製）が挙げられる。 Examples of the cresol novolac epoxy resin include EOCN1020 (55) and EOCN1020 (65) (both trade names, manufactured by Nippon Kayaku Co., Ltd.). Examples of the bisphenol-type epoxy resin include EPIKOTE 1001 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.).
成分（Ｂ）：フェノール樹脂
本発明の組成物は、硬化剤として、フェノール樹脂を使用する。通常、ペースト型のエポキシ樹脂組成物では、硬化剤として脂肪族環を有する酸無水物や芳香族アミンが用いられる。しかし脂肪族環を有する酸無水物は、硬化物の気密性が低い。また、芳香族アミンは、エポキシ樹脂との反応性が高く、また、空気中の炭酸ガスとも反応するので、組成物の保存安定性が悪い。これらに対して、フェノール樹脂は、組成物として及びＢステージでの保存安定性が高く、また、緻密な硬化物を与える。
Component (B): Phenolic resin The composition of the present invention uses a phenolic resin as a curing agent. Usually, in a paste type epoxy resin composition, an acid anhydride or an aromatic amine having an aliphatic ring is used as a curing agent. However, the acid anhydride having an aliphatic ring has low hermeticity of the cured product. In addition, the aromatic amine has high reactivity with the epoxy resin and also reacts with carbon dioxide in the air, so that the storage stability of the composition is poor. On the other hand, the phenol resin has high storage stability as a composition and at the B stage, and gives a dense cured product.
該フェノール樹脂（Ｂ）は、芳香族エポキシ樹脂（Ａ）と同様の理由から、軟化点が５０℃〜１００℃、好ましくは６０〜９０℃である。 The phenol resin (B) has a softening point of 50 to 100 ° C., preferably 60 to 90 ° C., for the same reason as the aromatic epoxy resin (A).
好ましくは、式（４）で表されるフェノールノボラック樹脂が使用される。
上式において、ｃは０以上の整数、好ましくは１〜８の整数である。
Preferably, a phenol novolac resin represented by the formula (4) is used.
In the above formula, c is an integer of 0 or more, preferably an integer of 1-8.
上記フェノールノボラック樹脂としては、例えばＤＬ-９２（商品名、明和化成製）が挙げられる。 Examples of the phenol novolac resin include DL-92 (trade name, manufactured by Meiwa Kasei).
このフェノール樹脂は、成分（Ａ）のエポキシ樹脂のエポキシ基モル量に対する、フェノール性水酸基のモル量の比が０．８〜１．２となる量で配合される。ここで、前記比が前記範囲外である場合は、硬化物の気密性が不十分となり得る。 This phenol resin is blended in such an amount that the ratio of the molar amount of the phenolic hydroxyl group to the molar amount of the epoxy group of the epoxy resin of the component (A) is 0.8 to 1.2. Here, when the ratio is out of the range, the airtightness of the cured product may be insufficient.
成分（Ｃ）：熱可塑性樹脂
本発明の樹脂組成物は、熱可塑性樹脂を含有することが好ましい。該熱可塑性樹脂は、接着剤組成物を硬化させるための加熱により、組成物の粘度が低下し過ぎて、被着対象の位置がずれるのを防止する効果を奏する。該熱可塑性樹脂として好ましいものは、重量平均分子量（ポリスチレン換算）が５０００〜１５００００、より好ましくは１００００〜１０００００のフェノキシ樹脂である。重量平均分子量が前記下限値未満である場合は、上記位置ずれ防止効果を奏することができない恐れがある。一方、重量平均分子量が前記上限値より大きい場合は、接着剤組成物の粘度が高くなりすぎ、電子部品等に十分に接着しない恐れがある。
Component (C): Thermoplastic resin The resin composition of the present invention preferably contains a thermoplastic resin. The thermoplastic resin has an effect of preventing the position of the deposition target from shifting due to the viscosity of the composition being excessively lowered by heating for curing the adhesive composition. The thermoplastic resin is preferably a phenoxy resin having a weight average molecular weight (polystyrene conversion) of 5,000 to 150,000, more preferably 10,000 to 100,000. When the weight average molecular weight is less than the lower limit value, there is a possibility that the effect of preventing the displacement cannot be achieved. On the other hand, when the weight average molecular weight is larger than the upper limit, the viscosity of the adhesive composition becomes too high, and there is a possibility that the adhesive composition is not sufficiently bonded to an electronic component or the like.
フェノキシ樹脂は、芳香族系樹脂であり、脂肪族環、炭化水素鎖、シロキサン鎖等を含む熱可塑性樹脂よりも剛直であるので、気密性の高い硬化物を形成することができるものと考えられる。さらに、成分（Ａ）、特にクレゾールノボラック型エポキシ樹脂、或いはビスフェノール型エポキシ樹脂と、成分（Ｂ）のフェノール樹脂、特にフェノールノボラック樹脂と良好に相溶する。 The phenoxy resin is an aromatic resin, and is more rigid than a thermoplastic resin containing an aliphatic ring, a hydrocarbon chain, a siloxane chain, etc., and is considered to be capable of forming a highly airtight cured product. . Furthermore, the component (A), particularly a cresol novolac type epoxy resin or a bisphenol type epoxy resin, and the phenol resin of the component (B), particularly a phenol novolac resin, are well compatible.
該熱可塑性樹脂は、成分（Ａ）エポキシ樹脂と成分（Ｂ）フェノール樹脂の合計量の１００重量部に対して１〜１００重量部、好ましくは２〜５０重量部、より好ましくは３〜１０重量部である。含有量が前記下限値未満である場合は、接着剤組成物の適切な粘度を維持することが困難となる。一方、熱可塑性樹脂の添加量が前記上限値より多い場合は、接着剤組成物の粘度を高くしすぎ、組成物の接着性を阻害する場合がある。 The thermoplastic resin is 1 to 100 parts by weight, preferably 2 to 50 parts by weight, more preferably 3 to 10 parts by weight, based on 100 parts by weight of the total amount of component (A) epoxy resin and component (B) phenol resin. Part. When the content is less than the lower limit, it is difficult to maintain an appropriate viscosity of the adhesive composition. On the other hand, when the addition amount of the thermoplastic resin is larger than the upper limit, the viscosity of the adhesive composition may be excessively increased and the adhesiveness of the composition may be hindered.
成分（Ｄ）：硬化促進剤
本発明の組成物は、成分（Ａ）エポキシ樹脂のグリシジル基と成分（Ｂ）フェノール樹脂の水酸基との反応を速くするために、（Ｄ）硬化促進剤を含むことができる。好ましい硬化促進剤としては、下式（１）のテトラフェニルホスフィン・テトラフェニルボロン誘導体が挙げられる。
上記テトラフェニルホスフィン・テトラフェニルボロン誘導体は、成分（Ａ）のグリシジル基と成分（Ｂ）の水酸基の反応に対する活性温度が２００℃近辺と高温であるために、組成物が、後述する成分（Ｆ）を含む場合に、該希釈剤を除去してＢステージ化する際の温度或いは時間の条件の幅を広く設定することを可能にすると共にＢステージで組成物を保存する際の安定性を達成する。 The tetraphenylphosphine / tetraphenylboron derivative has an active temperature near 200 ° C. and a high temperature for the reaction between the glycidyl group of component (A) and the hydroxyl group of component (B). ), It is possible to set a wide range of temperature or time conditions when removing the diluent to form a B stage, and at the same time achieving stability when storing the composition in the B stage. To do.
（Ｄ）硬化促進剤は、成分（Ａ）のエポキシ樹脂と成分（Ｂ）のフェノール樹脂の合計量の１００重量部に対して０．１〜１０重量部とすることが望ましい。ここで硬化促進剤の含有量が前記下限値重量未満である場合は、十分迅速に硬化反応が進行しない場合がある。一方、硬化促進剤の含有量が前記上限値より多い場合は、組成物の保存安定性が損なわれる場合がある。 (D) It is desirable that the curing accelerator is 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the epoxy resin of component (A) and the phenol resin of component (B). Here, when the content of the curing accelerator is less than the lower limit weight, the curing reaction may not proceed sufficiently rapidly. On the other hand, when there is more content of a hardening accelerator than the said upper limit, the storage stability of a composition may be impaired.
成分（Ｅ）：無機充填剤
本発明の組成物は、無機充填剤を含むことができる。その種類は特に限定されず、組成物の用途に応じて適宜選択される。電気絶縁性が要求される場合には、シリカ、酸化チタン、アルミナ等の絶縁性粉末を用いる。
Component (E): Inorganic filler The composition of the present invention may contain an inorganic filler. The kind is not specifically limited, It selects suitably according to the use of a composition. When electrical insulation is required, an insulating powder such as silica, titanium oxide, or alumina is used.
この無機充填剤は、その最大粒径が接着剤組成物の予定される厚み、希釈剤を含む場合には希釈剤除去後の厚み、の半分以下且つ平均粒径が１／５以下であることが望ましい。ここで無機充填剤の最大粒径、或いは平均粒径が夫々上述の大きさを超える場合は、無機充填剤粒子と周辺の樹脂成分との界面近辺で応力が発生し、電子部品、及び光学部品を破損する恐れがある。 This inorganic filler has a maximum particle size that is less than half of the expected thickness of the adhesive composition, and when the diluent is included, the thickness after removal of the diluent, and the average particle size is 1/5 or less. Is desirable. Here, when the maximum particle size or the average particle size of the inorganic filler exceeds the above-mentioned size, stress is generated in the vicinity of the interface between the inorganic filler particles and the peripheral resin component, and the electronic component and the optical component. There is a risk of damage.
この無機充填剤の含有量は、（Ａ）芳香族エポキシ樹脂と（Ｂ）フェノール樹脂と（Ｃ）熱可塑性樹脂、（Ｄ）硬化促進剤の合計量の１００重量部に対して、１００〜９００重量部であり、好ましくは２００〜５００重量部である。ここで無機充填剤の含有量が前記下限値未満である場合は、接着剤組成物と被着体との界面付近で、熱膨張の差違に起因するストレスが発生し、また相対的に樹脂成分が多くなる為に、吸湿量が増して硬化物気密性が損なわれる場合がある。一方、無機充填剤の含有量が前記上限値よりも多い場合は、無機充填剤の粒子同士の間に存在する空隙の一部に樹脂成分が満たされないものが発生し、その箇所を起因として接着した部分の気密性が損なわれる場合がある。 Content of this inorganic filler is 100-900 with respect to 100 weight part of the total amount of (A) aromatic epoxy resin, (B) phenol resin, (C) thermoplastic resin, and (D) hardening accelerator. Parts by weight, preferably 200 to 500 parts by weight. Here, when the content of the inorganic filler is less than the lower limit, stress due to the difference in thermal expansion occurs near the interface between the adhesive composition and the adherend, and the resin component is relatively Therefore, the amount of moisture absorption increases and the airtightness of the cured product may be impaired. On the other hand, when the content of the inorganic filler is larger than the above upper limit value, some of the voids existing between the particles of the inorganic filler are not filled with the resin component, and adhesion is caused by the location. The airtightness of the damaged part may be impaired.
成分（Ｆ）：希釈剤
本発明の組成物は、該組成物を被着対象物に塗付する際の作業性を向上するために、希釈剤を含むことが好ましい。より好ましくは、該希釈剤は、室温で、（Ａ）芳香族エポキシ樹脂、（Ｂ）フェノール樹脂、（Ｃ）熱可塑性樹脂を実質的に溶解し、且つ（Ｄ）硬化促進剤と（Ｅ）無機充填剤を溶解しない。これにより、組成物の保存安定性が高く、且つ、該組成物を塗付する際の、いわゆる「糸引き」現象を防止することができる。なお、本発明において、各成分の希釈剤への溶解性は、所定量の希釈剤に所定量の各成分を加えたときの外観から判断する。
Component (F): Diluent The composition of the present invention preferably contains a diluent in order to improve workability when the composition is applied to an adherend. More preferably, the diluent substantially dissolves (A) an aromatic epoxy resin, (B) a phenol resin, (C) a thermoplastic resin at room temperature, and (D) a curing accelerator and (E). Does not dissolve inorganic fillers. Thereby, the storage stability of the composition is high, and the so-called “stringing” phenomenon when the composition is applied can be prevented. In the present invention, the solubility of each component in the diluent is determined from the appearance when a predetermined amount of each component is added to a predetermined amount of diluent.
上記条件を満たす希釈剤としては、沸点が１８０℃〜２３０℃のグリコールエステル、特にカルビトールアセテートが好ましい。 As a diluent satisfying the above conditions, a glycol ester having a boiling point of 180 ° C. to 230 ° C., particularly carbitol acetate is preferable.
この希釈剤の含有量は、樹脂組成物全体を１００重量部として、５〜９０重量部、好ましくは５〜３０重量部である。ここで希釈剤の含有量が前記下限値未満である場合は、組成物の粘度が十分に低くならず、作業性に支障をきたす恐れがある。一方、希釈剤の含有量が前記上限値より多い場合は、（Ｅ）無機充填剤が長期保存中に沈降する恐れがある。 The content of the diluent is 5 to 90 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the entire resin composition. Here, when the content of the diluent is less than the lower limit value, the viscosity of the composition is not sufficiently lowered, and there is a risk that workability may be hindered. On the other hand, when there is more content of a diluent than the said upper limit, there exists a possibility that (E) inorganic filler may settle during long-term storage.
その他の成分
本発明の接着剤組成物は先述の６種類の必須成分以外にも、アルコキシシラン等の接着助剤、難燃助剤、イオントラップ剤等が目的や用途に応じて任意に添加される。
Other components In addition to the six essential components described above, the adhesive composition of the present invention includes an adhesion aid such as alkoxysilane, a flame retardant aid, and an ion trap agent depending on the purpose and application. Optionally added.
接着剤組成物の製造方法
本発明の樹脂組成物の製造方法は、成分や目的に応じて公知の方法から選択してよい。通常はミキサー、ロール等を用い、混合して得られる。必要に応じて混合順序、時間、温度、気圧等の条件を設定する。
Method for producing adhesive composition The method for producing the resin composition of the present invention may be selected from known methods according to the components and purpose. Usually, it is obtained by mixing using a mixer, roll or the like. Set conditions such as mixing order, time, temperature, and pressure as required.
接着剤組成物の使用方法
本発明の接着剤組成物は、気密性が要求される密閉容器の形成に好適であり、特に、センサーもしくは検出器、例えば、光センサー、ＣＣＤ、高周波受信器・送信器等のハウジング封止剤、液晶ディスプレイのセル、有機エレクトロルミネッセンス（ＥＬ）物質のセルのシール剤として好適である。特に、センサーもしくは検出器のハウジングの蓋をシールするための、リッドシール剤に好適であり、該リッドシール剤は以下の工程を含む方法で使用する。
内部にセンサーもしくは検出器を備えた密閉容器を形成する方法であって、前記容器は本体と蓋からなり、及び、前記センサーもしくは検出器は本体内部に備えられており、下記工程を含む方法
（工程１）該蓋の、該本体に接着する部分に、本発明の接着剤を施与し、
（工程２）前記接着剤組成物が施与された蓋を８０〜１２０℃で３０〜９０分間加熱し、
（工程３）前記蓋を、施与された接着剤組成物を介して、そのキャビティ内にセンサーもしくは検出器が配置されている本体の上端面に圧着し、
（工程４）得られた密閉容器を１５０〜２００℃で６０〜２４０分間加熱する。
ここで工程１では組成物が、ディスペンサー、プリンター等によって蓋に施与され、工程２では開閉式や連続式のオーブンで加熱されて、成分（Ｆ）希釈剤が除去されて固形状にされ（Ｂステージ化）、工程３では必要に応じて加熱、加圧が可能なボンダーで蓋がハウジング本体上に搭載され、工程４では開閉式や連続式のオーブンで樹脂組成物が硬化される。
Method of using adhesive composition The adhesive composition of the present invention is suitable for forming a sealed container requiring airtightness, and in particular, a sensor or a detector such as a photosensor, CCD, high frequency It is suitable as a sealant for housing sealants such as receivers / transmitters, liquid crystal display cells, and organic electroluminescent (EL) substance cells. Particularly, it is suitable for a lid sealant for sealing a lid of a sensor or detector housing, and the lid sealant is used in a method including the following steps.
A method of forming a sealed container having a sensor or a detector therein, wherein the container is composed of a main body and a lid, and the sensor or detector is provided in the main body, and includes the following steps ( Step 1) Applying the adhesive of the present invention to the portion of the lid that adheres to the body,
(Step 2) The lid to which the adhesive composition is applied is heated at 80 to 120 ° C. for 30 to 90 minutes,
(Step 3) The lid is crimped to the upper end surface of the main body in which a sensor or a detector is disposed in the cavity through the applied adhesive composition,
(Step 4) The obtained sealed container is heated at 150 to 200 ° C. for 60 to 240 minutes.
Here, in step 1, the composition is applied to the lid by a dispenser, a printer, or the like, and in step 2, it is heated in an open / close or continuous oven to remove the component (F) diluent and solidify ( In step 3, the lid is mounted on the housing body with a bonder that can be heated and pressurized as required. In step 4, the resin composition is cured in an open / close or continuous oven.
本発明の組成物は、Ｂステージでの保存安定性に優れるので、工程２で得られるＢステージの組成物が施与された状態で、封止部を保存し、必要な時に工程３以降を行ってもよい。また、本発明の組成物は、工程４における揮発分が少なく、該揮発分によって、容器内に備える素子等を汚染することがほとんど無い。該揮発分は、例えば、硬化中に発生されるガス分を、ガスクロマト分析にて定量することによって測定することができる。 Since the composition of the present invention is excellent in storage stability at the B stage, the sealing part is stored in a state where the composition of the B stage obtained in Step 2 is applied, and Step 3 and subsequent steps are performed when necessary. You may go. Further, the composition of the present invention has a small amount of volatile matter in Step 4, and the volatile matter hardly contaminates elements and the like provided in the container. The volatile matter can be measured, for example, by quantifying the gas content generated during curing by gas chromatographic analysis.
以下に実施例及び比較例を挙げて本発明を更に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited to these examples.
使用物質
下記の物質を使用した。
エポキシ樹脂１（クレゾールノボラック型エポキシ樹脂、軟化点６８℃、日本化薬製ＥＯＣＮ１０２０（６５））
エポキシ樹脂２（ビスフェノールＡ型エポキシ樹脂、軟化点８９℃、油化シェルエポキシ社製ＥＰＩＫＯＴＥ１００１）
エポキシ樹脂３（クレゾールノボラック型エポキシ樹脂、軟化点５７℃、日本化薬製ＥＯＣＮ１０２０（５５））
フェノール樹脂１（フェノールノボラック樹脂、軟化点７２℃、明和化成製ＤＬ-９２）
熱可塑性樹脂（下記式（６）で表されるフェノキシ樹脂、ジャパンエポキシレジン製ＹＬ１２５６、重量平均分子量５１０００、ガラス転移温度９８℃）
硬化促進剤（テトラフェニルホスフィン・テトラフェニルボレート、北興化学製ＴＰＰ-Ｋ）
無機充填剤１（球状溶融シリカ、ＳＥ６２００、平均粒径２ミクロン、最大粒径１０μｍ、アドマテックス社製）
無機充填剤２（酸化チタン、堺化学社製）
接着助剤（γ-グリシドキシプロピルトリメトキシシラン、信越化学工業製ＫＢＭ−４０３）
希釈剤（カルビトールアセテート）
参考例、比較例で使用した物質
エポキシ樹脂４（液状ビスフェノールＡ型エポキシ樹脂、エポキシ当量１８０、日本化薬製ＲＥ３１０Ｓ）
フェノール樹脂２（フェノールノボラック樹脂、軟化点４８℃、明和化成製ＰＬ−６３２８）
Substances used The following substances were used.
Epoxy resin 1 (cresol novolac type epoxy resin, softening point 68 ° C., Nippon Kayaku EOCN1020 (65))
Epoxy resin 2 (bisphenol A type epoxy resin, softening point 89 ° C., EPIKOTE 1001 manufactured by Yuka Shell Epoxy)
Epoxy resin 3 (cresol novolac type epoxy resin, softening point 57 ° C., Nippon Kayaku EOCN1020 (55))
Phenolic resin 1 (phenol novolac resin, softening point 72 ° C, Meiwa Kasei DL-92)
Thermoplastic resin (phenoxy resin represented by the following formula (6), Japan Epoxy Resin YL1256, weight average molecular weight 51000, glass transition temperature 98 ° C.)
Curing accelerator (tetraphenylphosphine / tetraphenylborate, TPP-K manufactured by Hokuko Chemical)
Inorganic filler 1 (spherical fused silica, SE6200, average particle size 2 microns, maximum particle size 10 μm, manufactured by Admatechs)
Inorganic filler 2 (titanium oxide, manufactured by Sakai Chemical Co., Ltd.)
Adhesion aid (γ-glycidoxypropyltrimethoxysilane, Shin-Etsu Chemical KBM-403)
Diluent (carbitol acetate)
Substance epoxy resin 4 used in reference examples and comparative examples (liquid bisphenol A type epoxy resin, epoxy equivalent 180, Nippon Kayaku RE310S)
Phenol resin 2 (phenol novolac resin, softening point 48 ° C., Meiwa Kasei PL-6328)
実施例１〜３、参考例１及び比較例１
表１に示す量（重量部）の各物質を、２５℃で、プラネタリーミキサーで混合した後、３本ロールで混練後、プラネタリーミキサーで再度混合して、各樹脂組成物を得た。これらの樹脂組成物について、以下の（ａ）〜（ｄ）の諸試験を行い、表１に示す結果を得た。
Examples 1 to 3, Reference Example 1 and Comparative Example 1
Each substance (part by weight) shown in Table 1 was mixed at 25 ° C. with a planetary mixer, kneaded with three rolls, and then mixed again with a planetary mixer to obtain each resin composition. These resin compositions were subjected to the following tests (a) to (d), and the results shown in Table 1 were obtained.
試験方法
（ａ）溶解性
各組成物において使用した希釈剤１０ｇを透明なガラス瓶に秤量し、そこに、該組成物で使用した他の物質１０ｇを秤り入れ、２５℃において、振とう機で２４時間攪拌したのちに外観を観測した。全体が透明で均一であれば可溶、不透明或いは不均一であれば不溶とした。
Test method
(A) Solubility 10 g of the diluent used in each composition was weighed into a transparent glass bottle, and 10 g of the other substance used in the composition was weighed therein, and the mixture was shaken at 25 ° C. for 24 hours. After stirring, the appearance was observed. If the whole was transparent and uniform, it was soluble, and if it was opaque or non-uniform, it was insoluble.
（ｂ）糸引き、（ｃ）気密性
図１に示す半導体装置を下記方法により作成した。
（工程１）ガラス蓋（７ｍｍ×７ｍｍ×０．３ｍｍ）の外周部分に組成物を塗布（ニードル：ＥＦＤ製Ｇ２２、速度：５０ｍｍ／秒、２５℃／５０％ＲＨ下）し、
（工程２）組成物が塗付されたガラス蓋を１００℃のオーブン中で６０分間加熱し、
（工程３）シリコンチップ（３ｍｍ×３ｍｍ×０．３ｍｍ）を搭載したセラミックケース（外寸：７ｍｍ×７ｍｍ×１．２ｍｍ、底面及び壁面厚み：０．５ｍｍ）の上端部分に、上基ガラス蓋を、組成物を介して圧着（８０℃、１００ｇ／ｍｍ２、０．５秒）し、
（工程４）得られた試験片を１７５℃のオーブン中で１２０分間加熱した。
(B) Stringing, (c) Airtightness The semiconductor device shown in FIG. 1 was prepared by the following method.
(Step 1) The composition is applied to the outer periphery of a glass lid (7 mm × 7 mm × 0.3 mm) (needle: G22 made by EFD, speed: 50 mm / sec, under 25 ° C./50% RH),
(Step 2) The glass lid coated with the composition is heated in an oven at 100 ° C. for 60 minutes,
(Process 3) Upper base glass lid on the upper end of a ceramic case (outside dimension: 7 mm x 7 mm x 1.2 mm, bottom and wall thickness: 0.5 mm) mounted with silicon chips (3 mm x 3 mm x 0.3 mm) Is pressed through the composition (80 ° C., 100 g / mm 2 , 0.5 seconds),
(Step 4) The obtained test piece was heated in an oven at 175 ° C. for 120 minutes.
上記方法で試験片１００個を作成する際に、ディスペンサーのニードルの先端部分に糸引きが発生する試験片数／総試験片数（１００個）を数えた。尚其々の試験片を作成する時間間隔は５分とし、またニードルの先端部分に付着した組成物は除去せずに放置した。 When 100 test pieces were prepared by the above method, the number of test pieces / total number of test pieces (100 pieces) in which stringing occurred at the tip of the dispenser needle was counted. The time interval for preparing each test piece was 5 minutes, and the composition adhering to the tip of the needle was left without being removed.
上記方法で得られた試験片１００個を、８５℃／８５％ＲＨの条件下で、１６８時間放置した後、２５℃にし、試験片内部に結露等の外観不良が見られる試験片数／総試験片数（１００個）を数えた。 100 test pieces obtained by the above method were allowed to stand for 168 hours under the condition of 85 ° C./85% RH, then set to 25 ° C., and the number of test pieces in which appearance defects such as condensation were observed inside the test piece / total The number of test pieces (100 pieces) was counted.
（ｄ）揮発分
各組成物を、アルミ製板（５ｍｍ×６６ｍｍ）２枚の表面上に、厚みが１５０μｍになるように夫々塗布し、１００℃で１時間乾燥した。得られた試料を、１５０℃に設定したヘッドスペースサンプラー内で１時間保持し、その間に揮発される成分をガスサンプリングして、ガスクロマトグラフィー（ＳＥ−３０キャピラリカラム、注入温度２５０℃、５０℃で２分間保持後１０℃／分で２７０℃まで昇温、検出器ＦＩＤ）で、ベンゼン及びフェノールについて定量し、試料１ｃｍ２当たりの試料の重量に対する揮発量（重量％）を計算した。
(D) Each volatile matter composition was applied on the surface of two aluminum plates (5 mm × 66 mm) so as to have a thickness of 150 μm, and dried at 100 ° C. for 1 hour. The obtained sample is held in a headspace sampler set at 150 ° C. for 1 hour, and gas components are volatilized during that time, and gas chromatography is performed (SE-30 capillary column, injection temperature 250 ° C., 50 ° C.). Then, the temperature was raised to 270 ° C. at 10 ° C./min, and benzene and phenol were quantified with a detector FID), and the volatilization amount (% by weight) relative to the weight of the sample per 1 cm 2 of the sample was calculated.
上表から分かるように、本発明の接着剤組成物は糸ひきが無く、気密性の高い接着部を形成する。また、本発明の組成物は、硬化の間の揮発分が少なく、該揮発分による光学素子、電子部品を汚染することが無い。これに対して、液状エポキシ樹脂を含む比較例１の組成物からの硬化物は、気密性に劣り、また、揮発分が多かった。 As can be seen from the above table, the adhesive composition of the present invention has no stringiness and forms a highly airtight adhesive portion. Further, the composition of the present invention has a small amount of volatile components during curing, and does not contaminate optical elements and electronic components due to the volatile components. On the other hand, the hardened | cured material from the composition of the comparative example 1 containing a liquid epoxy resin was inferior to airtightness, and there were many volatile matters.
本発明の接着剤組成物は、気密性が要求される密閉容器、特に電子素子用の容器を形成するのに好適である。 The adhesive composition of the present invention is suitable for forming an airtight container requiring airtightness, particularly an electronic device container.
Claims (15)
成分（Ａ）のエポキシ基モル量に対するフェノール性水酸基のモル量の比が０．８〜１．２となる量の、（Ｂ）軟化点が５０℃〜１００℃のフェノールノボラック樹脂、
成分（Ａ）と成分（Ｂ）の合計量の１００重量部に対して、１〜１００重量部の（Ｃ）熱可塑性樹脂、
成分（Ａ）と成分（Ｂ）の合計量の１００重量部に対して、０．１〜１０重量部の下記式（１）：
（Ｒ １ 〜Ｒ ８ は、互いに独立に、水素原子、炭素数１〜１０の炭化水素基、又はハロゲン原子である）、
で表される（Ｄ）硬化促進剤、及び
（Ｆ）希釈剤を含み、
室温で、成分（Ａ）、（Ｂ）及び（Ｃ）は成分（Ｆ）に実質的に可溶であり、成分（Ｄ）は実質的に不溶である、密閉容器形成用接着剤組成物。 (A) Cresol novolac type epoxy resin or bisphenol type epoxy resin having a softening point of 50 ° C to 100 ° C ,
(B) a phenol novolac resin having a softening point of 50 ° C. to 100 ° C. in an amount such that the ratio of the molar amount of the phenolic hydroxyl group to the molar amount of the epoxy group of the component (A) is 0.8 to 1.2,
1 to 100 parts by weight of (C) thermoplastic resin with respect to 100 parts by weight of the total amount of component (A) and component (B),
0.1 to 10 parts by weight of the following formula (1) with respect to 100 parts by weight of the total amount of the components (A) and (B):
(R 1 to R 8 are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom),
(D) a curing accelerator represented by:
(F) including a diluent,
An adhesive composition for forming a sealed container, wherein components (A), (B) and (C) are substantially soluble in component (F) and component (D) is substantially insoluble at room temperature .
で表される、請求項１記載の接着剤組成物。 (A) Cresol novolac type epoxy resin is represented by the following formula (2):
The adhesive composition of Claim 1 represented by these.
（ｂは１〜５の整数であり、Ｘはメチレン基または２、２-プロピレン基である。）
で表される、請求項１又は２記載の接着剤組成物。 (A) The bisphenol type epoxy resin has the following formula (3):
(B is an integer of 1 to 5, and X is a methylene group or 2,2-propylene group.)
The adhesive composition of Claim 1 or 2 represented by these.
で表される、請求項１〜３のいずれか１項記載の接着剤組成物。 (B) Phenol novolac resin is represented by the following formula (4):
The adhesive composition of any one of Claims 1-3 represented by these.
（工程１）該蓋の、ハウジング本体に接着する部分に、請求項１〜１３のいずれか１項記載の接着剤組成物を施与し、
（工程２）前記接着剤組成物が施与された蓋を８０〜１２０℃で３０〜９０分間加熱し、
（工程３）前記蓋を、施与された接着剤組成物を介して、そのキャビティ内にセンサーもしくは検出器が配置されている本体の上端面に圧着し、
（工程４）得られた密閉容器を１５０〜２００℃で６０〜２４０分間加熱する。 A method of sealing a sensor or detector in a housing, wherein the housing comprises a main body and a lid, and the sensor or detector is provided inside the main body, and includes the following steps (step 1): Applying the adhesive composition according to any one of claims 1 to 13 to a portion of the lid that adheres to the housing body,
(Step 2) The lid to which the adhesive composition is applied is heated at 80 to 120 ° C. for 30 to 90 minutes,
(Step 3) The lid is crimped to the upper end surface of the main body in which a sensor or a detector is disposed in the cavity through the applied adhesive composition,
(Step 4) The obtained sealed container is heated at 150 to 200 ° C. for 60 to 240 minutes.
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