JP5352955B2 - Adhesive composition - Google Patents
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本発明は接着剤組成物に関する。該接着剤は、Ａステージでの安定性、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接着部を形成する。 The present invention relates to an adhesive composition. The adhesive forms an adhesive portion having excellent stability at the A stage, stability at the B stage, and excellent airtightness and moisture resistance.
電子部品を接着するための接着剤として、エポキシ樹脂にシリカやアルミナ等の無機フィラーを添加した接着剤が知られている。該接着剤を電子部品上に塗布した後に、比較的低温で加熱して流動性を失わせ、いわゆるＢステージ状態とした後に完全に硬化させる方式が提案されている。このＢステージ化の方法には、（１）硬化反応を途中で強制的に停止させる方法、（２）硬化温度領域が低い反応系を共存させて、該反応系を硬化させる方法（例えば特許文献１）がある。このうち（１）の方法は適応可能である反応系の種類が多く、且つ容易な方法であるが、Ｂステージ状態の安定性が不十分である。一方、（２）の方法は反応系の種類が制限され、且つＢステージ状態の安定性が、必ずしも十分ではないという問題がある。ここで、安定性とはＢステージ状態で所定期間放置された後であっても、初期とほぼ同じ挙動を示すことを意味する。この安定性が悪いと、製品をＢステージ状態で保存しておくことができず、製品歩留まりが低下する。 As an adhesive for bonding electronic parts, an adhesive in which an inorganic filler such as silica or alumina is added to an epoxy resin is known. There has been proposed a method in which the adhesive is applied onto an electronic component, and then heated at a relatively low temperature to lose fluidity, and then completely cured after being brought into a so-called B-stage state. This B-stage method includes (1) a method for forcibly stopping the curing reaction in the middle, and (2) a method for curing the reaction system in the presence of a reaction system having a low curing temperature range (for example, Patent Documents). 1). Among these, the method (1) is an easy method with many types of reaction systems that can be applied, but the stability of the B stage state is insufficient. On the other hand, the method (2) has a problem that the type of reaction system is limited and the stability of the B stage state is not always sufficient. Here, the stability means that even after being left in a B stage state for a predetermined period, the same behavior as the initial stage is exhibited. If this stability is poor, the product cannot be stored in the B-stage state, and the product yield decreases.
また、溶剤を含むエポキシ樹脂組成物の溶剤を揮発させてＢステージ化することも知られている。しかし、溶剤を含む接着剤は、接着剤を被着物体に施与する際に、主として増粘に因る、いわゆる「糸引き」を起こす場合がある。糸引きが生じると、被着体を汚染し、また、被着体の位置ずれ等を起こす。
そこで本発明は保存安定性に優れ、糸引き等の無い良好な作業性を維持する接着剤を提供する。 Therefore, the present invention provides an adhesive that is excellent in storage stability and maintains good workability without stringing or the like.
即ち本発明は、下記成分を含む接着剤組成物であって、
（Ａ）芳香族エポキシ樹脂、
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）フェノール樹脂、
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（Ｄ）硬化促進剤、及び
（Ｆ）希釈剤
を含み、
室温で（Ａ）、（Ｂ）及び（Ｃ）は（Ｆ）に実質的に可溶であり、（Ｄ）は実質的に不溶であり、
該接着剤組成物約５ｍｇをアルミセルに秤量し、空のアルミセルを参照試料として、空気中で２５℃から３００℃まで１０℃／分で昇温しながら熱天秤測定を行い、５０℃〜１５０℃の範囲内のＴ〜（Ｔ＋５）（℃）の範囲での重量減量が、前記秤量重量の０．５％未満である最も低い温度ＴをＴ１（℃）とし、
該接着剤組成物約５ｍｇをアルミセルに秤量し、空のアルミセルを参照試料として、空気中で２５℃から３００℃まで１０℃／分で昇温しながら示差走査熱分析測定による硬化発熱ピークのピーク温度をＴ２（℃）とした場合に、
Ｔ１が８０℃〜１２０℃であり且つＴ２がＴ１より８０℃以上高いことを特徴とする接着剤組成物である。
That is, the present invention is an adhesive composition containing the following components,
(A) aromatic epoxy resin,
(B) a phenol resin 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 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 (D) a curing accelerator and (F) a diluent with respect to 100 parts by weight of the total amount of component (A) and component (B),
(A), (B) and (C) are substantially soluble in (F) and (D) is substantially insoluble at room temperature;
About 5 mg of the adhesive composition is weighed into an aluminum cell, and an empty aluminum cell is used as a reference sample, and a thermal balance measurement is performed while raising the temperature from 25 ° C. to 300 ° C. at a rate of 10 ° C./min. T1 (° C.) is the lowest temperature T at which weight loss in the range of T to (T + 5) (° C.) is less than 0.5% of the weighed weight,
About 5 mg of the adhesive composition was weighed into an aluminum cell, and the peak of the curing exothermic peak was measured by differential scanning calorimetry while the temperature was raised from 25 ° C. to 300 ° C. at 10 ° C./min using an empty aluminum cell as a reference sample When the temperature is T2 (° C.)
The adhesive composition is characterized in that T1 is 80 ° C. to 120 ° C. and T2 is 80 ° C. or more higher than T1.
本発明の接着剤組成物は、所定の熱的特性、さらには溶解性を備える希釈剤を含み、Ａステージ及びＢステージでの保存安定性に優れ、精密な部品、特に電子部品或いは光学部品の接着に好適である。 The adhesive composition of the present invention contains a diluent having predetermined thermal characteristics and further solubility, is excellent in storage stability at the A stage and the B stage, and is used for precision parts, particularly electronic parts or optical parts. Suitable for bonding.
（Ａ）：芳香族エポキシ樹脂
芳香族系エポキシ樹脂としては種々のものがあるが、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が好ましく使用される。
好ましくは、該エポキシ樹脂は、５０℃〜１００℃、より好ましくは６０〜９０℃の軟化点を有する。軟化点が、前記下限値未満では、（Ｆ）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、組成物が粘着性であり、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。 Preferably, the epoxy resin has a softening point of 50 to 100 ° C, more preferably 60 to 90 ° C. When the softening point is less than the lower limit, the composition is sticky in the state after removing the diluent (F) (hereinafter sometimes referred to as “B stage”), and it becomes difficult to store. 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).
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ＲＥ３１０Ｓ（日本化薬（株）製）、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 type 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 RE310S (manufactured by Nippon Kayaku Co., Ltd.) and 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。ペースト型のエポキシ樹脂組成物では、通常、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、密閉性の高い接着部を与え、且つ、保存安定性が高い。
Component (B): Phenolic resin The composition of the present invention uses a phenolic resin as a curing agent. In paste-type epoxy resin compositions, acid anhydrides and aromatic amines having an aliphatic ring are usually used as curing agents. 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 phenolic resin provides an adhesive part with high hermeticity and has high storage stability.
フェノール樹脂としては、成分（Ａ）のエポキシ樹脂と同様の理由で、軟化点が５０℃以上であり、式（４）で表されるフェノールノボラック樹脂が特に好適である。
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。
As the phenol resin, a phenol novolac resin represented by the formula (4) having a softening point of 50 ° C. or higher is particularly suitable for the same reason as the epoxy resin of the component (A).
In the above formula, c is an integer of 0 or more, preferably an integer of 1-8.
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、ハウジング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, if the ratio is out of the range, the airtightness of the housing may be insufficient.
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).
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).
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。該熱可塑性樹脂は、接着剤組成物を硬化させる工程で、組成物の粘度が低下し過ぎて、電子部品のズレ等が発生すること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を高くしすぎ、電子部品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 contains a thermoplastic resin. The thermoplastic resin has an effect of preventing the occurrence of misalignment of electronic parts due to excessive decrease in the viscosity of the composition in the step of 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, the above effects may not be achieved. On the other hand, when the weight average molecular weight is larger than the upper limit, the viscosity of the adhesive composition may be too high, and the adhesive may not be sufficiently adhered to the electronic component.
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、気密性の高い接着部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）のエポキシ樹脂、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., so it is considered that a highly airtight adhesive portion can be formed. . Furthermore, the epoxy resin of component (A), particularly cresol novolac type epoxy resin or bisphenol type epoxy resin, and the phenol resin of component (B), particularly phenol novolac resin, are well compatible.
該熱可塑性樹脂は、（Ａ）エポキシ樹脂と（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１０〜１００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維持しすぎ、電子部品に十分に接着しない恐れがある。 The thermoplastic resin is 1 to 100 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the total amount of (A) epoxy resin and (B) phenol resin. 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 value, the viscosity of the adhesive composition is kept too high, and there is a possibility that it is not sufficiently adhered to the electronic component.
成分（Ｄ）：硬化促進剤
硬化促進剤は、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の触媒である。本発明の組成物において、（Ｄ）硬化促進剤は、上記成分（Ａ）、（Ｂ）及び（Ｃ）と異なり、成分（Ｆ）希釈剤に実質的に不溶である。これにより、保存中に、成分（Ａ）と（Ｂ）との反応が促進されず、安定に保存することができ、また、糸引きを防止する。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 (D): Curing accelerator The curing accelerator is a catalyst for the reaction between the glycidyl group of the component (A) epoxy resin and the hydroxyl group of the component (B) phenol resin. In the composition of the present invention, the (D) curing accelerator is substantially insoluble in the component (F) diluent, unlike the components (A), (B) and (C). Thereby, during the storage, the reaction between the components (A) and (B) is not promoted and can be stored stably, and stringing is 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.
斯かる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特に好適である。
さらに、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）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、成分（Ｆ）の希釈剤を除去してＢステージ化する際の温度或いは時間の条件の幅が広くすることを可能にし、さらにＢステージで組成物を保存する際の安定性を達成する。 Furthermore, the tetraphenylphosphine / tetraphenylboron derivative has a high activity temperature for the reaction between the glycidyl group of component (A) and the hydroxyl group of component (B), which is as high as about 200 ° C. It is possible to widen the range of temperature or time conditions for removal and B-stage, and to achieve stability when the composition is stored in the B-stage.
（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０．１重量未満である場合は、十分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１０重量部より多い場合は、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 0.1 weight, the curing reaction may not sufficiently proceed. On the other hand, when there is more content of a hardening accelerator than 10 weight part, storage stability 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に選択される。電気絶縁性が要求される場合には、シリカ、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 or alumina is used.
この無機充填剤は、その最大粒径がシール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。 The inorganic filler should have a maximum particle size that is less than half of the expected thickness of the sealant composition, and when the diluent is included, the thickness after removal of the diluent, and the average particle size should be 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）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、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１００重量部未満である場合は、接着剤組成物と電子部品、及び光学部品の構成部材との界面付近で、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９００重量部よりも多い場合は、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部の気密性が損なわれる場合がある。 Content of this inorganic filler is 100-900 weight part with respect to 100 weight part of the total amount of (A) epoxy resin, (B) phenol resin, (C) thermoplastic resin, and (D) hardening accelerator. The amount is preferably 200 to 500 parts by weight. Here, when the content of the inorganic filler is less than 100 parts by weight, stress due to the difference in thermal expansion occurs in the vicinity of the interface between the adhesive composition and the electronic component and the component of the optical component, Further, since the resin component is relatively increased, the amount of moisture absorption is increased and the airtightness may be impaired. On the other hand, when the content of the inorganic filler is more than 900 parts by weight, some of the voids existing between the particles of the inorganic filler are not filled with the resin component, and the bonded portion is caused by the location. The airtightness of the may be impaired.
成分（Ｆ）：希釈剤
本発明の組成物において、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ものである。これにより、組成物を塗付する際に、組成物の増粘による、いわゆる「糸引き」現象を防止することができる。
Component (F): Diluent In the composition of the present invention, 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) an inorganic filler are not dissolved. Thereby, when applying the composition, the so-called “stringing” phenomenon due to thickening of the composition can be prevented.
さらに、該希釈剤は、該接着剤組成物約５ｍｇをアルミセルに秤量し、空のアルミセルを参照試料として、空気中で２５℃から３００℃まで１０℃／分で昇温しながら熱天秤測定を行い、５０℃〜１５０℃の範囲内のＴ〜（Ｔ＋５）（℃）の範囲での重量減量が、前記秤量重量の０．５％未満である最も低い温度ＴをＴ１（℃）としたときに、Ｔ１が８０℃〜１２０℃、好ましくは１００〜１２０℃であるような揮発性を有する。秤量重量の０．５％未満は、約０．０２５ｍｇの重量減少であり、希釈剤の揮発がほぼ完了し、重量減少を示すカーブがほぼ水平になった点に相当する。例として、図２に、実施例１の組成物のＴ１を測定した熱天秤チャートを示す。同図において、１１４℃〜１１９℃で、重量減少が初期重量の０．４５％である。Ｔ１が８０℃以上であることにより、室温にてシール剤組成物を電子部品に塗布する際に、希釈剤の揮発に起因する塗布ムラが防止される。さらに上述の糸引き問題を防止する。 Furthermore, the diluent is prepared by weighing about 5 mg of the adhesive composition in an aluminum cell, and using an empty aluminum cell as a reference sample, measure the thermobalance while raising the temperature from 25 ° C. to 300 ° C. at 10 ° C./min. When the lowest temperature T at which the weight loss in the range of T to (T + 5) (° C.) within the range of 50 ° C. to 150 ° C. is less than 0.5% of the weighed weight is T1 (° C.) Furthermore, it has volatility such that T1 is 80 to 120 ° C, preferably 100 to 120 ° C. Less than 0.5% of the weighed weight is a weight loss of about 0.025 mg, which corresponds to the point where the diluent volatilization is almost completed and the curve indicating the weight reduction is almost horizontal. As an example, FIG. 2 shows a thermobalance chart in which T1 of the composition of Example 1 was measured. In the figure, the weight loss is 0.45% of the initial weight at 114 ° C. to 119 ° C. When T1 is 80 ° C. or higher, uneven application due to the volatilization of the diluent is prevented when the sealant composition is applied to the electronic component at room temperature. Furthermore, the above-described yarn drawing problem is prevented.
さらに、Ｔ１は、該接着剤組成物約５ｍｇをアルミセルに秤量し、空のアルミセルを参照試料として、空気中で２５℃から３００℃まで１０℃／分で昇温しながら示差走査熱分析（ＤＳＣ）測定による硬化発熱ピークのピーク温度をＴ２（℃）とした場合に、Ｔ２より、８０℃以上低温である。これにより、接着剤組成物のＢステージでの保存安定性を十分に確保することが可能になる。図３に、本組成物のＤＳＣチャートの概念図を示す。最初の吸熱ピークが、希釈剤の揮発を示す。このピークによって、上記Ｔ１を測定することを試みたが、試料の採取量、より正確には表面積、に依存してピーク位置が変化し、再現良く測定することが困難であった。そこで、本発明では、Ｔ１は上述のとおり熱天秤で測定し、Ｔ２はＤＳＣにて測定する。 Further, T1 was obtained by weighing about 5 mg of the adhesive composition in an aluminum cell, and using a blank aluminum cell as a reference sample, differential scanning calorimetry (DSC) while raising the temperature from 25 ° C. to 300 ° C. at 10 ° C./min. ) When T2 (° C.) is the peak temperature of the curing exothermic peak measured, the temperature is 80 ° C. or more lower than T2. Thereby, it is possible to sufficiently ensure the storage stability of the adhesive composition at the B stage. In FIG. 3, the conceptual diagram of the DSC chart of this composition is shown. The first endothermic peak indicates diluent volatilization. Although an attempt was made to measure the T1 with this peak, the peak position varied depending on the amount of sample collected, more precisely the surface area, and it was difficult to measure with good reproducibility. Therefore, in the present invention, T1 is measured with a thermobalance as described above, and T2 is measured with DSC.
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、樹脂組成物全体の１００重量部に対して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５重量部未満である場合は、樹脂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９０重量部より多い場合は、（Ｅ）無機充填剤が長期保存中に沈降する恐れがある。 Content of this diluent is 5-90 weight part with respect to 100 weight part of the whole resin composition, Preferably it is 5-30 weight part. Here, when the content of the diluent is less than 5 parts by weight, the viscosity of the resin composition is not sufficiently lowered, and there is a possibility that the workability may be hindered. On the other hand, when there is more content of a diluent than 90 weight part, 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、気圧等の条件を制御することができる。
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. Conditions such as mixing order, time, temperature, and atmospheric pressure can be controlled as necessary.
接着剤組成物の使用方法
本発明の接着剤組成物は、保存性が要求される用途に好適であり、電子部品に施与した後、８０〜１２０℃で３０〜９０分間加熱してＢステージ状態にして、保存することができる。接着剤組成物の施与は、ディスペンサー、プリンター等によって行うことができ、Ｂステージ化は、開閉式や連続式のオーブンで加熱することによって行うことができる。次いで、加熱、加圧が可能なボンダー等で上記電子部品が基板等に搭載された後、開閉式や連続式のオーブンで硬化される。
Method of using adhesive composition The adhesive composition of the present invention is suitable for applications requiring storage stability, and is applied to an electronic component and then heated at 80 to 120C for 30 to 90 minutes. Then, it can be stored in the B stage state. The application of the adhesive composition can be performed by a dispenser, a printer, or the like, and the B-stage can be performed by heating in an open / close or continuous oven. Next, after the electronic component is mounted on a substrate or the like using a bonder or the like that can be heated and pressurized, it is cured in an openable or continuous oven.
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、エポキシ当量２００、軟化点５７℃、日本化薬製ＥＯＣＮ１０２０（５５））
エポキシ樹脂２（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（フェノールノボラック樹脂、フェノール性水酸基当量１１０、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１（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（球状溶融シリカ、平均粒径２ミクロン、最大粒径１０ミクロン、アドマッテクス製ＳＥ６２００）
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１（カルビトールアセテート）
比較例で使用した物質
エポキシ樹脂３（水添ビスフェノールＡ型エポキシ樹脂、エポキシ当量２００、大日本インキ化学製、ＥＸＡ−７０１５）
硬化促進剤２（トリフェニルホスフィン、北興化学製ＴＰＰ）
希釈剤２（シクロヘキサノン）
Substances used The following substances were used.
Epoxy resin 1 (cresol novolac type epoxy resin, epoxy equivalent 200, softening point 57 ° C., Nippon Kayaku EOCN1020 (55))
Epoxy resin 2 (bisphenol A type epoxy resin, epoxy equivalent 180, Nippon Kayaku RE310S),
Phenol resin (phenol novolac resin, phenolic hydroxyl group equivalent 110, 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 1 (tetraphenylphosphine / tetraphenylborate, TPP-K manufactured by Hokuko Chemical)
Inorganic filler (spherical fused silica, average particle size 2 microns, maximum particle size 10 microns, Admatex SE6200)
Adhesion aid (γ-glycidoxypropyltrimethoxysilane, Shin-Etsu Chemical KBM-403)
Diluent 1 (carbitol acetate)
Substance epoxy resin 3 used in comparative example (hydrogenated bisphenol A type epoxy resin, epoxy equivalent 200, manufactured by Dainippon Ink & Chemicals, EXA-7015)
Curing accelerator 2 (Triphenylphosphine, TPP manufactured by Hokuko Chemical)
Diluent 2 (cyclohexanone)
実施例１〜４及び比較例１〜４
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）〜（ｇ）の諸試験を行い、表１及び２に示す結果を得た。
Examples 1-4 and Comparative Examples 1-4
Each substance (parts 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 (g), and the results shown in Tables 1 and 2 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。
（ｂ）希釈剤の揮発温度：Ｔ１
各組成物の約５ｍｇをアルミセルに秤量した後、空のアルミセルを参照試料として、空気中で２５℃から３００℃まで１０℃／分で昇温しながらＴＧＡ（熱質量分析／メトラー製）測定を行った。５０℃〜１５０℃の範囲内のＴ℃〜（Ｔ＋５）℃の範囲での重量減量が、初期重量の０．５％未満であるような最も低いＴ℃を希釈剤の揮発温度Ｔ１（℃）とした。
（ｃ）硬化促進剤の活性温度：Ｔ２
各組成物の約５ｍｇをアルミセルに採取し、空のアルミセルを参照試料として、空気中で２５℃から３００℃まで１０℃／分で昇温しながらＤＳＣ（示差走査熱分析計、メトラー社製）を行った。１５０℃〜２５０℃の温度領域における発熱ピークのピーク温度をＴ２（℃）とした。
（ｄ）希釈剤の揮発温度と硬化促進剤の活性化温度の関係：Ｔ２-Ｔ１
上述のＴ１とＴ２の差を算出した。
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) Diluent volatilization temperature: T1
About 5 mg of each composition was weighed into an aluminum cell, and TGA (Thermal Mass Spectrometry / Metler) measurement was performed while raising the temperature from 25 ° C. to 300 ° C. at 10 ° C./min using an empty aluminum cell as a reference sample. went. The lowest T ° C in which the weight loss in the range of 50 ° C to 150 ° C in the range of T ° C to (T + 5) ° C is less than 0.5% of the initial weight is the volatilization temperature T1 (° C) of the diluent. It was.
(C) Activation accelerator activation temperature: T2
About 5 mg of each composition was collected in an aluminum cell, DSC (Differential Scanning Calorimeter, manufactured by Mettler) while raising the temperature from 25 ° C. to 300 ° C. at 10 ° C./min using an empty aluminum cell as a reference sample. Went. The peak temperature of the exothermic peak in the temperature range of 150 ° C. to 250 ° C. was defined as T2 (° C.).
(D) Relationship between diluent volatilization temperature and curing accelerator activation temperature: T2-T1
The difference between T1 and T2 described above was calculated.
（ｅ）糸引き及び（ｆ）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）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。
(E) Stringing and (f) 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 / second, 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.
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。 After 100 specimens were allowed to stand for 168 hours under the condition of 85 ° C./85% RH, the specimen was brought to 25 ° C. and the number of specimens in which appearance defects such as condensation were found inside the specimens / total number of specimens (100 specimens) ).
（ｇ）保存安定性
試験片１００個を作成する際に、工程２と工程３の間で組成物の塗膜付きのガラス蓋を、Ｎ２ガス通気下で、２５℃で６ヶ月放置した後に、工程３以降の処置を行って試験片を得た。これに対して、上述の気密性試験を同様に実施し、不良が見られる試験片数／総試験片数（１００個）を数えた。
(G) when creating a storage stability <br/>
上表から分かるように、本発明の接着剤組成物はＡステージ及びＢステージでの保存安定性に優れ、糸引きも無い。これに対して、比較例２の組成物は、反応が進行して、糸ひきが見られた。さらに、硬化が進んでいたために、ガラス蓋を接着することができなかった。比較例３の組成物は、Ｔ１が低く、これも糸ひきを起こした。比較例４は、熱可塑性樹脂を欠き、工程３で流れ出した。 As can be seen from the above table, the adhesive composition of the present invention is excellent in storage stability at the A stage and B stage, and does not have stringing. On the other hand, in the composition of Comparative Example 2, the reaction proceeded and stringing was observed. Furthermore, since the curing was advanced, the glass lid could not be adhered. The composition of Comparative Example 3 had a low T1, which also caused stringing. Comparative Example 4 lacked the thermoplastic resin and flowed out in Step 3.
本発明の接着剤組成物は、組成物の精密な施与が要求され、且つ、Ｂステージの保存性が要求される電子部品の接着に好適である。 The adhesive composition of the present invention is suitable for adhesion of electronic parts that require precise application of the composition and that require B-stage storage.
Claims (3)
（Ａ）軟化点が５０℃〜１００℃のクレゾールノボラック型エポキシ樹脂又はビスフェノール型エポキシ樹脂、
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）ポリスチレン換算の重量平均分子量が５０００〜１５００００のフェノキシ樹脂、
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（Ｄ）下記の式（１）で表される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、
成分（Ａ）、（Ｂ）、（Ｃ）及び（Ｄ）の合計１００重量部に対して、１００〜９００重量部の（Ｅ）シリカ及びアルミナから選ばれる絶縁性無機充填剤、及び
（Ｆ）希釈剤を含み、
前記（Ｆ）希釈剤が常圧での沸点が１８０℃〜２３０℃のグリコールエステルのみから成り、
室温で成分（Ａ）、（Ｂ）及び（Ｃ）は成分（Ｆ）に可溶であり、成分（Ｄ）は不溶であり、
該接着剤組成物５ｍｇをアルミセルに秤量し、空のアルミセルを参照試料として、空気中で２５℃から３００℃まで１０℃／分で昇温しながら熱天秤測定を行い、５０℃〜１５０℃の範囲内のＴ〜（Ｔ＋５）（℃）の範囲での重量減量が、前記秤量重量の０．５％未満である最も低い温度ＴをＴ１（℃）とし、
該接着剤組成物５ｍｇをアルミセルに秤量し、空のアルミセルを参照試料として、空気中で２５℃から３００℃まで１０℃／分で昇温しながら示差走査熱分析測定による硬化発熱ピークのピーク温度をＴ２（℃）とした場合に、
Ｔ１が８０℃〜１２０℃であり且つＴ２がＴ１より８０℃以上高いことを特徴とする絶縁性接着剤組成物。 An insulating adhesive composition comprising the following components,
(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 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) polystyrene-converted phenoxy resin having a weight average molecular weight of 5000 to 150,000 relative to 100 parts by weight of the total amount of component (A) and component (B),
0.1 to 10 parts by weight of (D) tetraphenylphosphine / tetraphenylboron derivative represented by the following formula (1) with respect to 100 parts by weight of the total amount of component (A) and component (B),
Insulating inorganic filler selected from 100 to 900 parts by weight of (E) silica and alumina with respect to a total of 100 parts by weight of components (A), (B), (C) and (D), and (F) Including diluent,
The diluent (F) consists only of a glycol ester having a boiling point of 180 ° C. to 230 ° C. at normal pressure,
At room temperature components (A), (B) and (C) is soluble in component (F), component (D) is not soluble,
5 mg of the adhesive composition was weighed into an aluminum cell, and an empty aluminum cell was used as a reference sample, and a thermobalance measurement was performed while raising the temperature from 25 ° C. to 300 ° C. at a rate of 10 ° C./min. 50 ° C. to 150 ° C. T1 (° C.) is the lowest temperature T at which weight loss in the range of T to (T + 5) (° C.) is less than 0.5% of the weighed weight,
5 mg of the adhesive composition was weighed into an aluminum cell, and the peak of the curing exothermic peak was measured by differential scanning calorimetry while the temperature was raised from 25 ° C. to 300 ° C. at 10 ° C./min using an empty aluminum cell as a reference sample. When the temperature is T2 (° C.)
An insulating adhesive composition, wherein T1 is 80 ° C to 120 ° C and T2 is 80 ° C or more higher than T1.
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| JP2006328734A JP5352955B2 (en) | 2006-12-05 | 2006-12-05 | Adhesive composition |
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| JP2006328734A JP5352955B2 (en) | 2006-12-05 | 2006-12-05 | Adhesive composition |
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| JP5352955B2 true JP5352955B2 (en) | 2013-11-27 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101191111B1 (en) | 2008-09-24 | 2012-10-15 | 주식회사 엘지화학 | Adhesive composition, adhesive film, dicing die bonding film, semiconductor wafer and semiconductor device |
| JP2010116531A (en) * | 2008-10-15 | 2010-05-27 | Hitachi Chem Co Ltd | Adhesive composition, adhesive layer, and multilayer package |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03188180A (en) * | 1989-12-18 | 1991-08-16 | Hitachi Chem Co Ltd | Conductive film adhesive, method for adhesion, semiconductor device, and preparation of semiconductor device |
| JP3191243B2 (en) * | 1990-04-27 | 2001-07-23 | 日立化成工業株式会社 | Method of manufacturing conductive resin paste and semiconductor device |
| JPH06166852A (en) * | 1992-10-01 | 1994-06-14 | Nitto Denko Corp | Thermosetting adhesive sheet |
| JP3575934B2 (en) * | 1997-01-13 | 2004-10-13 | 住友ベークライト株式会社 | Conductive resin paste for bonding semiconductor elements |
| JPH10298526A (en) * | 1997-04-24 | 1998-11-10 | Hitachi Chem Co Ltd | Composition for connecting circuit and film using the same |
| JP3528639B2 (en) * | 1998-11-24 | 2004-05-17 | 日立化成工業株式会社 | Adhesive, adhesive member, wiring board for mounting semiconductor provided with adhesive member, and semiconductor device using the same |
| JP2002097439A (en) * | 2000-09-21 | 2002-04-02 | Hitachi Chem Co Ltd | Adhesive composition, circuit connection material, adhesive composition for circuit connection, connected body, and semiconductor device |
| JP5134747B2 (en) * | 2000-11-28 | 2013-01-30 | 日立化成工業株式会社 | Adhesive film and semiconductor device |
| JP4044349B2 (en) * | 2002-03-11 | 2008-02-06 | 新日鐵化学株式会社 | Thin film adhesive |
| JP2003286390A (en) * | 2002-03-28 | 2003-10-10 | Nippon Steel Chem Co Ltd | Epoxy resin composition, varnish, film adhesive made by using epoxy resin composition, and its cured material |
| JP4083601B2 (en) * | 2003-03-10 | 2008-04-30 | 住友ベークライト株式会社 | Adhesive film, semiconductor package using the same, and semiconductor device |
| JP4603774B2 (en) * | 2003-05-29 | 2010-12-22 | 日東電工株式会社 | Adhesive composition and adhesive film using the same |
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