JP5585760B2 - Liquid resin composition for adhesive, semiconductor device, and method for manufacturing semiconductor device - Google Patents

Description

  The present invention relates to a liquid resin composition for an adhesive, a semiconductor device produced using the same, and a method for producing the semiconductor device.

In recent years, there has been a remarkable progress in higher functionality, smaller size, and lighter weight of mobile phones, personal digital assistants, DVCs (digital video cameras), and there has been a strong demand for higher functionality, smaller size, and lighter weight of semiconductor packages. ing. Therefore, a plurality of semiconductor elements having different functions or a plurality of semiconductor elements having the same function are mounted on a single package to enhance the function of the semiconductor package, and the size of the semiconductor element and the size of the package are reduced in order to reduce the size and weight. Attempts have been made to get as close as possible. For this reason, the thickness of the semiconductor element is further reduced, and the distance between the semiconductor element and the wire bond pad of the support such as a metal or an organic substrate is becoming closer.
In the conventional die attach process in the semiconductor assembly process, a liquid die attach material is applied to the support, and the semiconductor element is bonded to the support by mounting after heating the semiconductor element at room temperature. The problem of adhesion of die attach material to wire bond pads, and the problem of contamination due to bleed of the die attach material (a phenomenon in which only the liquid component of the die attach material is transmitted by capillary action) are becoming ignorable.
Therefore, instead of using a liquid die attach material, a film die attach material is used. After the film die attach material is attached to a support, a semiconductor element is mounted while heating. A method for mounting a semiconductor element with a die attach material obtained by pasting on a dicing sheet after being attached to a dicing sheet in a state where the touch material is attached to a support while heating, a die attach film having a dicing sheet function For example, a method of mounting a semiconductor element with a die attach material obtained by pasting a semiconductor wafer and mounting it on a support while heating is employed. (For example, see Patent Documents 1 and 2.)
On the other hand, the film-like die attach material must have a suitable film for each size of the semiconductor element to be used and the thickness of the die attach material. A method of forming a material layer on a supporting substrate by printing and semi-curing it to substitute for a film material has also been performed. Adhesives for such applications must always proceed to a certain semi-cured state where they must be stopped. For this reason, it is often used to design a curing system up to a semi-cured state and a curing system up to the complete curing thereafter. (For example, refer to Patent Document 3.)
As such a two-stage curable adhesive, a mixed system of an acrylic resin and an epoxy resin can be considered. When the semiconductor element is mounted on the support substrate, the thickness of the adhesive layer tends to be about 30 μm or even thinner, and with such a thickness, it is difficult to control the curing reaction of the acrylic resin, and the stickiness near room temperature. Will remain. The stickiness near room temperature causes the support substrates printed with the adhesive to adhere to each other, which causes a problem in the automatic conveyance of the support substrate in the process of mounting the semiconductor element.
However, when a one-stage curable adhesive is used, a problem due to the reaction temperature occurs. In other words, when a high boiling point solvent that takes time to dry is used, the curing of the adhesive proceeds before the semiconductor element is mounted, and the semiconductor element mounting property is lowered. On the other hand, if the solvent is changed to one having a low boiling point, it dries during printing and the continuous printability is poor. Also, in order to prioritize the semiconductor element mounting property, it is not preferable to introduce a large amount of high molecular weight rubber or the like because thread-like residue is generated during continuous printing (see, for example, Patent Document 4). As described above, it has been difficult to realize an adhesive that eliminates stickiness around room temperature during semi-curing, and achieves both continuous printability and semiconductor element mounting property.
JP 2002-294177 A JP 2003-347321 A JP 2005-513192 A JP 2001-220556 A

  Accordingly, an object of the present invention is to provide a liquid resin composition for an adhesive which is excellent in continuous printability at the time of printing and has a good semiconductor element mounting property after solvent volatilization and which is not sticky at room temperature. is there.

（式中、Ｒ^１、Ｒ^２およびＲ^３は、それぞれ、水素原子、メチル基、メトキシ基およびフェノール性水酸基から選択される１種を示し、互いに同一であっても異なっていてもよい。ｎは、０〜２である。Ａは、ナフタレン環または下記一般式（２）で表される芳香族基を示す。）

（式中、Ｒ^４、Ｒ^５、Ｒ^６およびＲ^７は、それぞれ、水素原子、ハロゲン原子および炭素数１〜６の有機基から選択される１種を示し、互いに同一であっても異なっていてもよい。Ｖは、単結合、エーテル基、スルホン基、スルフィド基、カルボニル基または炭素数１〜１３の有機基を示す。）
（４）前記カチオン部と、アニオン部を有する硬化促進剤が、下記一般式（４）で表される硬化促進剤であることを特徴とする（１）または（２）に記載の接着剤用液状樹脂組成物。

（式中、Ｒ^１、Ｒ^２およびＲ^３は、それぞれ、水素原子、メチル基、メトキシ基およびフェノール性水酸基から選択される１種を示し、互いに同一であっても異なっていてもよい。Ｙ^１およびＹ^２は、酸素原子、窒素原子、硫黄原子のいずれかであり、互いに同一であっても異なっていてもよい。Ｘは、有機基を示し、同一であっても異なっていてもよい。Ｚは、置換または無置換の芳香族環式有機基または複素環式有機基を表す。）
（５）前記カチオン部と、アニオン部を有する硬化促進剤が、下記一般式（６）で表される硬化促進剤であることを特徴とする（１）または（２）に記載の接着剤用液状樹脂組成物。

（式中、Ｒ^１、Ｒ^２およびＲ^３は、それぞれ、水素原子、メチル基、メトキシ基およびフェノール性水酸基から選択される１種を示し、互いに同一であっても異なっていてもよい。Ｙ^３、Ｙ^４、Ｙ^５およびＹ^６のうち少なくとも１つは、分子外に放出するプロトンを少なくとも１個有するプロトン供与体がプロトンを１個放出してなる基であり、それらは互いに同一であっても異なっていてもよい。）
（６）前記エポキシ樹脂（Ｂ）が、常温で固形のエポキシ樹脂であることを特徴とする（１）〜（５）のいずれか記載の接着剤用液状樹脂組成物。
（７）前記エポキシ樹脂硬化剤（Ｃ）が、常温で固形のエポキシ樹脂硬化剤であることを特徴とする（１）〜（６）のいずれか記載の接着剤用液状樹脂組成物。
（８）前記溶剤（Ａ）の沸点が２００℃以上であることを特徴とする（１）〜（７）のいずれか記載の接着剤用液状樹脂組成物。
（９）前記硬化促進剤の硬化反応開始温度が、１３０℃以上であることを特徴とする（１）〜（８）のいずれか記載の接着剤用液状樹脂組成物。
（１０）（１）〜（９）いずれか記載の接着剤用液状樹脂組成物を、支持基板に印刷する印刷工程と、接着剤用液状樹脂組成物から、溶剤を揮発させて、接着剤層を形成させる揮発工程と、半導体素子を搭載する搭載工程と、該接着剤層を硬化させる硬化工程と、を有することを特徴とする半導体装置の製造方法。
（１１）（１）〜（９）のいずれか記載の接着剤用液状樹脂組成物を用いて作製したことを特徴とする半導体装置。
本発明により、印刷時の連続印刷性に優れ、かつ溶剤揮発後に良好な半導体素子搭載性を有しつつも、室温ではべたつきのない接着剤用液状樹脂組成物を提供することができる。Such an object is achieved by the present invention described in the following (1) to (11).
(1) at least a solvent (A), an epoxy resin (B) having two or more epoxy groups in one molecule, and an epoxy resin curing agent (C) having two or more phenolic hydroxyl groups in one molecule; A liquid resin composition for an adhesive containing a curing accelerator (D),
The epoxy resin (B) and the epoxy resin curing agent (C) are dissolved in the solvent (A),
In the temperature range from room temperature to the temperature at which the solvent (A) is volatilized, the curing accelerator (D) converts the epoxy resin (B) and the epoxy resin curing agent (C) into the solvent (A). In the dissolved varnish (W) and in the adhesive layer obtained by volatilizing the solvent (A) from the varnish (W), the solvent (A) is present in a size that can be visually observed. ) In a temperature range from a temperature higher than the temperature at which the solvent is volatilized to a curing temperature, or a size that cannot be visually observed, or is dissolved in the adhesive layer.
(2) at least a solvent (A), an epoxy resin (B) having two or more epoxy groups in one molecule, and an epoxy resin curing agent (C) having two or more phenolic hydroxyl groups in one molecule; A liquid resin composition for an adhesive containing a curing accelerator (E),
The epoxy resin (B) and the epoxy resin curing agent (C) are dissolved in the solvent (A),
A liquid resin composition for an adhesive, wherein the curing accelerator (E) is a curing accelerator having a cation part and an anion part.
(3) The curing accelerator having the cation part and the anion part is a curing accelerator represented by the following general formula (1), for an adhesive according to (1) or (2) Liquid resin composition.

(In the formula, R ¹ , R ² and R ³ each represents one selected from a hydrogen atom, a methyl group, a methoxy group and a phenolic hydroxyl group, and may be the same or different from each other.) Is 0 to 2. A represents a naphthalene ring or an aromatic group represented by the following general formula (2).

(Wherein R ⁴ , R ⁵ , R ⁶ and R ⁷ each represent one selected from a hydrogen atom, a halogen atom and an organic group having 1 to 6 carbon atoms, and are the same or different from each other) V represents a single bond, an ether group, a sulfone group, a sulfide group, a carbonyl group, or an organic group having 1 to 13 carbon atoms.)
(4) For the adhesive according to (1) or (2), the curing accelerator having the cation part and the anion part is a curing accelerator represented by the following general formula (4): Liquid resin composition.

(Wherein R ¹ , R ² and R ³ each represent one selected from a hydrogen atom, a methyl group, a methoxy group and a phenolic hydroxyl group, and may be the same as or different from each other. ¹ and Y ² are each an oxygen atom, a nitrogen atom, or a sulfur atom, and may be the same or different from each other, and X represents an organic group, and may be the same or different. Z represents a substituted or unsubstituted aromatic or heterocyclic organic group.)
(5) For the adhesive according to (1) or (2), the curing accelerator having the cation part and the anion part is a curing accelerator represented by the following general formula (6): Liquid resin composition.

(Wherein R ¹ , R ² and R ³ each represent one selected from a hydrogen atom, a methyl group, a methoxy group and a phenolic hydroxyl group, and may be the same as or different from each other. ³ , at least one of Y ⁴ , Y ⁵ and Y ⁶ is a group formed by releasing one proton from a proton donor having at least one proton released from the molecule, and they are identical to each other. Or different.)
(6) The liquid resin composition for adhesives according to any one of (1) to (5), wherein the epoxy resin (B) is an epoxy resin that is solid at room temperature.
(7) The liquid resin composition for adhesives according to any one of (1) to (6), wherein the epoxy resin curing agent (C) is an epoxy resin curing agent that is solid at room temperature.
(8) The liquid resin composition for adhesives according to any one of (1) to (7), wherein the solvent (A) has a boiling point of 200 ° C. or higher.
(9) The liquid resin composition for an adhesive according to any one of (1) to (8), wherein a curing reaction start temperature of the curing accelerator is 130 ° C. or higher.
(10) A printing process for printing the adhesive liquid resin composition according to any one of (1) to (9) on a support substrate, and an adhesive layer by volatilizing a solvent from the adhesive liquid resin composition. A method for manufacturing a semiconductor device, comprising: a volatilizing step for forming a semiconductor element; a mounting step for mounting a semiconductor element; and a curing step for curing the adhesive layer.
(11) A semiconductor device produced using the liquid resin composition for adhesives according to any one of (1) to (9).
According to the present invention, it is possible to provide a liquid resin composition for an adhesive which is excellent in continuous printability at the time of printing and has a good semiconductor element mounting property after solvent volatilization and which is not sticky at room temperature.

（式（１）中、Ｒ^１、Ｒ^２およびＲ^３は、それぞれ、水素原子、メチル基、メトキシ基およびフェノール性水酸基から選択される１種を示し、互いに同一であっても異なっていてもよい。ｎは、０〜２である。Ａは、ナフタレン環または下記一般式（２）で表される芳香族基を示す。

（式（２）中、Ｒ^４、Ｒ^５、Ｒ^６およびＲ^７は、それぞれ、水素原子、ハロゲン原子および炭素数１〜６の有機基から選択される１種を示し、互いに同一であっても異なっていてもよい。Ｖは、単結合、エーテル基、スルホン基、スルフィド基、カルボニル基または炭素数１〜１３の有機基を示す。）
なお、上記一般式（１）で表される硬化促進剤において、ｎが０の場合は、アニオン部は、１分子内に１個以上のフェノール性水酸基およびフェノキシド基を有する化合物の共役塩基であり、また、ｎが０より大きい場合は、アニオン部は、１分子内に２個以上のフェノール性水酸基を有する化合物と、１分子内に１個以上のフェノール性水酸基およびフェノキシド基を有する化合物の共役塩基との分子会合体である。
前記一般式（１）で表される硬化促進剤としては、下記一般式（３）が挙げられる。

（式（３）中、Ｒ^１、Ｒ^２およびＲ^３は、それぞれ、水素原子、メチル基、メトキシ基およびフェノール性水酸基から選択される１種を示し、互いに同一であっても異なっていてもよい。ｎは、０〜２である。）
また、本発明の接着剤用液状樹脂組成物（２）に係るカチオン部と、アニオン部を有する硬化促進剤（Ｅ）としては、下記一般式（４）で表される硬化促進剤が挙げられる。

（式（４）中、Ｒ^１、Ｒ^２およびＲ^３は、それぞれ、水素原子、メチル基、メトキシ基およびフェノール性水酸基から選択される１種を示し、互いに同一であっても異なっていてもよい。Ｙ^１およびＹ^２は、酸素原子、窒素原子、硫黄原子のいずれかであり、互いに同一であっても異なっていてもよい。Ｘは、有機基を示す。Ｚは、置換または無置換の芳香族環式有機基または複素環式有機基を表す。）
前記一般式（４）中、Ｘ、Ｙ^１およびＹ^２は、珪素原子とキレート構造を形成する。
前記一般式（４）で表される硬化促進剤としては、下記一般式（５）が挙げられる。

（式中、Ｒ^１、Ｒ^２およびＲ^３は、それぞれ、水素原子、メチル基、メトキシ基およびフェノール性水酸基から選択される１種を示し、互いに同一であっても異なっていてもよい。Ｐｈは、フェニル基である。）
また、本発明の接着剤用液状樹脂組成物（２）に係るカチオン部と、アニオン部を有する硬化促進剤（Ｅ）としては、下記一般式（６）で表される硬化促進剤が挙げられる。

（式（６）中、Ｒ^１、Ｒ^２およびＲ^３は、それぞれ、水素原子、メチル基、メトキシ基およびフェノール性水酸基から選択される１種を示し、互いに同一であっても異なっていてもよい。Ｙ^３、Ｙ^４、Ｙ^５およびＹ^６のうち少なくとも１つは、分子外に放出するプロトンを少なくとも１個有するプロトン供与体がプロトンを１個放出してなる基であり、それらは互いに同一であっても異なっていてもよい。）
前記一般式（６）のＹ^３、Ｙ^４、Ｙ^５およびＹ^６は、芳香環若しくは複素環を有する有機基または脂肪族基であって、Ｙ^３、Ｙ^４、Ｙ^５およびＹ^６のうち少なくとも１つは、１個以上のカルボキシル基を有する芳香族カルボン酸、１分子内に酸無水物基および／またはカルボキシル基とをそれぞれ少なくとも１個有する芳香族カルボン酸、１分子内に１個以上の水酸基を有するフェノール化合物、および１分子内にカルボキシル基とフェノール性水酸基とをそれぞれ少なくとも１個有する芳香族化合物の群から選ばれるプロトン供与体がプロトンを１個放出してなる基であり、それらは互いに同一であっても異なっていてもよい。
前記一般式（６）で表される硬化促進剤としては、下記一般式（７）が挙げられる。

（式（７）中、Ｒ^１、Ｒ^２およびＲ^３は、それぞれ、水素原子、メチル基、メトキシ基およびフェノール性水酸基から選択される１種を示し、互いに同一であっても異なっていてもよい。Ｂは、ホウ素原子である。）
本発明の接着剤用液状樹脂組成物（２）は、連続印刷によって、支持基板に接着剤用液状樹脂組成物層を印刷する印刷工程、次いで、支持基板に印刷された接着剤用液状樹脂組成物層から、溶剤（Ａ）を揮発させることにより、支持基板に接着剤層を形成させる揮発工程、次いで、接着剤層が形成された支持基板に、半導体素子を搭載した後、接着剤層を硬化する硬化工程を行うことにより、半導体素子を支持基板上に接着する工程を有する半導体装置の製造方法に用いられる。
このとき、揮発工程で、溶剤（Ａ）を揮発させる揮発温度は、２５〜１５０℃、好ましくは８０〜１２０℃である。また、硬化工程で、接着剤層を硬化させる硬化温度は、９０〜１７０℃、好ましくは１４０〜１６０℃である。また、搭載工程で、半導体素子を搭載する温度は、揮発温度と同程度の温度である。なお、硬化温度は、揮発温度より高い。
硬化促進剤（Ｅ）は、揮発工程において、揮発温度では、ワニス（Ｗ）中およびワニス（Ｗ）から溶剤（Ａ）を揮発させて得られる接着剤層中で、目視で観察できる程度の大きさで存在している。このような状態では、硬化促進剤（Ｅ）は、殆ど硬化反応を促進させない。そして、硬化促進剤（Ｅ）は、硬化工程を行うために、硬化温度まで加熱される間に、つまり、揮発温度より高い温度から硬化温度までの温度範囲のどこかの温度で、目視では観察できない程度の大きさになるか、または接着剤層に溶解する。このことにより、硬化促進剤（Ｅ）は、硬化反応を促進させる。
本発明の接着剤用液状樹脂組成物（２）では、このような硬化促進剤（Ｅ）の作用を利用することにより、揮発工程では、硬化反応が殆ど起こさせず、専ら硬化工程で、硬化反応を起こさせるという、硬化反応の制御が容易となる。
本発明において、目視で観察できる大きさで存在していた硬化促進剤（Ｅ）が、目視で観察できない大きさになるか、または接着剤層に溶解する温度を、硬化促進剤（Ｅ）の状態変化温度と記載する。この硬化促進剤（Ｅ）の状態変化温度は、硬化促進剤（Ｅ）の種類によって異なるため、揮発温度より状態変化温度が高い硬化促進剤（Ｅ）を選択すればよいが、硬化促進剤（Ｅ）の状態変化温度は、好ましくは１００〜１６０℃、特に好ましくは１２０〜１５０℃である。なお、硬化促進剤（Ｅ）の状態変化温度とは、９５重量％のワニス（Ｗ）に対し、５重量％の硬化促進剤（Ｄ）を混ぜ、加熱し、目視で観察できる大きさで存在していた硬化促進剤（Ｄ）が、目視で観察できない大きさになる温度、または９０重量％のワニス（Ｗ）に対し、１０重量％の硬化促進剤（Ｅ）を混ぜ、ＤＳＣ（示差走査熱量計、セイコーインスツルメンツ社製、ＤＳＣ２２０）により昇温速度５℃／分で測定し、溶解する際の吸熱ピークが表れる温度のことである。
硬化促進剤（Ｅ）の硬化反応開始温度は、１３０℃以上が好ましく、さらに好ましくは１４０℃以上である。なお、硬化反応開始温度とは、接着剤用液状樹脂組成物をＤＳＣ（示差走査熱量計、セイコーインスツルメンツ社製、ＤＳＣ２２０）により昇温速度７℃／分で測定し、反応ピークの裾を結んだ線の始まる温度である。
本発明の接着剤用液状樹脂組成物（１）および（２）の粘度は、１０〜６００Ｐａ・ｓ、好ましくは２０〜３００Ｐａ・ｓ、より好ましくは３０〜２００Ｐａ・ｓである。なお、本発明において、液状樹脂組成物の粘度は、Ｅ型粘度計（東洋産業株式会社製、３度コーン）を用いて、２５℃、２．５ｒｐｍで測定された値である。
本発明の接着剤用液状樹脂組成物（１）および（２）は、さらにフィラーを含有することができる。フィラーとしては、シリコーンやウレタン粒子などの有機フィラーや、シリカや炭酸カルシウムなどの無機フィラーであり、印刷性を向上させる為に使用される。即ち、印刷物の形状保持やマスクの開孔部以外の場所への移動を抑制するための粘度調整材として機能するものなら何でも用いることができる。
本発明の接着剤用液状樹脂組成物（１）および（２）は、さらに必要によりカップリング剤、レベリング剤、消泡剤、界面活性剤などを含有することもできる。
本発明の接着剤用液状樹脂組成物（１）および（２）は、印刷時の連続印刷性に優れ、かつ溶剤揮発後に良好な半導体素子搭載性を有しつつも、室温ではべたつきのない接着剤用液状樹脂組成物である。
本発明の接着剤用液状樹脂組成物（１）および（２）を用いる半導体装置の製造方法について説明する。
先ず、本発明の接着剤用液状樹脂組成物（１）および（２）を、半導体素子を搭載する支持基板上に印刷する。ここで、支持基板としては、リードフレームや有機基板、フレキシブル基板などのプリント基板であり、支持基板に半導体素子を搭載し、金線により電気的接続を行うものであるが、半導体素子自体やその他のものであっても構わない。接着剤用液状樹脂組成物の印刷方法としてはスクリーン印刷、ステンシル印刷などが可能であるが、表面の平滑性の観点からステンシルマスクを使ったステンシル印刷法により塗布されることが好ましい。ステンシル印刷法は公知の方法にて行うことが可能である。
次いで、接着剤用液状樹脂組成物が印刷された支持基板を、オーブンや熱盤上で加熱することにより、溶剤（Ａ）を揮発させる揮発工程を行う。揮発工程で溶剤を揮発させて得られた接着剤層が、揮発分を多量に含んでいる場合、接着剤層のべたつきの原因、半導体素子搭載工程でのボイドの原因となりうるので、揮発工程後の接着剤層の揮発分が１重量％以下であることが好ましい。揮発工程の温度は、溶剤が蒸発し、かつ硬化促進剤の状態変化温度未満の範囲であれば良いが、生産性などの観点から、１２０分以内に完了させる為に８０℃以上が好ましい。また、封止前の支持基板を高温に晒すことで、反りが発生するのを防ぐ為に、１５０℃以下が好ましく、１２０℃以下がより好ましい。
揮発工程後の接着剤層の揮発分とは、５０μｍ厚みのステンシルマスク、長さ２７ｃｍのウレタンスキージを用い、スキージ荷重２ｋｇ、スキージ速度２０ｍｍ／ｓで支持基板上に印刷し、揮発工程、即ち１００℃±５℃の乾燥機中で８０±３分間加熱処理した後、取り出した支持基板が冷却される前にスパチュラにてサンプリングした接着剤層５〜３０ｍｇを、熱天秤法（ＴＧＡ）で室温から３００℃まで１０℃／分で昇温して測定した重量減少曲線における２００℃での重量減少率である。より好ましい重量減少率は０．５重量％以下であり、特に好ましいのは０．１重量％以下である。
また接着剤層は室温でタック（べたつき）がないことが好ましい。べたつきがある場合には支持基板同士を重ねて置いた時に互いにくっ付き合い、半導体素子搭載装置の支持基板ピックアップ工程において不具合が発生する恐れがある。このため接着剤用液状樹脂組成物を、５０μｍ厚みのステンシルマスク、長さ２７ｃｍのウレタンスキージを用い、スキージ荷重２ｋｇ、スキージ速度２０ｍｍ／ｓで支持基板上に印刷し、１００℃±５℃の乾燥機中で８０±３分間加熱処理した後の接着剤層は、べたつきの指標となる２５℃でのタック力が０．０５Ｎ以下であることが好ましい。タック力はタック力測定機（ＲＨＥＳＣＡ社製）を用いプローブ下降速度（Ｉｍｍｅｒｓｉｏｎ Ｓｐｅｅｄ）３０ｍｍ／ｍｉｎ、テスト速度６００ｍｍ／ｍｉｎ、密着荷重（Ｐｒｅｌｏａｄ）０．２Ｎ、密着保持時間（Ｐｒｅｓｓ Ｔｉｍｅ）１．０秒、プローブ５．１ｍｍΦ（ＳＵＳ３０４）で測定した値である。
このようにして得られた接着剤層付き半導体素子搭載用支持基板は、通常ダイボンダーに重ねてセットし、ピックアップ（支持基板を上から一枚ずつ取る工程）され、ヒーターブロック上へ運ばれ、加熱状態で半導体素子が搭載される。支持基板のピックアップ時には、ピックアップする支持基板上に印刷された接着剤層と他の支持基板の接着剤が印刷されていない裏面（裏側）との界面で剥がれる必要がある。接着剤層の２５℃でのタック力が０．０５Ｎより大きい場合には重ねられた接着剤層付き半導体素子搭載用支持基板がくっつき、支持基板がピックアップできない、支持基板のピックアップ時に支持基板が二枚重なって取れてしまう、接着剤層の一部が支持基板の裏面に残るなどの問題が生じる恐れがある。
接着剤層付き半導体素子搭載用支持基板とは、リードフレーム、有機基板などに接着剤用液状樹脂組成物を印刷し、溶剤を揮発させたものであり、半導体素子を積層する場合には、リードフレーム、有機基板などに搭載された第２の半導体素子に接着剤用液状樹脂組成物を印刷し、揮発させたものである。半導体素子搭載温度は１５０℃以下が好ましく、より好ましいのは１３０℃以下である。高温での半導体素子搭載はしばしば反りの原因となる。また半導体素子搭載工程においては荷重をかけるが、荷重はダイボンダーの種類により支配される。一部ＬＯＣ（Ｌｅａｄ Ｏｎ Ｃｈｉｐ）ボンダーのように半導体素子あたり２０Ｎほどの荷重をかけられる機種もあるが、通常は３〜５Ｎ程度の荷重で行われる。半導体素子の薄型化、機械的強度の低い半導体素子を考慮すると５Ｎ以下、より好ましくは１〜４Ｎで搭載できることが好ましい。搭載時間（半導体素子を支持体に加圧している時間）は生産性の観点から１０秒以下が好ましく、より好ましいのは３秒以下で、特に好ましくは１秒以下である。
このように半導体素子を低温で搭載するためには、接着剤用液状樹脂組成物を、５０μｍ厚みのステンシルマスク、長さ２７ｃｍのウレタンスキージを用い、スキージ荷重２ｋｇ、スキージ速度２０ｍｍ／ｓで支持基板上に印刷し、１００℃±５℃の乾燥機中で８０±３分間加熱処理後の接着剤層に半導体素子（ダミー素子も含まれる）を１００℃で搭載し、１００℃でせん断強度が１Ｎ以上であることが好ましい。これは加熱処理後の接着剤層の１００℃でのせん断強度の異なる種々の接着剤層付き支持基板に半導体素子を搭載する実験を行った結果、１００℃でのせん断強度が１Ｎ以上であれば搭載後の半導体素子のずれがなかったのに対し、１Ｎに満たない場合にはしばしば半導体素子がずれてしまったからである。
ここでせん断強度の測定は、６×６ｍｍに個片化された半導体素子をダイボンダー上でピックアップしボンド加重１．０Ｎ、支持基板加熱温度１００℃、搭載時間８秒（支持基板表面の温度が１００℃まで昇温する時間７秒を含む）の条件でＰＢＧＡ（Ｐｌａｓｔｉｃ Ｂａｌｌ Ｇｒｉｄ Ａｒｒａｙ）基板（パッケージサイズ３５×３５ｍｍ、コア材：ＢＴ（ビスマレイミド−トリアジン）樹脂、ソルダーレジスト：ＰＳＲ４０００ＡＵＳ３０８（太陽インキ製造（株）製）、厚み０．５６ｍｍ）に搭載したサンプルの１００℃でのせん断強度である。せん断強度の測定はダイシェアテスター（Ｄａｇｅ社製、シリーズ４０００）にて行った値である。
半導体素子を搭載後に接着剤層の硬化を行い、金線で電気的接続を行う。接着剤層の硬化は、硬化促進剤の状態変化温度以上の温度で行う。この温度は、支持基板の反りや接着剤層の分解温度を考慮して、好ましくは２００℃以下、更に好ましくは１８０℃以下、特に好ましいのは１６０℃以下である。
この様にして電気的接続を行った後は樹脂封止をし、支持基板としてリードフレームを使用する場合には必要に応じてリード加工、外装めっきなどを施し半導体装置を得る。また支持基板として有機基板を用いる場合には必要に応じて半田ボールアタッチなどを行い半導体装置を得る。The liquid resin composition for adhesives of the first form of the present invention (hereinafter also referred to as the liquid resin composition for adhesives of the present invention (1)) is at least a solvent (A) and two in one molecule. Liquid for adhesive containing epoxy resin (B) having one or more epoxy groups, epoxy resin curing agent (C) having two or more phenolic hydroxyl groups in one molecule, and curing accelerator (D) A resin composition comprising:
The epoxy resin (B) and the epoxy resin curing agent (C) are dissolved in the solvent (A),
In the temperature range from room temperature to the temperature at which the solvent (A) is volatilized, the curing accelerator (D) converts the epoxy resin (B) and the epoxy resin curing agent (C) into the solvent (A). In the dissolved varnish (W) and in the adhesive layer obtained by volatilizing the solvent (A) from the varnish (W), the solvent (A) is present in a size that can be visually observed. ) In a temperature range from a temperature higher than the temperature at which the solvent is volatilized to the curing temperature, or a liquid resin composition for an adhesive that becomes invisible or can be dissolved in the adhesive layer.
In the present invention, the temperature at which the solvent (A) is volatilized may be equal to or lower than the boiling point of the solvent (A) as long as the solvent (A) is volatilized. The curing temperature is a temperature at which the adhesive layer obtained by volatilizing the solvent (A) from the liquid resin composition for adhesive of the present invention is cured.
The liquid resin composition for adhesives (1) of the present invention is a liquid resin composition for adhesives used for bonding a semiconductor element onto a support substrate. And the liquid resin composition for adhesives (1) of this invention is a liquid process for adhesives printed on the support substrate, then the printing process which prints the liquid resin composition layer for adhesives on a support substrate by continuous printing. A volatilization step for forming an adhesive layer on the support substrate by volatilizing the solvent (A) from the resin composition layer, and then a mounting step for mounting the semiconductor element on the support substrate on which the adhesive layer is formed are performed. Then, it is used for the manufacturing method of the semiconductor device which has the process of adhere | attaching a semiconductor element on a support substrate by performing the hardening process which hardens an adhesive bond layer.
At this time, the volatilization temperature for volatilizing the solvent (A) in the volatilization step is 25 to 150 ° C, preferably 80 to 120 ° C. In addition, the curing temperature for curing the adhesive layer in the curing step is 90 to 170 ° C, preferably 140 to 160 ° C. In the mounting process, the temperature for mounting the semiconductor element is about the same as the volatilization temperature. The curing temperature is higher than the volatilization temperature.
The solvent (A) according to the liquid resin composition for adhesives (1) of the present invention is a solvent for dissolving the epoxy resin (B) and the epoxy resin curing agent (C). And since the liquid resin composition for adhesives of this invention is printed on the semiconductor element mounting surface side of this support substrate by screen printing, stencil printing, etc., the boiling point of a solvent (A) shall be 200 degreeC or more. Is preferable, 200 to 260 ° C is particularly preferable, and 210 to 250 ° C is more preferable. When the epoxy resin (B) and the epoxy resin curing agent (C) are not dissolved in the solvent (A), the surface after printing is not smooth, and when the semiconductor element is mounted, May not occur horizontally), and air may remain when mounted on the support substrate. In addition, when the boiling point of the solvent (A) is less than 200 ° C., the viscosity change due to the volatilization of the solvent becomes too large during printing, which may cause the thickness to become non-uniform and cause blurring. When the boiling point of the solvent (A) is higher than 260 ° C., it may take too much time for the solvent to volatilize, the amount of residual volatile components may increase, and stickiness may remain.
The solvent (A) is not particularly limited as long as it can dissolve the epoxy resin (B) and the epoxy resin curing agent (C). However, a solvent having a halogen atom is not preferable because it is used for semiconductors. Moreover, the solvent which deteriorates the preservability of the liquid resin composition for adhesives like the solvent containing a primary amine or a secondary amine is not preferable. The solvent (A) may be used alone or in combination of two or more.
Examples of the solvent (A) include ethyl benzoate, propyl benzoate, butyl benzoate, γ-butyrolactone, dibutyl oxalate, dimethyl maleate, diethyl maleate, ethylene glycol monobutyrate, propylene carbonate, and N-methylpyrrolidone. 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethyl glycol monomethyl ether, dipropylene glycol, tripropylene glycol monomethyl ether, methyl salicylate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate Etc. Among them, ethyl benzoate having a boiling point of 210 to 250 ° C., propyl benzoate, butyl benzoate, γ-butyrolactone, dibutyl oxalate, diethyl maleate, ethylene glycol monobutyrate, propylene carbonate, diethylene glycol, diethylene glycol monobutyl ether, Triethylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol monomethyl ether, methyl salicylate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and the like are preferable.
As an epoxy resin (B) having two or more epoxy groups in one molecule according to the liquid resin composition for an adhesive (1) of the present invention (hereinafter also simply referred to as an epoxy resin (B)), Phenol novolac type epoxy resin, cresol novolak type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, other epoxy resin having triphenylmethine skeleton, epoxy resin having naphthalene skeleton, anthracene skeleton An epoxy resin having Of these, epoxy resins that are solid at room temperature are preferred. The epoxy resin (B) may be used alone or in combination of two or more. Among the epoxy resins (B), examples of the epoxy resins that are solid at room temperature include epoxy resins having a softening point of 55 ° C. or higher, such as cresol novolac type epoxy resins, phenol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins, and dicyclopentadiene. Type epoxy resin and the like, and cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, and dicyclopentadiene type epoxy resin are preferable.
Epoxy resin curing agent (C) having two or more phenolic hydroxyl groups in one molecule according to the liquid resin composition for adhesives (1) of the present invention (hereinafter, also simply referred to as epoxy resin curing agent (C)). .) Can be obtained by reacting phenol or a derivative thereof with formaldehyde, such as bisphenols such as bisphenol A, bisphenol F, and bisphenol S, phenol novolak, cresol novolak, and the like, and reacting with phenol or its derivative and benzaldehyde. Examples thereof include compounds, phenol aralkyl type phenol resins, biphenyl aralkyl type phenol resins, compounds having a naphthalene skeleton, compounds having an anthracene skeleton, and having two or more phenolic hydroxyl groups in one molecule. Of the epoxy resin curing agent (C), an epoxy resin curing agent that is solid at room temperature is preferable. The epoxy resin curing agent (C) may be used alone or in combination. Among the epoxy resin curing agents (C), examples of the epoxy resin curing agent that is solid at room temperature include epoxy resin curing agents having a softening point of 55 ° C. or higher, such as phenol novolac, phenol aralkyl type phenol resin, biphenyl aralkyl type phenol resin, Bisphenol F etc. are mentioned, Phenol novolac and phenol aralkyl type phenol resin are preferable.
Even if the softening point of the epoxy resin curing agent (C) is high, when mixed with the epoxy resin (B), the softening point of the mixture decreases. For example, the epoxy resin curing agent (C) has a softening point of about 150 ° C. It may be. If neither the epoxy resin (B) nor the epoxy resin curing agent (C) is sticky near room temperature after the solvent (A) is volatilized, a part of the epoxy resin (B) or liquid The epoxy resin curing agent (C) may be used. Liquid epoxy resin (B) or liquid epoxy resin curing agent (C) includes a semi-solid resin having a softening point of less than 55 ° C., and is a cresol novolac type epoxy resin, bisphenol A type epoxy resin, allylphenol type epoxy resin cured. Agents and the like.
The ratio of the epoxy resin (B) and the epoxy resin curing agent (C) is preferably such that the phenolic hydroxyl group is 0.7 to 1.3 with respect to the epoxy group 1. A more desirable ratio is 0.9 to 1.2 in terms of phenolic hydroxyl group with respect to epoxy group 1.
The curing accelerator (D) according to the liquid resin composition for adhesives (1) of the present invention is a curing accelerator that promotes the reaction between the epoxy group of the epoxy resin (B) and the phenolic hydroxyl group of the epoxy resin curing agent (C). It is an agent.
The curing accelerator (D) is a varnish (W) in which the epoxy resin (B) and the epoxy resin curing agent (C) are dissolved in the solvent (A) in the temperature range from room temperature to the temperature at which the solvent (A) is volatilized. ) And in the adhesive layer obtained by volatilizing the solvent (A) from the varnish (W), and present in a size that can be visually observed, and from a temperature higher than the temperature at which the solvent (A) is volatilized. Somewhere in the temperature range up to the curing temperature, it becomes a size that cannot be visually observed or dissolves in the adhesive layer. For example, when the temperature at which the solvent (A) is volatilized is 100 ° C. and the curing temperature is 175 ° C., the curing accelerator (D) is a solvent (A at 100 ° C. in the temperature range from room temperature to 100 ° C. ) In the varnish (W) during volatilization, and in the adhesive layer obtained by volatilizing the solvent (A) from the varnish (W), it exists in a size that can be visually observed. And in order to harden an adhesive bond layer, it becomes a magnitude | size which cannot be observed visually at some temperature during heating from 100 degreeC to 175 degreeC, or melt | dissolves in an adhesive bond layer.
In the liquid resin composition for adhesives (1) of the present invention, by using the curing accelerator (D) having such properties, the curing reaction hardly occurs in the printing step and the volatilization step, and after the mounting step, In the curing process, a curing reaction occurs when heating to the curing temperature. If the curing accelerator (D) becomes a size that cannot be visually observed in the temperature range from room temperature to the temperature at which the solvent (A) is volatilized or dissolved in the varnish (W) or adhesive layer, Since the reaction gradually proceeds even at room temperature, the storage stability at room temperature deteriorates, the curing reaction proceeds in the volatilization process, and sufficient adhesion cannot be obtained in the subsequent semiconductor element mounting process. Even if the volatilization step is finished with adhesive strength, the storage stability when left at room temperature after the volatilization step is extremely short.
In this invention, the hardening accelerator (D) which existed in the size which can be visually observed becomes the size which cannot be observed visually, or the temperature which melt | dissolves in an adhesive bond layer is a hardening accelerator (D). Stated as state change temperature. Since the state change temperature of the curing accelerator (D) varies depending on the type of the curing accelerator (D), the curing accelerator (D) having a higher state change temperature than the volatilization temperature may be appropriately selected. The state change temperature of (D) is preferably 100 to 160 ° C, particularly preferably 120 to 150 ° C. In the present invention, the state change temperature of the curing accelerator (D) can be visually observed by mixing 5% by weight of the curing accelerator (D) with 95% by weight of the varnish (W), heating. The curing accelerator (D) present in the size is mixed with a temperature at which the curing accelerator (D) becomes a size that cannot be visually observed, or 90% by weight of the varnish (W), and 10% by weight of the curing accelerator (D) is mixed. (Differential scanning calorimeter, manufactured by Seiko Instruments Inc., DSC220) is a temperature at which an endothermic peak appears when the curing accelerator (D) is dissolved, as measured at a heating rate of 5 ° C./min.
The curing reaction start temperature of the curing accelerator (D) is preferably 130 ° C. or higher, more preferably 140 ° C. or higher. The curing reaction start temperature was measured by DSC (differential scanning calorimeter, manufactured by Seiko Instruments Inc., DSC220) at a heating rate of 7 ° C./min. The temperature at which the line begins.
The liquid resin composition for an adhesive according to the second embodiment of the present invention (hereinafter also referred to as the liquid resin composition for an adhesive of the present invention (2)) is at least a solvent (A) and two in one molecule. Liquid for adhesive containing epoxy resin (B) having one or more epoxy groups, epoxy resin curing agent (C) having two or more phenolic hydroxyl groups in one molecule, and curing accelerator (E) A resin composition comprising:
The epoxy resin (B) and the epoxy resin curing agent (C) are dissolved in the solvent (A),
The curing accelerator (E) is a liquid resin composition for adhesives, which is a curing accelerator having a cation part and an anion part.
The liquid resin composition for adhesives (2) of the present invention is a liquid resin composition for adhesives used for bonding a semiconductor element onto a support substrate.
The solvent (A), the epoxy resin (B) and the epoxy resin curing agent (C) according to the liquid resin composition for adhesives (2) of the present invention relate to the liquid resin composition for adhesives (1) of the present invention. The same as the solvent (A), the epoxy resin (B), and the epoxy resin curing agent (C).
The curing accelerator (E) according to the liquid resin composition for an adhesive (2) of the present invention is a curing accelerator having a cation part and an anion part. The curing accelerator (E) is represented by the following general formula ( Examples thereof include a curing accelerator represented by 1).

(In formula (1), R ¹ , R ² And R ³ Each represents one selected from a hydrogen atom, a methyl group, a methoxy group, and a phenolic hydroxyl group, and may be the same or different. n is 0-2. A represents a naphthalene ring or an aromatic group represented by the following general formula (2).

(In formula (2), R ⁴ , R ⁵ , R ⁶ And R ⁷ Each represents one selected from a hydrogen atom, a halogen atom and an organic group having 1 to 6 carbon atoms, and may be the same or different from each other. V represents a single bond, an ether group, a sulfone group, a sulfide group, a carbonyl group, or an organic group having 1 to 13 carbon atoms. )
In the curing accelerator represented by the general formula (1), when n is 0, the anion moiety is a conjugate base of a compound having one or more phenolic hydroxyl groups and phenoxide groups in one molecule. When n is larger than 0, the anion moiety is a conjugate of a compound having two or more phenolic hydroxyl groups in one molecule and a compound having one or more phenolic hydroxyl groups and a phenoxide group in one molecule. A molecular association with a base.
Examples of the curing accelerator represented by the general formula (1) include the following general formula (3).

(In formula (3), R ¹ , R ² And R ³ Each represents one selected from a hydrogen atom, a methyl group, a methoxy group, and a phenolic hydroxyl group, and may be the same or different. n is 0-2. )
Moreover, as a hardening accelerator (E) which has a cation part which concerns on the liquid resin composition for adhesives (2) of this invention, and an anion part, the hardening accelerator represented by following General formula (4) is mentioned. .

(In formula (4), R ¹ , R ² And R ³ Each represents one selected from a hydrogen atom, a methyl group, a methoxy group, and a phenolic hydroxyl group, and may be the same or different. Y ¹ And Y ² Are either an oxygen atom, a nitrogen atom, or a sulfur atom, and may be the same or different. X represents an organic group. Z represents a substituted or unsubstituted aromatic cyclic organic group or a heterocyclic organic group. )
In the general formula (4), X, Y ¹ And Y ² Forms a chelate structure with a silicon atom.
Examples of the curing accelerator represented by the general formula (4) include the following general formula (5).

(Wherein R ¹ , R ² And R ³ Each represents one selected from a hydrogen atom, a methyl group, a methoxy group, and a phenolic hydroxyl group, and may be the same or different. Ph is a phenyl group. )
Moreover, as a hardening accelerator (E) which has the cation part which concerns on the liquid resin composition for adhesives (2) of this invention, and an anion part, the hardening accelerator represented by following General formula (6) is mentioned. .

(In formula (6), R ¹ , R ² And R ³ Each represents one selected from a hydrogen atom, a methyl group, a methoxy group, and a phenolic hydroxyl group, and may be the same or different. Y ³ , Y ⁴ , Y ⁵ And Y ⁶ At least one of them is a group formed by releasing a proton from a proton donor having at least one proton released from the molecule, and they may be the same or different from each other. )
Y in the general formula (6) ³ , Y ⁴ , Y ⁵ And Y ⁶ Is an organic or aliphatic group having an aromatic ring or a heterocyclic ring, and Y ³ , Y ⁴ , Y ⁵ And Y ⁶ At least one of them is an aromatic carboxylic acid having one or more carboxyl groups, an aromatic carboxylic acid having at least one acid anhydride group and / or a carboxyl group in one molecule, and one in one molecule. A proton donor selected from the group of phenol compounds having at least one hydroxyl group and aromatic compounds each having at least one carboxyl group and phenolic hydroxyl group in one molecule is a group formed by releasing one proton. , They may be the same as or different from each other.
Examples of the curing accelerator represented by the general formula (6) include the following general formula (7).

(In formula (7), R ¹ , R ² And R ³ Each represents one selected from a hydrogen atom, a methyl group, a methoxy group, and a phenolic hydroxyl group, and may be the same or different. B is a boron atom. )
The liquid resin composition for adhesives (2) of the present invention is a printing process for printing a liquid resin composition layer for adhesives on a support substrate by continuous printing, and then the liquid resin composition for adhesives printed on a support substrate. The volatilization step of forming an adhesive layer on the support substrate by volatilizing the solvent (A) from the physical layer, and then mounting the semiconductor element on the support substrate on which the adhesive layer is formed, By performing the hardening process which hardens | cures, it is used for the manufacturing method of the semiconductor device which has the process of adhere | attaching a semiconductor element on a support substrate.
At this time, the volatilization temperature for volatilizing the solvent (A) in the volatilization step is 25 to 150 ° C, preferably 80 to 120 ° C. In addition, the curing temperature for curing the adhesive layer in the curing step is 90 to 170 ° C, preferably 140 to 160 ° C. In the mounting process, the temperature for mounting the semiconductor element is about the same as the volatilization temperature. The curing temperature is higher than the volatilization temperature.
In the volatilization step, the curing accelerator (E) is large enough to be visually observed in the varnish (W) and in the adhesive layer obtained by volatilizing the solvent (A) from the varnish (W). It exists. In such a state, the curing accelerator (E) hardly accelerates the curing reaction. The curing accelerator (E) is visually observed while being heated to the curing temperature in order to perform the curing process, that is, at any temperature in the temperature range from the temperature higher than the volatilization temperature to the curing temperature. Unusable size or dissolves in the adhesive layer. Thereby, a hardening accelerator (E) accelerates | stimulates hardening reaction.
In the liquid resin composition for adhesives (2) of the present invention, by utilizing the action of such a curing accelerator (E), the curing reaction hardly occurs in the volatilization process, and the curing is performed exclusively in the curing process. It is easy to control the curing reaction to cause the reaction.
In the present invention, the temperature at which the curing accelerator (E) that has been present in a size that can be visually observed becomes a size that cannot be visually observed or dissolves in the adhesive layer is set to the temperature of the curing accelerator (E). Stated as state change temperature. Since the state change temperature of the curing accelerator (E) varies depending on the type of the curing accelerator (E), a curing accelerator (E) having a higher state change temperature than the volatilization temperature may be selected. The state change temperature of E) is preferably 100 to 160 ° C., particularly preferably 120 to 150 ° C. The state change temperature of the curing accelerator (E) is present in a size that can be visually observed by mixing, heating, and heating 5% by weight of the curing accelerator (D) to 95% by weight of the varnish (W). 10% by weight of the curing accelerator (E) was mixed with the temperature at which the curing accelerator (D) had a size that could not be visually observed, or 90% by weight of the varnish (W), and DSC (differential scanning) It is a temperature at which an endothermic peak appears when it is dissolved by a calorimeter, manufactured by Seiko Instruments Inc., DSC220) at a heating rate of 5 ° C./min.
The curing reaction start temperature of the curing accelerator (E) is preferably 130 ° C. or higher, more preferably 140 ° C. or higher. The curing reaction start temperature was measured by DSC (differential scanning calorimeter, manufactured by Seiko Instruments Inc., DSC220) at a heating rate of 7 ° C./min. The temperature at which the line begins.
The viscosity of the liquid resin composition for adhesives (1) and (2) of the present invention is 10 to 600 Pa · s, preferably 20 to 300 Pa · s, more preferably 30 to 200 Pa · s. In the present invention, the viscosity of the liquid resin composition is a value measured at 25 ° C. and 2.5 rpm using an E-type viscometer (manufactured by Toyo Sangyo Co., Ltd., 3 ° cone).
The liquid resin composition for adhesives (1) and (2) of the present invention can further contain a filler. Examples of the filler include organic fillers such as silicone and urethane particles, and inorganic fillers such as silica and calcium carbonate, which are used for improving printability. That is, any material can be used as long as it functions as a viscosity adjusting material for maintaining the shape of the printed material and suppressing the movement of the mask to a place other than the aperture portion.
The liquid resin composition for adhesives (1) and (2) of the present invention may further contain a coupling agent, a leveling agent, an antifoaming agent, a surfactant, and the like as necessary.
The liquid resin compositions for adhesives (1) and (2) of the present invention are excellent in continuous printability at the time of printing, and have good semiconductor element mounting property after solvent volatilization, but have no stickiness at room temperature. It is a liquid resin composition for an agent.
A method for manufacturing a semiconductor device using the liquid resin composition for adhesives (1) and (2) of the present invention will be described.
First, the liquid resin composition for adhesives (1) and (2) of the present invention is printed on a support substrate on which a semiconductor element is mounted. Here, the support substrate is a printed circuit board such as a lead frame, an organic substrate, or a flexible substrate. A semiconductor element is mounted on the support substrate and electrically connected by a gold wire. It doesn't matter. Screen printing, stencil printing, and the like are possible as the printing method for the liquid resin composition for adhesive, but it is preferably applied by a stencil printing method using a stencil mask from the viewpoint of surface smoothness. The stencil printing method can be performed by a known method.
Subsequently, the support substrate on which the liquid resin composition for the adhesive is printed is heated on an oven or a hot platen to perform a volatilization step for volatilizing the solvent (A). If the adhesive layer obtained by volatilizing the solvent in the volatilization process contains a large amount of volatile components, it may cause stickiness of the adhesive layer and voids in the semiconductor element mounting process. The volatile content of the adhesive layer is preferably 1% by weight or less. The temperature of the volatilization step may be in the range below the temperature at which the solvent evaporates and the state of the curing accelerator changes, but from the viewpoint of productivity and the like, 80 ° C. or higher is preferable in order to complete within 120 minutes. Further, in order to prevent warping from occurring by exposing the support substrate before sealing to a high temperature, 150 ° C. or lower is preferable, and 120 ° C. or lower is more preferable.
The volatile content of the adhesive layer after the volatilization process is a stencil mask with a thickness of 50 μm, a urethane squeegee with a length of 27 cm, printed on a support substrate with a squeegee load of 2 kg and a squeegee speed of 20 mm / s, and the volatilization process, ie 100 After heat treatment for 80 ± 3 minutes in a dryer at 5 ° C. ± 5 ° C., 5-30 mg of an adhesive layer sampled with a spatula before the taken out support substrate is cooled is heated from room temperature by a thermobalance method (TGA). It is the weight reduction rate at 200 ° C. in the weight reduction curve measured by raising the temperature up to 300 ° C. at 10 ° C./min. A more preferred weight loss rate is 0.5% by weight or less, and particularly preferred is 0.1% by weight or less.
The adhesive layer preferably has no tack (stickiness) at room temperature. If there is stickiness, the support substrates may stick to each other when they are placed on top of each other, which may cause problems in the support substrate pickup process of the semiconductor element mounting apparatus. For this purpose, the liquid resin composition for adhesives was printed on a support substrate with a squeegee load of 2 kg and a squeegee speed of 20 mm / s using a 50 μm thick stencil mask and a 27 cm long urethane squeegee, and dried at 100 ° C. ± 5 ° C. The adhesive layer after heat treatment for 80 ± 3 minutes in the machine preferably has a tack force at 25 ° C. of 0.05 N or less, which is a stickiness index. The tack force is measured using a tack force measuring machine (manufactured by RHESCA) at a probe descending speed (Immersion Speed) of 30 mm / min, a test speed of 600 mm / min, a contact load (Preload) of 0.2 N, and a contact holding time (Press Time) of 1.0. This is a value measured with a probe of 5.1 mmΦ (SUS304).
The thus obtained support substrate for mounting a semiconductor element with an adhesive layer is usually set on a die bonder, picked up (a step of taking the support substrate one by one from the top), transported onto a heater block, and heated. A semiconductor element is mounted in a state. When picking up the support substrate, it is necessary to peel off at the interface between the adhesive layer printed on the support substrate to be picked up and the back surface (back side) where the adhesive of the other support substrate is not printed. When the tack force at 25 ° C. of the adhesive layer is greater than 0.05 N, the stacked support substrate for semiconductor element mounting with the adhesive layer sticks together, and the support substrate cannot be picked up. There is a possibility that a problem such as a part of the adhesive layer remaining on the back surface of the support substrate may occur.
A support substrate for mounting a semiconductor element with an adhesive layer is a liquid resin composition for adhesive printed on a lead frame, an organic substrate, etc., and the solvent is volatilized. A liquid resin composition for an adhesive is printed and volatilized on a second semiconductor element mounted on a frame, an organic substrate, or the like. The semiconductor element mounting temperature is preferably 150 ° C. or lower, and more preferably 130 ° C. or lower. Mounting a semiconductor element at a high temperature often causes warping. A load is applied in the semiconductor element mounting process, but the load is governed by the type of die bonder. Some models, such as some LOC (Lead On Chip) bonders, can apply a load of about 20 N per semiconductor element, but are usually performed with a load of about 3 to 5 N. In consideration of thin semiconductor elements and low mechanical strength semiconductor elements, it is preferable that the semiconductor elements can be mounted at 5N or less, more preferably 1 to 4N. The mounting time (time during which the semiconductor element is pressed against the support) is preferably 10 seconds or less, more preferably 3 seconds or less, and particularly preferably 1 second or less from the viewpoint of productivity.
In order to mount the semiconductor element at a low temperature in this way, the liquid resin composition for adhesive is a support substrate using a stencil mask having a thickness of 50 μm and a urethane squeegee having a length of 27 cm, a squeegee load of 2 kg, and a squeegee speed of 20 mm / s. A semiconductor element (including a dummy element) is mounted at 100 ° C. on the adhesive layer printed on and heated in a dryer at 100 ° C. ± 5 ° C. for 80 ± 3 minutes, and the shear strength is 1N at 100 ° C. The above is preferable. As a result of conducting an experiment of mounting a semiconductor element on a support substrate with various adhesive layers having different shear strength at 100 ° C. of the adhesive layer after the heat treatment, the shear strength at 100 ° C. is 1 N or more. This is because there was no deviation of the semiconductor element after mounting, whereas the semiconductor element often shifted when less than 1N.
Here, the shear strength is measured by picking up a semiconductor element separated into 6 × 6 mm pieces on a die bonder, bonding weight 1.0 N, supporting substrate heating temperature 100 ° C., mounting time 8 seconds (the temperature of the supporting substrate surface is 100). PBGA (Plastic Ball Grid Array) substrate (package size 35 × 35 mm, core material: BT (bismaleimide-triazine) resin, solder resist: PSR4000AUS308 (solar ink production) It is the shear strength at 100 ° C. of the sample mounted on the product (made by Co., Ltd.), thickness 0.56 mm. The shear strength was measured with a die shear tester (manufactured by Dage, series 4000).
After mounting the semiconductor element, the adhesive layer is cured and electrically connected with a gold wire. The adhesive layer is cured at a temperature equal to or higher than the state change temperature of the curing accelerator. This temperature is preferably 200 ° C. or less, more preferably 180 ° C. or less, and particularly preferably 160 ° C. or less in consideration of the warp of the support substrate and the decomposition temperature of the adhesive layer.
After electrical connection is made in this manner, resin sealing is performed, and when a lead frame is used as the support substrate, lead processing, exterior plating, or the like is performed as necessary to obtain a semiconductor device. When an organic substrate is used as the support substrate, a solder ball attachment or the like is performed as necessary to obtain a semiconductor device.

得られた接着剤用液状樹脂組成物Ａの粘度は４５Ｐａ・ｓであった。なお粘度の測定はＥ型粘度計（東機産業（株）製、３度コーン）を用いて２５℃、２．５ｒｐｍでの値である（以下に示す粘度も同様に測定した）。
・接着剤用液状樹脂組成物Ｂ
ジエチレングリコールモノブチルエーテルアセタート（沸点２４７℃）
２２．５重量部
オルソクレゾールノボラック型エポキシ樹脂（軟化点７０℃、エポキシ
当量２１０） ３３．４重量部
フェノールノボラック樹脂（軟化点１１０℃、水酸基当量１０４）
１６．６重量部
上記の原料をセパラブルフラスコに配合し、８０℃、２時間攪拌することで褐色透明のワニスを得た。これを室温まで冷却した後に以下の原料を添加し、室温で三本ロールにより混練し接着剤用液状樹脂組成物Ｂを得た。
３−グリシドキシプロピルトリメトキシシラン ０．２重量部
下記式（９）の硬化促進剤（状態変化温度１２０℃、硬化反応開始温度
１４０℃） ０．２重量部
アエロジル２００Ｖ（ＤＥＧＵＳＳＡ社製） ４．０重量部
平均粒径６μｍの有機フィラー（Ｃ−８００、根上工業（株）製）
２３．０重量部

得られた接着剤用液状樹脂組成物Ｂの粘度は４５Ｐａ・ｓであった。
・接着剤用液状樹脂組成物Ｃ
γ−ブチロラクトン（沸点２０６℃） ２２．５重量部
オルソクレゾールノボラック型エポキシ樹脂（軟化点７０℃、エポキシ
当量２１０） ３３．４重量部
フェノールノボラック樹脂（軟化点１１０℃、水酸基当量１０４）
１６．６重量部
上記の原料をセパラブルフラスコに配合し、８０℃、２時間攪拌することで褐色透明のワニスを得た。これを室温まで冷却した後に以下の原料を添加し、室温で三本ロールにより混練し接着剤用液状樹脂組成物Ｃを得た。
３−グリシドキシプロピルトリメトキシシラン ０．２重量部
前記式（８）の硬化促進剤（状態変化温度１４０℃、硬化反応開始温度
１６０℃） ０．２重量部
アエロジル２００Ｖ（ＤＥＧＵＳＳＡ社製） ４．０重量部
平均粒径６μｍの有機フィラー（Ｃ−８００、根上工業（株）製）
２３．０重量部
得られた接着剤用液状樹脂組成物Ｃの粘度は４０Ｐａ・ｓであった。
・接着剤用液状樹脂組成物Ｄ
ジエチレングリコールモノエチルエーテルアセタート（沸点２１７℃）
２２．５重量部
オルソクレゾールノボラック型エポキシ樹脂（軟化点７０℃、エポキシ
当量２１０） ３３．４重量部
フェノールノボラック樹脂（軟化点１１０℃、水酸基当量１０４）
１６．６重量部
上記の原料をセパラブルフラスコに配合し、８０℃、２時間攪拌することで褐色透明のワニスを得た。これを室温まで冷却した後に以下の原料を添加し、室温で三本ロールにより混練し接着剤用液状樹脂組成物Ｄを得た。
３−グリシドキシプロピルトリメトキシシラン ０．２重量部
前記式（８）の硬化促進剤（状態変化温度１４０℃、硬化反応開始温度
１６０℃） ０．２重量部
アエロジル２００Ｖ （ＤＥＧＵＳＳＡ社製） ４．０重量部
平均粒径６μｍの有機フィラー（Ｃ−８００、根上工業（株）製）
２３．０重量部
得られた接着剤用液状樹脂組成物Ｄの粘度は４５Ｐａ・ｓであった。
・接着剤用液状樹脂組成物Ｅ
ジエチレングリコールモノブチルエーテルアセタート（沸点２４７℃）
２２．５重量部
オルソクレゾールノボラック型エポキシ樹脂（軟化点７０℃、エポキシ
当量２１０） ３３．４重量部
フェノールノボラック樹脂（軟化点１１０℃、水酸基当量１０４）
１６．６重量部
上記の原料をセパラブルフラスコに配合し、８０℃、２時間攪拌することで褐色透明のワニスを得た。これを室温まで冷却した後に以下の原料を添加し、室温で三本ロールにより混練し接着剤用液状樹脂組成物Ｅを得た。
３−グリシドキシプロピルトリメトキシシラン ０．２重量部
下記式（１０）の硬化促進剤（状態変化温度１４０℃、硬化反応開始温
度１６０℃、ｎ＝０．５） ０．２重量部
アエロジル２００Ｖ （ＤＥＧＵＳＳＡ社製） ４．０重量部
平均粒径６μｍの有機フィラー（Ｃ−８００、根上工業（株）製）
２３．０重量部
得られた接着剤用液状樹脂組成物Ｅの粘度は４７Ｐａ・ｓであった。

（式（１０）中、ｎ＝０．５である。）
・接着剤用液状樹脂組成物Ｆ
シクロヘキサノン（沸点１５６℃） ２２．５重量部
オルソクレゾールノボラック型エポキシ樹脂（軟化点７０℃、エポキシ
当量２１０） ３３．４重量部
フェノールノボラック樹脂（軟化点１１０℃、水酸基当量１０４）
１６．６重量部
上記の原料をセパラブルフラスコに配合し、８０℃、２時間攪拌することで褐色透明の液体を得た。これを室温まで冷却した後に以下の原料を添加し、室温で三本ロールにより混練し接着剤用液状樹脂組成物Ｆを得た。
３−グリシドキシプロピルトリメトキシシラン ０．２重量部
前記式（８）の硬化促進剤（状態変化温度１４０℃、硬化反応開始温度１
６０℃） ０．２重量部
アエロジル２００Ｖ（ＤＥＧＵＳＳＡ社製） ４．０重量部
平均粒径６μｍの有機フィラー（Ｃ−８００、根上工業（株）製）
２３．０重量部
得られた接着剤用液状樹脂組成物Ｆの粘度は１０Ｐａ・ｓであった。
・接着剤用液状樹脂組成物Ｇ
シクロヘキサノン（沸点１５６℃） ２２．５重量部
オルソクレゾールノボラック型エポキシ樹脂（軟化点７０℃、エポキシ
当量２１０） ３３．４重量部
フェノールノボラック樹脂（軟化点１１０℃、水酸基当量１０４）
１６．６重量部
上記の原料をセパラブルフラスコに配合し、８０℃、２時間攪拌することで褐色透明のワニスを得た。これを室温まで冷却した後に以下の原料を添加し、室温で三本ロールにより混練し接着剤用液状樹脂組成物Ｇを得た。
３−グリシドキシプロピルトリメトキシシラン ０．２重量部
２，４−ジアミノ−６−［２’−メチルイミダゾリル−（１’）］−エチ
ル−ｓ−トリアジン（状態変化温度８０℃以下、硬化反応開始温度１００
℃） ０．２重量部
アエロジル２００Ｖ （ＤＥＧＵＳＳＡ社製） ４．０重量部
平均粒径６μｍの有機フィラー（Ｃ−８００、根上工業（株）製）
２３．０重量部
得られた接着剤用液状樹脂組成物Ｇの粘度は１１Ｐａ・ｓであった。
・接着剤用液状樹脂組成物Ｈ
ジエチレングリコールモノブチルエーテルアセタート（沸点２４７℃）
２２．５重量部
オルソクレゾールノボラック型エポキシ樹脂（軟化点７０℃、エポキシ
当量２１０） ３３．４重量部
フェノールノボラック樹脂（軟化点１１０℃、水酸基当量１０４）
１６．６重量部
上記の原料をセパラブルフラスコに配合し、８０℃、２時間攪拌することで褐色透明のワニスを得た。これを室温まで冷却した後に以下の原料を添加し、室温で三本ロールにより混練し接着剤用液状樹脂組成物Ｈを得た。
３−グリシドキシプロピルトリメトキシシラン ０．２重量部
２，４−ジアミノ−６−［２’−メチルイミダゾリル−（１’）］−エチル
−ｓ−トリアジン（状態変化温度８０℃以下、硬化反応開始温度１００℃
） ０．２重量部
アエロジル２００Ｖ（ＤＥＧＵＳＳＡ社製） ４．０重量部
平均粒径６μｍの有機フィラー（Ｃ−８００、根上工業（株）製）
２３．０重量部
得られた接着剤用液状樹脂組成物Ｈの粘度は４５Ｐａ・ｓであった。
・接着剤用液状樹脂組成物Ｉ
ジエチレングリコールモノブチルエーテルアセタート（沸点２４７℃）
２２．５重量部
オルソクレゾールノボラック型エポキシ樹脂（軟化点７０℃、エポキシ
当量２１０） ３３．４重量部
フェノールノボラック樹脂（軟化点１１０℃、水酸基当量１０４）
１６．６重量部
上記の原料をセパラブルフラスコに配合し、８０℃、２時間攪拌することで褐色透明のワニスを得た。これを室温まで冷却した後に以下の原料を添加し、室温で三本ロールにより混練し接着剤用液状樹脂組成物Ｉを得た。
３−グリシドキシプロピルトリメトキシシラン ０．２重量部
トリフェニルフォスフィン（状態変化温度８０℃以下、硬化反応開始温
度１２０℃） ０．２重量部
アエロジル２００Ｖ（ＤＥＧＵＳＳＡ社製） ４．０重量部
平均粒径６μｍの有機フィラー（Ｃ−８００、根上工業（株）製）
２３．０重量部
得られた接着剤用液状樹脂組成物Ｉの粘度は４５Ｐａ・ｓであった。
・接着剤用液状樹脂組成物Ｊ
γ−ブチロラクトン（沸点２０６℃） ２２．５重量部
オルソクレゾールノボラック型エポキシ樹脂（軟化点７０℃、エポキシ
当量２１０） ３３．４重量部
フェノールノボラック樹脂（軟化点１１０℃、水酸基当量１０４）
１６．６重量部
上記の原料をセパラブルフラスコに配合し、８０℃、２時間攪拌することで褐色透明のワニスを得た。これを室温まで冷却した後に以下の原料を添加し、室温で三本ロールにより混練し接着剤用液状樹脂組成物Ｊを得た。
３−グリシドキシプロピルトリメトキシシラン ０．２重量部
２，４−ジアミノ−６−［２’−メチルイミダゾリル−（１’）］−エチル
−ｓ−トリアジン（状態変化温度８０℃以下、硬化反応開始温度１００℃
） ０．２重量部
アエロジル２００Ｖ（ＤＥＧＵＳＳＡ社製） ４．０重量部
平均粒径６μｍの有機フィラー（Ｃ−８００、根上工業（株）製）
２３．０重量部
得られた接着剤用液状樹脂組成物Ｊの粘度は４０Ｐａ・ｓであった。
上記の接着剤用液状樹脂組成物Ａ〜Ｊを、ＢＯＣ（Ｂｏａｒｄ Ｏｎ Ｃｈｉｐ）型半導体装置用の基板、即ちＢＴ（ビスマレイミド−トリアジン）樹脂基板（レジスト：ＰＳＲ４０００ＡＵＳ３０８（太陽インキ製造（株）製）、厚み０．５６ｍｍ）に印刷した。用いたステンシルマスクの厚みは５０μｍ、印刷厚みは、溶剤を揮発させた後の厚みが３５μ±５になるようにスキージ移動速度とスキージ荷重を調整した。これを１００℃、８０分加熱処理し、接着剤用液状樹脂組成物から溶剤を揮発させることで接着剤層付き半導体支持基板を得た。印刷は、印刷装置（トーレエンジニアリング製、ＶＥ５００）にメタルスキージ（ステンレスタイプ，長さ２７ｃｍ）を用い、荷重約２０Ｎ、スキージ移動速度２５ｍｍ／ｓで行った。
また、上記の接着剤用液状樹脂組成物Ａ〜Ｊを用いて、スライドガラス上に接着剤用液状樹脂組成物を５０μｍの厚さとなるように印刷し、１００℃８０分加熱処理を行い、接着剤用液状樹脂組成物から溶剤を揮発させることで接着剤層付きスライドガラスを得た。
［硬化促進剤の状態変化温度および評価］
上記接着剤用液状樹脂組成物Ａ〜Ｊの作製時のワニスを使用し、このワニス９５重量％に対し、５重量％の硬化促進剤を混ぜ、熱盤上で加熱し、目視で観察できる大きさで存在していた硬化促進剤が、目視で観察できない大きさになる温度を状態変化温度とした。以下の試験では、溶剤の揮発温度を１００℃として行ったので、状態変化温度が１００℃未満のものは×、状態変化温度が１００℃以上のものは○とした（常温〜揮発温度）。また、以下の試験では、硬化温度を１７５℃として行ったので、状態変化温度が１００℃より高い温度且つ１７５℃以下のものを○、状態変化温度が１７５℃を超えているものを×とした（揮発温度以上）。
硬化反応開始温度は、接着剤用液状樹脂組成物Ａ〜ＪをＤＳＣ（示差走査熱量計、セイコーインスツルメンツ社製、ＤＳＣ２２０）により昇温速度７℃／分で測定し、反応ピークの裾を結んだ線の始まる温度で測定した。
測定結果を第１表に示す。配合量は、重量部である。
［実施例１］
上記接着剤用液状樹脂組成物Ａを用いて作製した接着剤層付き半導体支持基板と接着剤層付きスライドガラスを用いて以下の試験を行った。
［揮発分］
揮発分は、揮発工程後の接着剤層の揮発分として測定した。５０μｍ厚みのステンシルマスク、長さ２７ｃｍのウレタンスキージを用い、スキージ荷重２ｋｇ、スキージ速度２０ｍｍ／ｓで支持基板上に印刷し、揮発工程、即ち１００℃±５℃の乾燥機中で８０±３分間加熱処理した後、取り出した支持基板が冷却される前にスパチュラにてサンプリングした接着剤層５〜３０ｍｇを、熱天秤法（ＴＧＡ）で室温から３００℃まで１０℃／分で昇温して測定した重量減少曲線における２００℃での重量減少率とした。
［半導体素子搭載性、タック性試験］
接着剤層付きスライドガラスの下からヒータで加熱し、ダイボンダーにて６×６ｍｍ角の半導体素子を、ボンド加重２．０Ｎ、加熱温度１００℃２０秒（スライドガラス表面の温度が１００℃まで昇温する時間１５秒を含む）の条件で搭載できるか確認した（半導体素子搭載性）。
この時６×６ｍｍ角半導体素子が、接着剤層と接触する面積が９０％以上であればＯＫとした。半導体素子を８個搭載し、１つでも９０％未満の半導体素子があればＮＧとした。なお、接触面積の求め方は、スライドガラスの裏面から、半導体素子の接触面を写真撮影し、接触部の面積から計算した。半導体素子搭載性試験でＮＧとならないものは、室温でのタック性試験を行った。
上記半導体素子を搭載した試験片を用い、タック力測定機（ＲＨＥＳＣＡ社製）にてプローブ下降速度（没入速度）３０ｍｍ／ｍｉｎ、テスト速度６００ｍｍ／ｍｉｎ、密着荷重（先行荷重）０．２Ｎ、密着保持時間（押し付け時間）１．０秒、プローブ５．１ｍｍφ（ＳＵＳ３０４）で行った。
［連続印刷性］
約２０ｇの接着剤用液状樹脂組成物を印刷に用いるステンシルマスク上に置き、２回連続で印刷後、そのままの状態で１時間休止するサイクルを１サイクルとして、１０サイクル行い、連続印刷性を評価した。このサイクル中に、接着剤用液状樹脂組成物が乾燥し、印刷物が掠れたらＮＧとし、また、ステンシルマスク上で乾燥し、掠れはしないが、溶剤揮発後の厚みが３５μｍ±５μｍから外れたらＮＧとした。
［常温放置試験］
上記の接着剤層付きスライドガラスを常温に放置した場合、半導体素子の搭載が出来る時間を、接着剤層のライフとした。半導体素子の搭載の要否は、半導体素子搭載性試験と同様に、接着剤層付きスライドガラスを用いｎ＝８で行った。
［耐湿半田性試験］
オートダイボンダーを用いて、回路面側をポリイミド樹脂（ＣＲＣ−８８００ 住友ベークライト（株）製）で保護した模擬半導体ウエハ（Ｐｈａｓｅ８ 日立ＵＬＳＩ社製）を、１０．５×５ｍｍに切断して用意した半導体素子を、搭載条件１００℃、８秒、荷重３００ｇにて、ポリイミド樹脂側の面を上記接着剤層付き半導体支持基板（ＢＯＣ（Ｂｏａｒｄ Ｏｎ Ｃｈｉｐ）型パッケージ）であるＢＴ樹脂基板の接着剤層に向けて搭載し、金線にて電気接続を行った。これを、半導体用封止材（ＥＭＥ−Ｇ７００ 住友ベークライト（株）製）にて１７５℃９０秒成形、４時間の後硬化を行い、１２．３×８．３ｍｍサイズの半導体装置に個片化した。この半導体装置を用いて、乾燥（１２５℃２０時間）、吸湿処理（８５℃、相対湿度８５％、１６８時間）、リフロー半田処理（最高温度２５５〜２６０℃、２０秒、ＪＥＤＥＣレベル１相当、連続３回処理）の耐湿半田性試験を行った。ｎ＝１０で試験し、内部不良について超音波探傷装置５ＭＨｚプローブを用いて透過観察した。内部剥離や割れがある半導体装置の数を不良として数えた。
結果は第１表の通りである。
［実施例２］
上記接着剤用液状樹脂組成物Ｂを用いて、接着剤層付き半導体支持基板と接着剤層付きスライドガラスを作製し、実施例１と同様に試験を行った。
［実施例３］
上記接着剤用液状樹脂組成物Ｃを用いて、接着剤層付き半導体支持基板と接着剤層付きスライドガラスを作製し、実施例１と同様に試験を行った。
［実施例４］
上記接着剤用液状樹脂組成物Ｄを用いて、接着剤層付き半導体支持基板と接着剤層付きスライドガラスを作製し、実施例１と同様に試験を行った。
［実施例５］
上記接着剤用液状樹脂組成物Ｅを用いて、接着剤層付き半導体支持基板と接着剤層付きスライドガラスを作製し、実施例１と同様に試験を行った。
［比較例１〜５］
上記接着剤用液状樹脂組成物Ｆ〜Ｊを用いて、接着剤層付き半導体支持基板と接着剤層付きスライドガラスを作製し実施例１と同様に試験を行った。
なお比較例１、２では連続印刷の途中で溶剤が乾いてしまい、掠れてしまったため、連続印刷性ＮＧとなった。比較例３〜５では、溶剤を揮発させたところで、硬化が進みすぎてしまい、半導体素子搭載が出来なかったため、半導体素子搭載性ＮＧとした。

[Liquid resin composition for adhesive]
・ Liquid resin composition A for adhesives
Diethylene glycol monobutyl ether acetate (boiling point 247 ° C)
22.5 parts by weight Orthocresol novolac type epoxy resin (softening point 70 ° C., epoxy equivalent 210) 33.4 parts by weight phenol novolac resin (softening point 110 ° C., hydroxyl equivalent 104)
16.6 parts by weight The above raw materials were blended in a separable flask and stirred at 80 ° C. for 2 hours to obtain a brown transparent varnish. After cooling this to room temperature, the following raw materials were added and kneaded with three rolls at room temperature to obtain a liquid resin composition A for adhesive.
3-glycidoxypropyltrimethoxysilane 0.2 parts by weight Curing accelerator of the following formula (8) (state change temperature 140 ° C., curing reaction start temperature 1
60 ° C) 0.2 parts by weight Aerosil 200V (manufactured by DEGUSSA) 4.0 parts by weight organic filler having an average particle size of 6 μm (C-800, manufactured by Negami Kogyo Co., Ltd.)
23.0 parts by weight

The viscosity of the obtained liquid resin composition A for adhesive was 45 Pa · s. The viscosity is measured at 25 ° C. and 2.5 rpm using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., 3 ° cone) (the viscosity shown below was also measured in the same manner).
・ Liquid resin composition B for adhesives
Diethylene glycol monobutyl ether acetate (boiling point 247 ° C)
22.5 parts by weight Orthocresol novolac type epoxy resin (softening point 70 ° C., epoxy equivalent 210) 33.4 parts by weight phenol novolac resin (softening point 110 ° C., hydroxyl equivalent 104)
16.6 parts by weight The above raw materials were blended in a separable flask and stirred at 80 ° C. for 2 hours to obtain a brown transparent varnish. After cooling this to room temperature, the following raw materials were added and kneaded with three rolls at room temperature to obtain a liquid resin composition B for adhesive.
3-glycidoxypropyltrimethoxysilane 0.2 parts by weight Curing accelerator of the following formula (9) (state change temperature 120 ° C., curing reaction start temperature 140 ° C.) 0.2 parts by weight Aerosil 200V (manufactured by DEGUSSA) 4 Organic filler with an average particle size of 6 parts by weight (C-800, manufactured by Negami Kogyo Co., Ltd.)
23.0 parts by weight

The viscosity of the obtained liquid resin composition B for adhesive was 45 Pa · s.
・ Liquid resin composition C for adhesive
γ-butyrolactone (boiling point 206 ° C.) 22.5 parts by weight orthocresol novolac type epoxy resin (softening point 70 ° C., epoxy equivalent 210) 33.4 parts by weight phenol novolac resin (softening point 110 ° C., hydroxyl group equivalent 104)
16.6 parts by weight The above raw materials were blended in a separable flask and stirred at 80 ° C. for 2 hours to obtain a brown transparent varnish. After cooling this to room temperature, the following raw materials were added, and kneaded with a three roll at room temperature to obtain a liquid resin composition C for adhesive.
3-glycidoxypropyltrimethoxysilane 0.2 part by weight Curing accelerator of the above formula (8) (state change temperature 140 ° C., curing reaction start temperature 160 ° C.) 0.2 part by weight Aerosil 200V (manufactured by DEGUSSA) 4 Organic filler with an average particle size of 6 parts by weight (C-800, manufactured by Negami Kogyo Co., Ltd.)
23.0 parts by weight The viscosity of the obtained liquid resin composition C for adhesive was 40 Pa · s.
-Liquid resin composition D for adhesives
Diethylene glycol monoethyl ether acetate (boiling point 217 ° C)
22.5 parts by weight Orthocresol novolac type epoxy resin (softening point 70 ° C., epoxy equivalent 210) 33.4 parts by weight phenol novolac resin (softening point 110 ° C., hydroxyl equivalent 104)
16.6 parts by weight The above raw materials were blended in a separable flask and stirred at 80 ° C. for 2 hours to obtain a brown transparent varnish. After cooling this to room temperature, the following raw materials were added and kneaded with three rolls at room temperature to obtain a liquid resin composition D for adhesive.
3-glycidoxypropyltrimethoxysilane 0.2 part by weight Curing accelerator of the above formula (8) (state change temperature 140 ° C., curing reaction start temperature 160 ° C.) 0.2 part by weight Aerosil 200V (manufactured by DEGUSSA) 4 Organic filler with an average particle size of 6 parts by weight (C-800, manufactured by Negami Kogyo Co., Ltd.)
23.0 parts by weight The viscosity of the obtained liquid resin composition D for adhesive was 45 Pa · s.
・ Liquid resin composition E for adhesives
Diethylene glycol monobutyl ether acetate (boiling point 247 ° C)
22.5 parts by weight Orthocresol novolac type epoxy resin (softening point 70 ° C., epoxy equivalent 210) 33.4 parts by weight phenol novolac resin (softening point 110 ° C., hydroxyl equivalent 104)
16.6 parts by weight The above raw materials were blended in a separable flask and stirred at 80 ° C. for 2 hours to obtain a brown transparent varnish. After cooling this to room temperature, the following raw materials were added and kneaded with three rolls at room temperature to obtain a liquid resin composition E for adhesive.
3-glycidoxypropyltrimethoxysilane 0.2 parts by weight Curing accelerator of the following formula (10) (state change temperature 140 ° C., curing reaction start temperature 160 ° C., n = 0.5) 0.2 parts by weight Aerosil 200V (Made by DEGUSSA) 4.0 parts by weight of organic filler having an average particle diameter of 6 μm (C-800, manufactured by Negami Industrial Co., Ltd.)
23.0 parts by weight The viscosity of the obtained liquid resin composition E for adhesive was 47 Pa · s.

(In formula (10), n = 0.5.)
・ Liquid resin composition F for adhesive
Cyclohexanone (boiling point 156 ° C.) 22.5 parts by weight Orthocresol novolac type epoxy resin (softening point 70 ° C., epoxy equivalent 210) 33.4 parts by weight phenol novolac resin (softening point 110 ° C., hydroxyl group equivalent 104)
16.6 parts by weight The above raw materials were blended in a separable flask and stirred at 80 ° C. for 2 hours to obtain a brown transparent liquid. After cooling this to room temperature, the following raw materials were added, and kneaded with three rolls at room temperature to obtain a liquid resin composition F for adhesive.
3-glycidoxypropyltrimethoxysilane 0.2 parts by weight Curing accelerator of the above formula (8) (state change temperature 140 ° C., curing reaction start temperature 1
60 ° C) 0.2 parts by weight Aerosil 200V (manufactured by DEGUSSA) 4.0 parts by weight organic filler having an average particle size of 6 μm (C-800, manufactured by Negami Kogyo Co., Ltd.)
23.0 parts by weight The viscosity of the obtained liquid resin composition F for adhesive was 10 Pa · s.
・ Liquid resin composition G for adhesive
Cyclohexanone (boiling point 156 ° C.) 22.5 parts by weight Orthocresol novolac type epoxy resin (softening point 70 ° C., epoxy equivalent 210) 33.4 parts by weight phenol novolac resin (softening point 110 ° C., hydroxyl group equivalent 104)
16.6 parts by weight The above raw materials were blended in a separable flask and stirred at 80 ° C. for 2 hours to obtain a brown transparent varnish. After cooling this to room temperature, the following raw materials were added, and kneaded with three rolls at room temperature to obtain a liquid resin composition G for adhesive.
3-glycidoxypropyltrimethoxysilane 0.2 parts by weight 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine (state change temperature of 80 ° C. or less, curing reaction Starting temperature 100
° C) 0.2 parts by weight Aerosil 200V (manufactured by DEGUSSA) 4.0 parts by weight of organic filler having an average particle size of 6 μm (C-800, manufactured by Negami Kogyo Co., Ltd.)
23.0 parts by weight The viscosity of the obtained adhesive liquid resin composition G was 11 Pa · s.
・ Liquid resin composition H for adhesive
Diethylene glycol monobutyl ether acetate (boiling point 247 ° C)
22.5 parts by weight Orthocresol novolac type epoxy resin (softening point 70 ° C., epoxy equivalent 210) 33.4 parts by weight phenol novolac resin (softening point 110 ° C., hydroxyl equivalent 104)
16.6 parts by weight The above raw materials were blended in a separable flask and stirred at 80 ° C. for 2 hours to obtain a brown transparent varnish. After cooling this to room temperature, the following raw materials were added, and kneaded with a three roll at room temperature to obtain a liquid resin composition H for adhesive.
3-glycidoxypropyltrimethoxysilane 0.2 parts by weight 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine (state change temperature of 80 ° C. or less, curing reaction Starting temperature 100 ° C
0.2 parts by weight Aerosil 200V (manufactured by DEGUSSA) 4.0 parts by weight of organic filler having an average particle size of 6 μm (C-800, manufactured by Negami Kogyo Co., Ltd.)
23.0 parts by weight The viscosity of the obtained liquid resin composition H for adhesive was 45 Pa · s.
-Liquid resin composition I for adhesives
Diethylene glycol monobutyl ether acetate (boiling point 247 ° C)
22.5 parts by weight Orthocresol novolac type epoxy resin (softening point 70 ° C., epoxy equivalent 210) 33.4 parts by weight phenol novolac resin (softening point 110 ° C., hydroxyl equivalent 104)
16.6 parts by weight The above raw materials were blended in a separable flask and stirred at 80 ° C. for 2 hours to obtain a brown transparent varnish. After cooling this to room temperature, the following raw materials were added and kneaded with three rolls at room temperature to obtain a liquid resin composition I for adhesive.
3-glycidoxypropyltrimethoxysilane 0.2 parts by weight Triphenylphosphine (state change temperature 80 ° C. or less, curing reaction start temperature 120 ° C.) 0.2 parts by weight Aerosil 200V (manufactured by DEGUSSA) 4.0 parts by weight Organic filler with an average particle size of 6 μm (C-800, manufactured by Negami Industrial Co., Ltd.)
23.0 parts by weight The viscosity of the obtained liquid resin composition I for adhesive was 45 Pa · s.
・ Liquid resin composition J for adhesives
γ-butyrolactone (boiling point 206 ° C.) 22.5 parts by weight orthocresol novolac type epoxy resin (softening point 70 ° C., epoxy equivalent 210) 33.4 parts by weight phenol novolac resin (softening point 110 ° C., hydroxyl group equivalent 104)
16.6 parts by weight The above raw materials were blended in a separable flask and stirred at 80 ° C. for 2 hours to obtain a brown transparent varnish. After cooling this to room temperature, the following raw materials were added, and kneaded with three rolls at room temperature to obtain a liquid resin composition J for adhesive.
3-glycidoxypropyltrimethoxysilane 0.2 parts by weight 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine (state change temperature of 80 ° C. or less, curing reaction Starting temperature 100 ° C
0.2 parts by weight Aerosil 200V (manufactured by DEGUSSA) 4.0 parts by weight of organic filler having an average particle size of 6 μm (C-800, manufactured by Negami Kogyo Co., Ltd.)
23.0 parts by weight The viscosity of the obtained liquid resin composition J for adhesive was 40 Pa · s.
The above-mentioned liquid resin compositions A to J for adhesives are used as substrates for BOC (Board On Chip) type semiconductor devices, that is, BT (bismaleimide-triazine) resin substrates (resist: PSR4000AUS308 (manufactured by Taiyo Ink Manufacturing Co., Ltd.)). , Thickness 0.56 mm). The squeegee moving speed and squeegee load were adjusted so that the thickness of the used stencil mask was 50 μm and the printing thickness was 35 μ ± 5 after the solvent was volatilized. This was heat-treated at 100 ° C. for 80 minutes, and the solvent was volatilized from the liquid resin composition for adhesive to obtain a semiconductor support substrate with an adhesive layer. Printing was performed using a metal squeegee (stainless steel type, length 27 cm) in a printing apparatus (Toray Engineering, VE500) at a load of about 20 N and a squeegee moving speed of 25 mm / s.
Moreover, using the liquid resin compositions A to J for the adhesive, the liquid resin composition for the adhesive is printed on a slide glass so as to have a thickness of 50 μm, and subjected to a heat treatment at 100 ° C. for 80 minutes. A glass slide with an adhesive layer was obtained by volatilizing the solvent from the liquid resin composition.
[Temperature change temperature and evaluation of curing accelerator]
Using the varnish at the time of preparation of the above liquid resin compositions A to J for adhesive, 5% by weight of a curing accelerator is mixed with 95% by weight of this varnish, heated on a hot platen, and can be visually observed. The temperature at which the curing accelerator that was present was so large that it could not be observed visually was defined as the state change temperature. In the following tests, since the volatilization temperature of the solvent was set to 100 ° C., those having a state change temperature of less than 100 ° C. were evaluated as “x”, and those having a state change temperature of 100 ° C. or more were evaluated as “O” (room temperature to volatilization temperature). In the following tests, since the curing temperature was 175 ° C., the case where the state change temperature was higher than 100 ° C. and 175 ° C. or less was rated as ◯, and the case where the state change temperature exceeded 175 ° C. was rated as x. (Above volatilization temperature).
Curing reaction start temperature measured liquid resin composition AJ for adhesive agents by DSC (Differential scanning calorimeter, Seiko Instruments Inc. make, DSC220) at the temperature increase rate of 7 degree-C / min, and tied the bottom of the reaction peak. Measured at the temperature where the line begins.
The measurement results are shown in Table 1. A compounding quantity is a weight part.
[Example 1]
The following tests were performed using the semiconductor support substrate with an adhesive layer and the slide glass with an adhesive layer, which were prepared using the above liquid resin composition A for adhesive.
[Volatile matter]
Volatile content was measured as the volatile content of the adhesive layer after the volatilization process. Using a stencil mask with a thickness of 50 μm and a urethane squeegee with a length of 27 cm, printing is performed on a support substrate at a squeegee load of 2 kg and a squeegee speed of 20 mm / s. After heat treatment, measure 5 to 30 mg of adhesive layer sampled with a spatula before cooling the taken out support substrate from room temperature to 300 ° C. at a rate of 10 ° C./min. The weight reduction rate at 200 ° C. in the weight reduction curve.
[Semiconductor element mountability, tackiness test]
Heated from under the glass slide with adhesive layer with a heater, a 6x6mm square semiconductor element was bonded with a die bonder, bond weight 2.0N, heating temperature 100 ° C for 20 seconds (temperature rise to 100 ° C on the surface of the slide glass) It was confirmed whether it could be mounted under the conditions of 15 seconds (including the time to perform the semiconductor device mounting).
At this time, if the area of the 6 × 6 mm semiconductor element in contact with the adhesive layer was 90% or more, it was determined as OK. If eight semiconductor elements are mounted and at least one semiconductor element is less than 90%, it is determined as NG. In addition, the method of calculating | requiring a contact area photographed the contact surface of the semiconductor element from the back surface of the slide glass, and computed from the area of the contact part. Those that did not become NG in the semiconductor device mounting test were subjected to a tack test at room temperature.
Using a test piece equipped with the above-described semiconductor element, a probe lowering speed (immersion speed) of 30 mm / min, a test speed of 600 mm / min, a contact load (preceding load) of 0.2 N, and a contact force are measured with a tack force measuring device (manufactured by RHESCA). The holding time (pressing time) was 1.0 second, and the probe was 5.1 mmφ (SUS304).
[Continuous printability]
About 20 g of the liquid resin composition for adhesive is placed on a stencil mask used for printing, and after 10 consecutive printings, the cycle of resting for 1 hour is performed as it is, and the continuous printing property is evaluated. did. During this cycle, the liquid resin composition for the adhesive dries and the printed material is NG, and it is NG when it is dried on the stencil mask and does not bleed, but NG when the thickness after evaporation of the solvent deviates from 35 μm ± 5 μm. It was.
[Normal temperature test]
When the above slide glass with an adhesive layer was left at room temperature, the time during which the semiconductor element could be mounted was defined as the life of the adhesive layer. The necessity of mounting the semiconductor element was determined at n = 8 using a slide glass with an adhesive layer, as in the semiconductor element mounting test.
[Moisture resistance test]
A semiconductor prepared by cutting a simulated semiconductor wafer (Phase 8 manufactured by Hitachi ULSI Co., Ltd.) with a circuit surface side protected with polyimide resin (CRC-8800 manufactured by Sumitomo Bakelite Co., Ltd.) to 10.5 × 5 mm using an auto die bonder. The device is mounted at 100 ° C. for 8 seconds under a load of 300 g, and the polyimide resin side surface is applied to the adhesive layer of the BT resin substrate, which is the semiconductor support substrate with the adhesive layer (BoC (Board On Chip) package). It was mounted and the electrical connection was made with a gold wire. This is molded at 175 ° C. for 90 seconds with a semiconductor sealing material (EME-G700, manufactured by Sumitomo Bakelite Co., Ltd.) and post-cured for 4 hours, and separated into a 12.3 × 8.3 mm size semiconductor device. did. Using this semiconductor device, drying (125 ° C. for 20 hours), moisture absorption treatment (85 ° C., relative humidity 85%, 168 hours), reflow soldering treatment (maximum temperature 255 to 260 ° C., 20 seconds, JEDEC level 1 equivalent, continuous A three-time treatment) wet solder resistance test was performed. The test was performed at n = 10, and internal defects were observed through transmission using an ultrasonic flaw detector 5 MHz probe. The number of semiconductor devices having internal peeling or cracks was counted as defective.
The results are shown in Table 1.
[Example 2]
Using the adhesive liquid resin composition B, a semiconductor support substrate with an adhesive layer and a slide glass with an adhesive layer were prepared and tested in the same manner as in Example 1.
[Example 3]
Using the liquid resin composition C for adhesive, a semiconductor support substrate with an adhesive layer and a slide glass with an adhesive layer were prepared and tested in the same manner as in Example 1.
[Example 4]
Using the liquid resin composition D for adhesive, a semiconductor support substrate with an adhesive layer and a slide glass with an adhesive layer were prepared and tested in the same manner as in Example 1.
[Example 5]
Using the adhesive liquid resin composition E, a semiconductor support substrate with an adhesive layer and a slide glass with an adhesive layer were prepared and tested in the same manner as in Example 1.
[Comparative Examples 1-5]
Using the adhesive liquid resin compositions F to J, a semiconductor support substrate with an adhesive layer and a slide glass with an adhesive layer were prepared and tested in the same manner as in Example 1.
In Comparative Examples 1 and 2, since the solvent was dried and drowned during continuous printing, continuous printability NG was obtained. In Comparative Examples 3 to 5, when the solvent was volatilized, the curing progressed too much and the semiconductor element could not be mounted.

  By using the liquid resin composition for adhesives used in the present invention, it is possible to provide a semiconductor support substrate with an adhesive layer in which the adhesive layer after solvent volatilization is not sticky at room temperature and has excellent continuous printability. Further, by providing a semiconductor device using a semiconductor support substrate with an adhesive layer, productivity can be improved.

Claims (4)

At least solvent (A), epoxy resin (B) having two or more epoxy groups in one molecule, epoxy resin curing agent (C) having two or more phenolic hydroxyl groups in one molecule, and curing acceleration A liquid resin composition for an adhesive containing an agent (D),
The boiling point of the solvent (A) is 200 to 260 ° C.,
The curing accelerator (D) is a curing accelerator represented by the following general formula (1), a curing accelerator represented by the following general formula (4), or a curing acceleration represented by the following general formula (6). Agent,
The epoxy resin (B) and the epoxy resin curing agent (C) are dissolved in the solvent (A),
A liquid resin composition for an adhesive, wherein the curing accelerator (D) has a state change temperature of 100 to 160 ° C.
General formula (1):

(In the formula, R ¹ , R ² and R ³ each represents one selected from a hydrogen atom, a methyl group, a methoxy group and a phenolic hydroxyl group, and may be the same or different from each other.) Is 0.5 to 2. A represents a naphthalene ring or an aromatic group represented by the following general formula (2).
General formula (2):

(Wherein R ⁴ , R ⁵ , R ⁶ and R ⁷ each represent one selected from a hydrogen atom, a halogen atom and an organic group having 1 to 6 carbon atoms, and are the same or different from each other) which may be .V represents a single bond, an ether group, a sulfonylamino group, a sulfide group, a carbonyl group or an organic group having a carbon number of 1 to 13.)
General formula (4):

(Wherein R ¹ , R ² and R ³ each represent one selected from a hydrogen atom, a methyl group, a methoxy group and a phenolic hydroxyl group, and may be the same as or different from each other. ¹ and Y ² are each an oxygen atom, a nitrogen atom, or a sulfur atom, and may be the same or different from each other, and X represents an organic group, and may be the same or different. Z represents a substituted or unsubstituted aromatic or heterocyclic organic group.)
General formula (6):

(Wherein R ¹ , R ² and R ³ each represent one selected from a hydrogen atom, a methyl group, a methoxy group and a phenolic hydroxyl group, and may be the same as or different from each other. ³ , at least one of Y ⁴ , Y ⁵ and Y ⁶ is a group formed by releasing one proton from a proton donor having at least one proton released from the molecule, and they are identical to each other. Or different.)   The liquid resin composition for an adhesive according to claim 1, wherein the epoxy resin (B) is an epoxy resin that is solid at room temperature.   The liquid resin composition for an adhesive according to claim 1, wherein the epoxy resin curing agent (C) is an epoxy resin curing agent that is solid at room temperature.   The liquid resin composition for an adhesive according to any one of claims 1 to 3, wherein a curing reaction start temperature of the curing accelerator is 130 ° C or higher.