TWI763902B - Semiconductor element and method of manufacturing the same - Google Patents

Semiconductor element and method of manufacturing the same

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Publication number
TWI763902B
TWI763902B TW107127711A TW107127711A TWI763902B TW I763902 B TWI763902 B TW I763902B TW 107127711 A TW107127711 A TW 107127711A TW 107127711 A TW107127711 A TW 107127711A TW I763902 B TWI763902 B TW I763902B
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Taiwan
Prior art keywords
sealing layer
wire
semiconductor element
substrate
resin
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TW107127711A
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Chinese (zh)
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TW201921610A (en
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佐藤英一
竹森大地
佐藤泉樹
戸川光生
山田和彦
関皓平
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日商昭和電工材料股份有限公司
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Publication of TW201921610A publication Critical patent/TW201921610A/en
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Publication of TWI763902B publication Critical patent/TWI763902B/en

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Abstract

一種半導體元件，包括：基板；配置於所述基板上的半導體器件；將所述基板與所述半導體器件電性連接的線；將所述線的頂點的下部空間密封的第1密封層；以及經由接合線設置於所述第1密封層的上部的第2密封層，且所述半導體元件中，所述第1密封層包含液狀密封材的硬化膜，所述第2密封層包含絕緣性樹脂塗佈材的乾燥塗膜。 A semiconductor element comprising: a substrate; a semiconductor device disposed on the substrate; a wire electrically connecting the substrate and the semiconductor device; a first sealing layer for sealing a lower space at an apex of the wire; and A second sealing layer provided on the upper part of the first sealing layer via a bonding wire, and in the semiconductor element, the first sealing layer includes a cured film of a liquid sealing material, and the second sealing layer includes an insulating property A dry coating film of a resin coating material.

Description

半導體元件及其製造方法 Semiconductor element and method of manufacturing the same

本揭示的實施形態是有關於一種半導體元件及其製造方法，更詳細而言，是有關於一種藉由利用不同的材料將線的上下方密封而達成薄型化的半導體元件及其製造方法。 Embodiments of the present disclosure relate to a semiconductor element and a method of manufacturing the same, and more specifically, to a semiconductor element that achieves thinning by sealing the upper and lower sides of lines with different materials and a method of manufacturing the same.

近年來，以行動電話為代表，利用半導體元件的電子設備的薄型化正在發展。另外，就安全保護的觀點而言，除基於密碼的安全管理以外，基於生物認證(生物統計(biometric)認證)的管理亦受到關注。例如，行動電話中，採用作為生物認證的一例的指紋認證感測器的機種有增加的傾向。此種新穎的電氣設備正不斷進行開發，另一方面確認到，對於靜電放電(ESD：Electro-static-Discharge)，半導體元件的特定部分容易變得脆弱。 In recent years, the reduction in thickness of electronic devices using semiconductor elements, represented by mobile phones, is progressing. In addition, from the viewpoint of security protection, in addition to security management based on passwords, management based on biometric authentication (biometric authentication) is also attracting attention. For example, in mobile phones, the number of models using a fingerprint authentication sensor, which is an example of biometric authentication, tends to increase. While development of such novel electrical equipment is progressing continuously, it has been confirmed that a specific part of a semiconductor element is likely to become vulnerable to electrostatic discharge (ESD: Electro-static-Discharge).

靜電放電(以下稱為ESD)成為半導體元件的損壞或誤動作發生等的一個原因。對於指紋認證感測器，亦無法忽視ESD的影響。因此，針對半導體元件中ESD耐性弱的部分，要求形成絕緣保護層。 Electrostatic discharge (hereinafter referred to as ESD) is one cause of damage to semiconductor elements, occurrence of malfunctions, and the like. For fingerprint authentication sensors, the impact of ESD cannot be ignored. Therefore, it is required to form an insulating protective layer for a portion of a semiconductor element having a weak ESD resistance.

另外，伴隨技術科技的進步，要求電子設備及半導體元件的薄型化，因此亦需要絕緣保護層自身的薄型化。 In addition, with the advancement of technology, thinning of electronic equipment and semiconductor elements is required, and thus thinning of the insulating protective layer itself is also required.

[現有技術文獻] [Prior Art Literature] [專利文獻] [Patent Literature]

專利文獻1：日本專利特開2013-166925號公報 Patent Document 1: Japanese Patent Laid-Open No. 2013-166925

一般而言，半導體元件中ESD集中的部分成為電荷容易集中的導電性的凸部的部位。例如，將基板與半導體元件電性連接的線的上部、以及電路基板上的金屬壁部分的錐形部(taper)與錐形部之間等的ESD耐性弱。為了提高ESD耐性而於線上部形成絕緣保護層的情況下，由於線的形狀複雜，因此產生若干課題。 In general, the portion of the semiconductor element where the ESD is concentrated is the portion of the conductive convex portion where the electric charge is likely to be concentrated. For example, the upper part of the line that electrically connects the substrate and the semiconductor element, the tapered portion of the metal wall portion on the circuit board, and the tapered portion are weak in ESD resistance. When an insulating protective layer is formed on the upper part of the wire in order to improve the ESD resistance, since the shape of the wire is complicated, some problems arise.

首先，於線上部形成絕緣保護層的材料(以下，亦稱為絕緣保護材料)較佳為塗佈後不流向線下部而維持於線上部。即，絕緣保護材料較佳為具有適度的觸變性。 First, the material for forming the insulating protective layer on the upper part of the wire (hereinafter, also referred to as an insulating protective material) is preferably maintained on the upper part of the wire without flowing to the lower part of the wire after coating. That is, the insulating protective material preferably has moderate thixotropy.

另外，針對絕緣保護層的薄型化的要求，較佳為絕緣保護材料具有優異的絕緣性。特別是就獲得充分的ESD耐性的觀點而言，絕緣保護材料較佳為於成膜後獲得150kV/mm以上的絕緣破壞電壓的材料。 In addition, in order to meet the requirement of thinning the insulating protective layer, it is preferable that the insulating protective material has excellent insulating properties. In particular, from the viewpoint of obtaining sufficient ESD resistance, the insulating protective material is preferably a material that obtains a dielectric breakdown voltage of 150 kV/mm or more after film formation.

相對於此，作為絕緣保護材料，例如已知有將聚醯亞胺樹脂作為基質(base)的材料，並根據其使用形態來控制流動性。例如，有為了賦予觸變性而使微細的二氧化矽填料等無機填料或其他有機填料分散於基質樹脂中而成的糊狀的絕緣保護材料。於為了形成絕緣保護層而使用不具有觸變性的液狀的絕緣保護材料的情況下，容易產生藉由塗佈後的流掛等而最需要靜電性保護的 線上部的膜厚變薄這一不良現象。實際上，於將以聚醯亞胺樹脂作為基質樹脂的不具有觸變性的液狀的絕緣保護材料塗佈於曲線形狀的線的情況下，絕緣保護材料自塗佈面流動，難以作為絕緣保護層來確保充分的厚度。因此，作為將絕緣保護材料維持於塗佈面上的方法，考慮到對絕緣保護材料賦予適當的觸變性的方法。 On the other hand, as an insulating protective material, for example, a material using a polyimide resin as a base is known, and its fluidity is controlled according to its usage form. For example, there is a paste-like insulating protective material in which an inorganic filler such as a fine silica filler or other organic filler is dispersed in a matrix resin in order to impart thixotropy. In the case of using a liquid insulating protective material without thixotropy for forming the insulating protective layer, it is easy to generate the most necessary electrostatic protection due to sagging after coating, etc. The problem is that the film thickness on the upper part of the line becomes thin. In fact, when a liquid insulating protective material having no thixotropy using a polyimide resin as a matrix resin is applied to a curved wire, the insulating protective material flows from the coated surface, making it difficult to act as an insulating protective material. layers to ensure adequate thickness. Therefore, as a method of maintaining the insulating protective material on the coating surface, a method of imparting appropriate thixotropy to the insulating protective material is considered.

但是，使微細的無機填料等分散於基質樹脂中而成的糊狀的絕緣保護材料於成膜後產生基質樹脂等絕緣成分與無機填料的界面。藉由膜中存在界面，即便於使用聚醯亞胺樹脂等高絕緣性樹脂的情況下，膜的絕緣破壞電壓亦大幅降低，難以獲得充分的絕緣性能。因此，為了保證半導體元件的絕緣性，需要將絕緣保護層的膜厚設計得大，並塗佈絕緣保護材料，從而難以實現薄型化。 However, in a paste-like insulating protective material in which fine inorganic fillers and the like are dispersed in a matrix resin, an interface between insulating components such as the matrix resin and the inorganic filler occurs after film formation. Since the interface exists in the film, even when a high insulating resin such as a polyimide resin is used, the dielectric breakdown voltage of the film is greatly reduced, and it is difficult to obtain sufficient insulating performance. Therefore, in order to ensure the insulating properties of the semiconductor element, it is necessary to design a large thickness of the insulating protective layer and apply an insulating protective material, which makes it difficult to achieve thinning.

作為改善由所述的絕緣成分與無機填料的界面所致的膜的絕緣性能下降的方法，揭示有一種包含加熱後溶解並與絕緣成分顯示出優異的相容性的有機填料(樹脂填料)的樹脂糊(專利文獻1)。根據所述樹脂糊，對平坦的基板進行印刷時，獲得優異的形狀穩定性，另外獲得優異的絕緣性。 As a method for improving the degradation of the insulating properties of the film due to the interface between the insulating component and the inorganic filler, there has been disclosed an organic filler (resin filler) containing an organic filler (resin filler) that dissolves after heating and exhibits excellent compatibility with the insulating component. Resin paste (Patent Document 1). According to the resin paste, when printing on a flat substrate, excellent shape stability and excellent insulating properties are obtained.

但是，於本發明者等人的研究中明確到，於將所述樹脂糊作為絕緣保護材料而塗佈於線的情況下，樹脂糊並不充分地延展於線下部的空間而於線下部容易產生孔隙(void)。若半導體元件中存在孔隙，則容易受到濕度的影響，另外，半導體元件的可靠性亦容易下降。 However, it became clear from the study by the inventors of the present invention that when the resin paste is applied to the wire as an insulating protective material, the resin paste does not sufficiently spread in the space below the wire, and it is easy to spread the resin paste in the lower part of the wire. Create voids. When a void exists in a semiconductor element, it is easy to be affected by humidity, and the reliability of a semiconductor element is also easy to fall.

根據以上，為了實現ESD耐性優異的薄型的半導體元件，謀求一種可於線上部使用高絕緣性的材料來形成薄型的絕緣保護層、且不產生孔隙地將線下部的空間密封的技術。因此，鑒於所述，本發明的課題是有關於使用可於線上部形成所述絕緣保護層且將線下部的空間密封的材料來提供一種ESD耐性優異且可靠性優異的薄型的半導體元件及其製造方法。 In view of the above, in order to realize a thin semiconductor element with excellent ESD resistance, a technique has been sought for which a thin insulating protective layer can be formed using a material with high insulating properties on the upper part of the wire, and the space below the wire can be sealed without generating voids. Therefore, in view of the above, the subject of the present invention is to provide a thin semiconductor element having excellent ESD resistance and reliability using a material capable of forming the insulating protective layer above the wire and sealing the space below the wire, and the same. Manufacturing method.

本發明的實施形態是有關於以下。但本發明並不限定於以下而是包含各種實施形態。 Embodiments of the present invention relate to the following. However, the present invention is not limited to the following, and includes various embodiments.

一實施形態是有關於一種半導體元件，包括：基板；配置於所述基板上的半導體器件；將所述基板與所述半導體器件電性連接的線；將所述線的頂點的下部空間密封的第1密封層；以及經由所述線設置於所述第1密封層的上部的第2密封層，且所述第1密封層包含液狀密封材的硬化膜，所述第2密封層包含絕緣性樹脂塗佈材的乾燥塗膜。 One embodiment relates to a semiconductor element, comprising: a substrate; a semiconductor device arranged on the substrate; a wire electrically connecting the substrate and the semiconductor device; a first sealing layer; and a second sealing layer provided on the upper part of the first sealing layer via the wire, wherein the first sealing layer includes a cured film of a liquid sealing material, and the second sealing layer includes an insulating The dry coating film of the resin coating material.

所述實施形態中，半導體元件較佳為進而包括以至少覆蓋所述第2密封層的方式設置的樹脂密封構件。 In the above-described embodiment, the semiconductor element preferably further includes a resin sealing member provided so as to cover at least the second sealing layer.

所述絕緣性樹脂塗佈材的乾燥塗膜的絕緣破壞電壓較佳為150kV/mm以上。 The dielectric breakdown voltage of the dry coating film of the insulating resin coating material is preferably 150 kV/mm or more.

所述絕緣性樹脂塗佈材較佳為包含平均粒徑0.1μm~5.0μm的樹脂填料。 The insulating resin coating material preferably contains a resin filler having an average particle diameter of 0.1 μm to 5.0 μm.

所述絕緣性樹脂塗佈材的25℃下的黏度較佳為30Pa．s~500 Pa．s。 The viscosity of the insulating resin coating material at 25°C is preferably 30Pa. s~500 Pa. s.

所述絕緣性樹脂塗佈材的25℃下的觸變係數較佳為2.0~10.0。 The thixotropic coefficient at 25° C. of the insulating resin coating material is preferably 2.0 to 10.0.

所述絕緣性樹脂塗佈材較佳為包含選自由聚醯胺、聚醯胺醯亞胺、及聚醯亞胺所組成的群組中的至少一種絕緣性樹脂。 The insulating resin coating material preferably includes at least one insulating resin selected from the group consisting of polyamide, polyamide imide, and polyimide.

所述第2密封層的膜厚較佳為100μm以下。所述第2密封層的膜厚更佳為50μm以下。 The film thickness of the second sealing layer is preferably 100 μm or less. The film thickness of the second sealing layer is more preferably 50 μm or less.

所述絕緣性樹脂的Tg(玻璃轉移溫度)較佳為150℃以上。 It is preferable that Tg (glass transition temperature) of the said insulating resin is 150 degreeC or more.

所述實施形態中，所述液狀密封材較佳為包含熱硬化性樹脂成分與無機填充劑，且當將於75℃、剪切速度5s-1的條件下所測定的黏度(Pa．s)設為黏度A，並將於75℃、剪切速度50s-1的條件下所測定的黏度(Pa．s)設為黏度B時，以黏度A/黏度B的值獲得的75℃下的觸變係數為0.1~2.5。 In the above-described embodiment, the liquid sealing material preferably contains a thermosetting resin component and an inorganic filler, and has a viscosity (Pa.s) measured at 75° C. and a shear rate of 5 s −1 . ) is set to viscosity A, and the viscosity (Pa·s) measured under the conditions of 75°C and shear rate of 50 s −1 is set to viscosity B, the value of viscosity A/viscosity B obtained at 75°C The thixotropic coefficient is 0.1~2.5.

所述液狀密封材中的氯離子量較佳為100ppm以下。 The amount of chloride ions in the liquid sealing material is preferably 100 ppm or less.

所述液狀密封材中的所述無機填充劑的最大粒徑較佳為75μm以下。 The maximum particle diameter of the inorganic filler in the liquid sealing material is preferably 75 μm or less.

所述液狀密封材的於75℃、剪切速度5s-1的條件下所測定的黏度較佳為3.0Pa．s以下。 The viscosity of the liquid sealing material measured under the conditions of 75°C and shear rate of 5s -1 is preferably 3.0Pa. s or less.

所述液狀密封材的於25℃、剪切速度10s-1的條件下所測定的黏度較佳為30Pa．s以下。 The viscosity of the liquid sealing material measured under the conditions of 25°C and shear rate of 10s -1 is preferably 30Pa. s or less.

以所述液狀密封材的總質量為基準，所述無機填充劑的含量較佳為50質量%以上。 The content of the inorganic filler is preferably 50 mass % or more based on the total mass of the liquid sealing material.

所述液狀密封材中的所述熱硬化性樹脂成分較佳為包含芳香族環氧樹脂與脂肪族環氧樹脂。 The thermosetting resin component in the liquid sealing material preferably contains an aromatic epoxy resin and an aliphatic epoxy resin.

所述芳香族環氧樹脂較佳為包含選自由液狀的雙酚型環氧樹脂及液狀的縮水甘油胺型環氧樹脂所組成的群組中的至少一種，且所述脂肪族環氧樹脂較佳為包含線狀脂肪族環氧樹脂。 The aromatic epoxy resin preferably comprises at least one selected from the group consisting of a liquid bisphenol-type epoxy resin and a liquid glycidylamine-type epoxy resin, and the aliphatic epoxy resin The resin preferably contains a linear aliphatic epoxy resin.

所述實施形態的半導體元件可較佳地用於指紋認證感測器中。但不限定於指紋認證感測器，亦設想將絕緣性樹脂塗佈材應用於薄型元件的線上部。另外，設想藉由本揭示的絕緣性樹脂塗佈材與液狀密封材的組合、以及使用了該些的製造方法，可製造新穎的薄型元件。 The semiconductor device of this embodiment can be preferably used in a fingerprint authentication sensor. However, it is not limited to the fingerprint authentication sensor, and it is also envisaged to apply an insulating resin coating material to the wire portion of the thin element. Moreover, it is envisaged that a novel thin element can be manufactured by the combination of the insulating resin coating material and the liquid sealing material of the present disclosure, and the manufacturing method using these.

另一實施形態是有關於一種半導體元件的製造方法，其為製造如下的半導體元件的方法，所述半導體元件包括：基板；配置於所述基板上的半導體器件；將所述基板與所述半導體器件電性連接的線；將所述線的頂點的下部空間密封的第1密封層；以及經由所述線設置於所述第1密封層的上部的第2密封層，且所述半導體元件的製造方法包括：藉由線將基板與配置於基板上的半導體器件電性連接的步驟；對所述線的頂點的下部空間供給液狀密封材並形成第1密封層的步驟；繼而，經由所述線對所述第1密封層的上部供給絕緣性樹脂塗佈材並形成第2密封層的步驟。 Another embodiment relates to a method of manufacturing a semiconductor element, which is a method of manufacturing a semiconductor element comprising: a substrate; a semiconductor device arranged on the substrate; A wire for electrical connection of devices; a first sealing layer for sealing the lower space of the vertex of the wire; and a second sealing layer provided on the upper part of the first sealing layer through the wire, and the semiconductor element The manufacturing method includes: the steps of electrically connecting a substrate and a semiconductor device arranged on the substrate by wires; the steps of supplying a liquid sealing material to the lower space of the vertex of the wire to form a first sealing layer; The wire is a step of supplying an insulating resin coating material to the upper portion of the first sealing layer to form a second sealing layer.

本申請案的揭示與2017年8月10日提出申請的日本專利特願2017-155891號所記載的主題相關聯，將其揭示的全部內容藉由引用而結合於本申請案中。 The disclosure of this application is related to the subject matter described in Japanese Patent Application No. 2017-155891 for which it applied on August 10, 2017, and the entire content of the disclosure is incorporated herein by reference.

根據本發明的實施形態，可提供一種ESD耐性優異且可靠性優異的薄型的半導體元件及其製造方法。 According to the embodiment of the present invention, it is possible to provide a thin semiconductor element excellent in ESD resistance and reliability, and a method for manufacturing the same.

1:基板 1: Substrate

2:半導體器件 2: Semiconductor devices

3:線(接合線) 3: Wire (bonding wire)

3a:線頂點(頂點) 3a: line vertex (vertex)

4a:第1密封層 4a: 1st sealing layer

4b:第2密封層 4b: 2nd sealing layer

5:樹脂密封構件 5: Resin sealing member

h:自基板起的線高度(高度) h: Line height from the substrate (height)

圖1是一實施形態的半導體元件的側面剖面圖。 FIG. 1 is a side sectional view of a semiconductor element according to an embodiment.

圖2是一實施形態的半導體元件的局部平面圖。 FIG. 2 is a partial plan view of a semiconductor element according to an embodiment.

圖3(a)~圖3(d)是對一實施形態的半導體元件的製造方法進行說明的概略剖面圖，圖3(a)~圖3(d)對應於各步驟。 FIGS. 3( a ) to 3 ( d ) are schematic cross-sectional views illustrating a method of manufacturing a semiconductor element according to an embodiment, and FIGS. 3 ( a ) to 3 ( d ) correspond to the respective steps.

以下，對本發明的實施形態進行具體說明。 Hereinafter, embodiments of the present invention will be specifically described.

<半導體元件> <Semiconductor element>

按照圖式對半導體元件進行說明。以下說明中，表示方向的「上」、「下」、「上部」、及「下部」等用語為了方便起見而用於特定圖式中的方向，並不限定裝置使用時的設置方向。 The semiconductor element will be described with reference to the drawings. In the following description, terms such as "upper", "lower", "upper", and "lower" indicating directions are used to specify the directions in the drawings for convenience, and do not limit the installation direction of the device in use.

圖1是一實施形態的半導體元件的側面剖面圖。圖2是一實施形態的半導體元件的局部平面圖。如圖1及圖2所示，半導體元件包括：基板1；配置於基板1上的半導體器件2；將基板1與半導體器件2電性連接的線3；將線3的頂點3a的下部空間 密封的第1密封層4a；以及經由接合線3設置於第1密封層4a的上部的第2密封層4b。如圖1所示，半導體元件較佳為進而包括以至少覆蓋第2密封層4b的方式設置的樹脂密封構件5。 FIG. 1 is a side sectional view of a semiconductor element according to an embodiment. FIG. 2 is a partial plan view of a semiconductor element according to an embodiment. As shown in FIGS. 1 and 2 , the semiconductor element includes: a substrate 1; a semiconductor device 2 arranged on the substrate 1; a wire 3 electrically connecting the substrate 1 and the semiconductor device 2; The sealed 1st sealing layer 4a; and the 2nd sealing layer 4b provided on the upper part of the 1st sealing layer 4a via the bonding wire 3. As shown in FIG. 1 , the semiconductor element preferably further includes a resin sealing member 5 provided so as to cover at least the second sealing layer 4b.

此處，所謂接合線的頂點3a是指，圖1中以參照符號「h」表示的自基板表面起的線的高度變得最大的部位。所述第1密封層4a包含液狀密封材的硬化膜，並藉由將液狀密封材注入至由基板1及半導體器件2的一部分與具有頂點3a的弧狀的線3所劃分的線下部的空間中而形成。另外，所述第2密封層4b包含絕緣性樹脂塗佈材的乾燥塗膜，並藉由第1密封層4a形成後塗佈所述絕緣性樹脂塗佈材而形成。 Here, the vertex 3a of the bonding wire refers to a portion where the height of the line from the substrate surface indicated by the reference sign "h" in FIG. 1 becomes the largest. The first sealing layer 4a includes a cured film of a liquid sealing material, and is formed by injecting the liquid sealing material to the lower part of the line divided by a part of the substrate 1 and the semiconductor device 2 and the arc-shaped line 3 having the vertex 3a formed in the space. Moreover, the said 2nd sealing layer 4b consists of the dry coating film of an insulating resin coating material, and is formed by coating the said insulating resin coating material after formation of the 1st sealing layer 4a.

如此，根據所述實施形態，於線頂點3a的下部空間、及線上部，分別使用不同的材料形成密封層，藉此可提供ESD耐性優異且可靠性優異的薄型的半導體元件。以下，對半導體元件的構成進行具體說明。 As described above, according to the above-described embodiment, the sealing layer is formed using different materials in the space below the line vertex 3a and the line portion, respectively, whereby a thin semiconductor element excellent in ESD resistance and reliability can be provided. Hereinafter, the configuration of the semiconductor element will be specifically described.

1.基板 1. Substrate

基板並無特別限定，只要為包含可將半導體器件安裝並加以線接合的材料的基板即可。基板的材料可根據半導體元件的用途而自本技術領域中眾所周知的材料中選擇。 The substrate is not particularly limited, as long as it is a substrate containing a material capable of mounting and wire bonding a semiconductor device. The material of the substrate may be selected from well-known materials in the art according to the use of the semiconductor element.

例如，於將半導體元件用於指紋認證感測器用途的情況下，可代表性地使用玻璃環氧基板等薄的剛性(rigid)基板。 For example, when a semiconductor element is used for a fingerprint authentication sensor, a thin rigid substrate such as a glass epoxy substrate is typically used.

作為另一例，於將半導體元件用於功率模組(Power Module)用途的情況下，通常可使用直接銅接合(Direct Copper Bond，DCB)基板、及氧化鋁系基板等陶瓷基板。於使銅電路等直接接合於陶瓷基板的情況下，不需要設置成為熱阻的接合層，因此容易獲得高放熱性及高絕緣性。因此，此種使銅電路等直接接合的陶瓷基板例如可較佳地用於車載用半導體、電氣鐵路用半導體、產業機械用半導體之類的高電壓及高電流的用途。 As another example, when a semiconductor element is used for a power module, a direct copper bonding (Direct Copper) is generally used. Bond, DCB) substrates, and ceramic substrates such as alumina substrates. When a copper circuit or the like is directly bonded to a ceramic substrate, it is not necessary to provide a bonding layer serving as a thermal resistance, so that high heat dissipation and high insulating properties are easily obtained. Therefore, such a ceramic substrate to which copper circuits and the like are directly bonded can be suitably used for high-voltage and high-current applications such as automotive semiconductors, electric railway semiconductors, and industrial machinery semiconductors.

2.半導體器件 2. Semiconductor devices

半導體器件經由線而電性連接於基板。 The semiconductor device is electrically connected to the substrate through wires.

半導體器件例如可為指紋認證感測器用半導體器件、功率模組用途的矽-絕緣閘極型雙極電晶體(Silicon-Insulated Gate Bipolar Transistor，Si-IGBT)、碳化矽(Silicon Carbide，SiC)、金屬氧化物半導體場效應電晶體(Metal Oxide Semiconductor Field Effect Transistor，MOSFET)(金屬氧化膜半導體場效應電晶體)。不限於該些半導體器件，於使用要求ESD耐性、或者針對高電壓高電流條件下的使用而要求高絕緣性般的半導體器件的情況下，可容易地獲得所述實施形態的效果。 The semiconductor devices can be, for example, semiconductor devices for fingerprint authentication sensors, silicon-insulated gate bipolar transistors (Si-IGBTs) for power modules, silicon carbide (SiC), Metal Oxide Semiconductor Field Effect Transistor (MOSFET) (Metal Oxide Semiconductor Field Effect Transistor). Not limited to these semiconductor devices, when using a semiconductor device requiring ESD resistance or requiring high insulation for use under high voltage and high current conditions, the effects of the above-described embodiment can be easily obtained.

半導體器件與基板通常藉由焊球等而被導電性地接合。於使用功率模組用途的半導體器件的情況下，半導體器件與基板的導電性接合除焊球以外，亦可使用燒結銀、及燒結銅等材料。 The semiconductor device and the substrate are generally conductively bonded by solder balls or the like. When a semiconductor device for a power module is used, materials such as sintered silver and sintered copper may be used for the conductive bonding between the semiconductor device and the substrate, in addition to solder balls.

3.線 3. Line

線用於將半導體器件與基板電性接合。線的材料可根據半導體元件的用途而自本技術領域中眾所周知的材料中選擇。例如， 於指紋認證感測器的用途中使用半導體元件的情況下，可使用金線、銀合金線、及銅線等。通常，主流為金線。作為另一例，於功率模組的用途中使用半導體元件的情況下，通常使用鋁線。 The wires are used to electrically bond the semiconductor device to the substrate. The material of the wire may be selected from materials well known in the art according to the use of the semiconductor element. E.g, When a semiconductor element is used for the application of a fingerprint authentication sensor, a gold wire, a silver alloy wire, a copper wire, or the like can be used. Usually, the mainstream is gold wire. As another example, when a semiconductor element is used in the application of a power module, an aluminum wire is generally used.

4a.第1密封層 4a. The first sealing layer

第1密封層包含液狀密封材的硬化膜。如圖1中所看到般，將液狀密封材注入至由基板1及半導體器件2的一部分與具有頂點3a的弧狀的線3所劃分的線下部的空間中，繼而使液狀密封材硬化，藉此形成第1密封層。 The first sealing layer includes a cured film of a liquid sealing material. As seen in FIG. 1 , the liquid sealing material is injected into the space below the line divided by a part of the substrate 1 and the semiconductor device 2 and the arc-shaped line 3 having the vertex 3 a, and then the liquid sealing material is injected. By hardening, the first sealing layer is formed.

一實施形態中，液狀密封材含有樹脂成分與無機填充材。液狀密封材較佳為，當將於75℃、剪切速度5s-1的條件下所測定的黏度(Pa．s)設為黏度A，並將於75℃、剪切速度50s-1的條件下所測定的黏度(Pa．s)設為黏度B時，以黏度A/黏度B的值獲得的75℃下的觸變係數為0.1~2.5。液狀密封材視需要亦可含有樹脂成分及無機填充材以外的成分。 In one embodiment, the liquid sealing material contains a resin component and an inorganic filler. Preferably, the liquid sealing material has a viscosity (Pa·s) measured under the conditions of 75°C and a shear rate of 5s -1 as viscosity A, and has a viscosity of 75°C and a shear rate of 50s -1 . When the viscosity (Pa.s) measured under the conditions is defined as viscosity B, the thixotropic coefficient at 75°C obtained by the value of viscosity A/viscosity B is 0.1 to 2.5. The liquid sealing material may contain components other than the resin component and the inorganic filler as necessary.

本揭示中所謂「液狀密封材」，是指可作為將半導體器件與基板之間填充的底部填充材而較佳地使用的、室溫下為液狀且藉由加熱等而硬化的樹脂材料。藉由使用液狀密封材將線下部的空間無間隙地密封，當利用絕緣性樹脂塗佈材將線上部密封時，可避免因該塗佈材而產生線流動等問題。另外，於塗佈絕緣性樹脂塗佈材時不產生流掛等不良現象，容易將塗佈材維持於線塗佈面上。 The term "liquid sealing material" in the present disclosure refers to a resin material that is liquid at room temperature and hardened by heating, etc., which can be preferably used as an underfill for filling between a semiconductor device and a substrate. . By using the liquid sealing material to seal the space under the wire without gaps, when the insulating resin coating material is used to seal the upper part of the wire, problems such as wire flow due to the coating material can be avoided. In addition, when coating the insulating resin coating material, there is no problem such as sagging, and it is easy to maintain the coating material on the line coating surface.

液狀密封材的75℃下的觸變係數為0.1~2.5，藉此容易 將線下部的空間無間隙地密封。 The thixotropic coefficient at 75°C of the liquid sealing material is 0.1 to 2.5, which makes it easy to Seal the space below the wire without any gaps.

雖然並不特別限定，但於一實施形態中，液狀密封材的75℃下的觸變係數更佳為0.5~2.0，進而佳為1.0~2.0。 Although not particularly limited, in one embodiment, the thixotropic coefficient at 75° C. of the liquid sealing material is more preferably 0.5 to 2.0, further preferably 1.0 to 2.0.

液狀密封材於75℃、剪切速度5s-1下所測定的黏度較佳為3.0Pa．s以下，更佳為2.0Pa．s以下。若液狀密封材於75℃、剪切速度5s-1下的黏度為3.0Pa．s以下，則有如下傾向：將液狀密封材賦予至線的周圍時，有效抑制線流動的發生。 The viscosity of the liquid sealing material measured at 75°C and a shear rate of 5s -1 is preferably 3.0Pa. s or less, more preferably 2.0Pa. s or less. If the viscosity of the liquid sealing material is 3.0Pa at 75℃ and shear rate of 5s -1 . When s is less than or equal to s, when the liquid sealing material is provided around the wire, the occurrence of wire flow is effectively suppressed.

所述黏度的下限並無特別限制，但就保持賦予至線周圍的狀態的觀點而言，較佳為0.01Pa．s以上。 The lower limit of the viscosity is not particularly limited, but is preferably 0.01 Pa from the viewpoint of maintaining the state imparted to the circumference of the line. s or more.

液狀密封材於25℃、剪切速度10s-1下所測定的黏度較佳為30Pa．s以下，更佳為20Pa．s以下。所述黏度的下限並無特別限制，但就保持賦予至線周圍的狀態的觀點而言，較佳為0.1Pa．s以上。 The viscosity of the liquid sealing material measured at 25°C and a shear rate of 10s -1 is preferably 30Pa. s or less, more preferably 20Pa. s or less. The lower limit of the viscosity is not particularly limited, but is preferably 0.1 Pa. s or more.

液狀密封材的25℃下的黏度為使用E型黏度計(例如，東京計器股份有限公司製造的維斯柯尼(VISCONIC)EHD型)測定所得的值，75℃下的黏度為使用流變儀(例如，TA儀器(TA Instruments)公司的商品名「AR2000」)測定所得的值。 The viscosity at 25°C of the liquid sealing material is a value measured using an E-type viscometer (for example, Visconic EHD type manufactured by Tokyo Keiki Co., Ltd.), and the viscosity at 75°C is a value obtained by using a rheology The obtained value was measured with an instrument (for example, trade name "AR2000" of TA Instruments).

關於液狀密封材的75℃下的觸變係數，當將於75℃、剪切速度5s-1的條件下所測定的黏度設為黏度A，並將於75℃、剪切速度50s-1的條件下所測定的黏度設為黏度B時，是以黏度A/黏度B的值而獲得。 Regarding the thixotropic coefficient of the liquid sealing material at 75°C, the viscosity measured under the conditions of 75°C and a shear rate of 5s -1 is defined as viscosity A, and the viscosity at 75°C and a shear rate of 50s -1 is defined as viscosity A. When the viscosity measured under the conditions of is referred to as viscosity B, it is obtained as the value of viscosity A/viscosity B.

用以使液狀密封材滿足所述黏度條件的方法並無特別 限制。例如，作為降低液狀密封材的黏度的方法，可列舉使用低黏度的樹脂成分的方法、添加溶劑的方法等，可將該些單獨使用或組合使用。 The method for making the liquid sealing material satisfy the above-mentioned viscosity conditions is not particularly limit. For example, as a method of reducing the viscosity of a liquid sealing material, the method of using a low-viscosity resin component, the method of adding a solvent, etc. are mentioned, and these can be used individually or in combination.

<樹脂成分> <resin component>

液狀密封材中所含的樹脂成分只要為可使液狀密封材滿足所述條件者，則無特別限制。就與現有設備的適合性、作為液狀密封材的特性的穩定性等觀點而言，較佳為使用熱硬化性的樹脂成分，更佳為使用環氧樹脂。另外，較佳為使用常溫(25℃)下為液狀(以下，亦簡稱為「液狀的」)的樹脂成分，更佳為使用液狀的環氧樹脂。樹脂成分亦可為環氧樹脂與硬化劑的組合。 The resin component contained in the liquid sealing material is not particularly limited as long as the liquid sealing material can satisfy the above-mentioned conditions. From the viewpoints of compatibility with existing equipment and stability of properties as a liquid sealing material, it is preferable to use a thermosetting resin component, and it is more preferable to use an epoxy resin. Moreover, it is preferable to use the resin component which is liquid (henceforth "liquid") at normal temperature (25 degreeC), and it is more preferable to use a liquid epoxy resin. The resin component may also be a combination of epoxy resin and hardener.

(環氧樹脂) (epoxy resin)

作為可於液狀密封材中使用的環氧樹脂，例如可列舉：雙酚A、雙酚F、雙酚AD、雙酚S、氫化雙酚A等二縮水甘油醚型環氧樹脂，以鄰甲酚酚醛清漆型環氧樹脂為代表的將酚類與醛類的酚醛清漆樹脂環氧化而成者(酚醛清漆型環氧樹脂)，藉由鄰苯二甲酸、二聚酸等多元酸與表氯醇的反應而獲得的縮水甘油酯型環氧樹脂，藉由對胺基苯酚、二胺基二苯基甲烷、異氰脲酸等胺化合物與表氯醇的反應而獲得的縮水甘油胺型環氧樹脂，藉由過乙酸等過酸將烯烴鍵氧化所得的線狀脂肪族環氧樹脂、脂環族環氧樹脂等。環氧樹脂可單獨使用一種，亦可將兩種以上組合使用。 Examples of epoxy resins that can be used for liquid sealing materials include diglycidyl ether-type epoxy resins such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, and hydrogenated bisphenol A. The cresol novolak epoxy resin is represented by the epoxidation of phenol and aldehyde novolak resin (novolak epoxy resin), and is made of polyacids such as phthalic acid and dimer acid. Glycidyl ester type epoxy resin obtained by the reaction of chlorohydrin, glycidylamine type epoxy resin obtained by the reaction of amine compounds such as p-aminophenol, diaminodiphenylmethane, isocyanuric acid, and epichlorohydrin Epoxy resins include linear aliphatic epoxy resins, alicyclic epoxy resins, and the like obtained by oxidizing olefin bonds with peracids such as peracetic acid. One type of epoxy resin may be used alone, or two or more types may be used in combination.

所述環氧樹脂中，就黏度、使用實績、材料價格等觀點而言，較佳為選自由二縮水甘油醚型環氧樹脂及縮水甘油胺型環 氧樹脂所組成的群組中的至少一種。其中，就流動性的觀點而言，較佳為液狀的雙酚型環氧樹脂，就耐熱性、接著性及流動性的觀點而言，較佳為液狀的縮水甘油胺型環氧樹脂。 Among the epoxy resins, those selected from the group consisting of diglycidyl ether-type epoxy resins and glycidylamine-type epoxy resins are preferably selected from the viewpoints of viscosity, use performance, material price, and the like. At least one of the group consisting of oxygen resins. Among them, from the viewpoint of fluidity, a liquid bisphenol-type epoxy resin is preferable, and from the viewpoint of heat resistance, adhesiveness, and fluidity, a liquid glycidylamine-type epoxy resin is preferable .

一實施形態中，液狀密封材使用具有芳香環的環氧樹脂(芳香族環氧樹脂)、與脂肪族環氧樹脂作為樹脂成分。例如，使用作為芳香族環氧樹脂的液狀的雙酚F型環氧樹脂及液狀的縮水甘油胺型環氧樹脂、與作為脂肪族環氧樹脂的線狀脂肪族環氧樹脂作為樹脂成分。 In one embodiment, the liquid sealing material uses an epoxy resin having an aromatic ring (aromatic epoxy resin) and an aliphatic epoxy resin as resin components. For example, liquid bisphenol F-type epoxy resins as aromatic epoxy resins, liquid glycidylamine-type epoxy resins, and linear aliphatic epoxy resins as aliphatic epoxy resins are used as resin components .

作為縮水甘油胺型環氧樹脂，可列舉：對(2,3-環氧丙氧基)-N,N-雙(2,3-環氧丙基)苯胺、二縮水甘油基苯胺、二縮水甘油基甲苯胺、二縮水甘油基甲氧基苯胺、二縮水甘油基二甲基苯胺、二縮水甘油基三氟甲基苯胺等。 Examples of glycidylamine-type epoxy resins include p-(2,3-glycidoxy)-N,N-bis(2,3-glycidyl)aniline, diglycidylaniline, diglycidyl Glyceryl toluidine, diglycidyl methoxyaniline, diglycidyl dimethylaniline, diglycidyl trifluoromethylaniline, etc.

作為線狀脂肪族環氧樹脂，可列舉：1,6-己二醇二縮水甘油醚、間苯二酚二縮水甘油醚、丙二醇二縮水甘油醚、1,3-雙(3-縮水甘油氧基丙基)四甲基二矽氧烷、環己烷二甲醇二縮水甘油醚等。 Examples of linear aliphatic epoxy resins include 1,6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, propylene glycol diglycidyl ether, 1,3-bis(3-glycidyloxy) propyl) tetramethyldisiloxane, cyclohexanedimethanol diglycidyl ether, etc.

於將液狀的雙酚F型環氧樹脂、液狀的縮水甘油胺型環氧樹脂、與線狀脂肪族環氧樹脂併用作為環氧樹脂的情況下，該些的調配比並無特別限制。所述調配比例如可為，液狀的縮水甘油胺型環氧樹脂為整體的40質量%~70質量%，液狀的雙酚F型環氧樹脂與線狀脂肪族環氧樹脂的合計為整體的30質量%~60質量%。 When a liquid bisphenol F-type epoxy resin, a liquid glycidylamine-type epoxy resin, and a linear aliphatic epoxy resin are used in combination as the epoxy resin, the mixing ratio of these is not particularly limited. . The mixing ratio may be, for example, the liquid glycidylamine-type epoxy resin is 40% by mass to 70% by mass of the whole, and the total of the liquid bisphenol F-type epoxy resin and the linear aliphatic epoxy resin is 30% by mass to 60% by mass of the whole.

所述例示的環氧樹脂佔環氧樹脂整體的含有率(於使用 兩種以上的所例示的環氧樹脂的情況下為其合計)就充分發揮其性能的觀點而言，較佳為20質量%以上，更佳為30質量%以上，進而佳為50質量%以上。該含有率的上限值並無特別限制，可於獲得液狀密封材的所期望的性狀及特性的範圍內決定。 The exemplified epoxy resin content in the entire epoxy resin (for use In the case of two or more exemplified epoxy resins, the total is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more, from the viewpoint of sufficiently exerting their performance. . The upper limit value of the content rate is not particularly limited, and can be determined within the range in which the desired properties and characteristics of the liquid sealing material are obtained.

作為環氧樹脂，較佳為使用液狀的環氧樹脂，但亦可併用常溫(25℃)下為固體的環氧樹脂。於併用常溫下為固體的環氧樹脂的情況下，其比例較佳為設為環氧樹脂整體的20質量%以下。 As the epoxy resin, it is preferable to use a liquid epoxy resin, but a solid epoxy resin at normal temperature (25° C.) may be used together. When using together the epoxy resin which is solid at normal temperature, it is preferable that the ratio shall be 20 mass % or less of the whole epoxy resin.

就抑制線的腐蝕的觀點而言，液狀密封材中的氯離子量越少越佳。具體而言，例如較佳為100ppm以下。 From the viewpoint of suppressing corrosion of the wire, the smaller the amount of chloride ions in the liquid sealing material, the better. Specifically, for example, 100 ppm or less is preferable.

本揭示中，液狀密封材中的氯離子量為藉由使用碳酸鈉溶液作為溶離液的離子層析法，於121℃、20小時的條件下進行處理，並以2.5g/50cc換算所得的值(ppm)。 In the present disclosure, the amount of chloride ions in the liquid sealing material is obtained by ion chromatography using a sodium carbonate solution as a chaotropic solution at 121° C. for 20 hours and converted to 2.5 g/50 cc. value (ppm).

(硬化劑) (hardener)

作為硬化劑，可無特別限制地使用胺系硬化劑、酚硬化劑、酸酐等作為環氧樹脂的硬化劑而一般所使用者。就抑制線流動的觀點而言，較佳為使用液狀的硬化劑。就耐溫度循環性及耐濕性等優異、且可提升半導體封裝的可靠性的觀點而言，硬化劑較佳為芳香族胺化合物，更佳為液狀的芳香族胺化合物。硬化劑可單獨使用一種，亦可將兩種以上組合使用。 As the curing agent, an amine-based curing agent, a phenolic curing agent, an acid anhydride, etc. can be used without particular limitation as a curing agent for epoxy resins, and are generally used. From the viewpoint of suppressing thread flow, it is preferable to use a liquid curing agent. The curing agent is preferably an aromatic amine compound, more preferably a liquid aromatic amine compound, from the viewpoint of being excellent in temperature cycle resistance, moisture resistance, and the like and improving the reliability of the semiconductor package. A hardener may be used individually by 1 type, and may be used in combination of 2 or more types.

作為液狀的芳香族胺化合物，可列舉：二乙基甲苯二胺、1-甲基-3,5-二乙基-2,4-二胺基苯、1-甲基-3,5-二乙基-2,6-二胺 基苯、1,3,5-三乙基-2,6-二胺基苯、3,3'-二乙基-4,4'-二胺基二苯基甲烷、3,5,3',5'-四甲基-4,4'-二胺基二苯基甲烷、二甲基硫代甲苯二胺等。 Examples of the liquid aromatic amine compound include diethyltoluenediamine, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5- Diethyl-2,6-diamine Benzene, 1,3,5-triethyl-2,6-diaminobenzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,5,3' , 5'-tetramethyl-4,4'-diaminodiphenylmethane, dimethylthiotoluenediamine, etc.

液狀的芳香族胺化合物可作為市售品而獲取。例如，可獲取JER固(cure)W(三菱化學股份有限公司製造的商品名)、卡亞哈德(Kayahard)A-A、卡亞哈德(Kayahard)A-B、卡亞哈德(Kayahard)A-S(日本化藥股份有限公司製造的商品名)、東都胺(Tohto Amine)HM-205(新日鐵住金化學股份有限公司的商品名)、艾迪科硬化劑(Adeka Hardner)EH-101(艾迪科(ADEKA)股份有限公司製造的商品名)、艾波米克(Epomik)Q-640、艾波米克(Epomik)Q-643(三井化學股份有限公司製造的商品名)、DETDA80(龍沙(Lonza)公司製造的商品名)等。 The liquid aromatic amine compound is available as a commercial item. For example, JER solid (cure) W (trade name manufactured by Mitsubishi Chemical Co., Ltd.), Kayahard A-A, Kayahard A-B, Kayahard A-S (Japan Adeka Hardner EH-101 (Adeka Hardner) (trade name manufactured by ADEKA), Epomik Q-640, Epomik Q-643 (trade name manufactured by Mitsui Chemicals Co., Ltd.), DETDA80 (Lonza ( Lonza) company's trade name) and so on.

液狀的芳香族胺化合物中，就液狀密封材的保存穩定性的觀點而言，較佳為3,3'-二乙基-4,4'-二胺基二苯基甲烷、二乙基甲苯二胺及二甲基硫代甲苯二胺。較佳為以該些中的任一者或該些的混合物作為硬化劑的主成分。作為二乙基甲苯二胺，可列舉3,5-二乙基甲苯-2,4-二胺及3,5-二乙基甲苯-2,6-二胺，該些可單獨使用，亦可組合使用，較佳為將3,5-二乙基甲苯-2,4-二胺的比例設為二乙基甲苯二胺整體的60質量%以上。 Among the liquid aromatic amine compounds, from the viewpoint of the storage stability of the liquid sealing material, 3,3'-diethyl-4,4'-diaminodiphenylmethane, diethyl toluenediamine and dimethylthiotoluenediamine. It is preferable to use any one of these or a mixture of these as the main component of the hardener. Examples of diethyltoluenediamine include 3,5-diethyltoluene-2,4-diamine and 3,5-diethyltoluene-2,6-diamine, and these may be used alone or may be When used in combination, the ratio of 3,5-diethyltoluene-2,4-diamine is preferably 60% by mass or more of the entire diethyltoluenediamine.

液狀密封材中的硬化劑的量並無特別限制，可考慮與環氧樹脂的當量比等而選擇。就將環氧樹脂或硬化劑的未反應部分抑制得低的觀點而言，硬化劑的量較佳為相對於環氧樹脂的環氧 基的當量數而言的硬化劑的官能基的當量數(例如，於胺系硬化劑的情況下，為活性氫的當量數)之比成為0.7~1.6的範圍的量，更佳為成為0.8~1.4的範圍的量，進而佳為成為0.9~1.2的範圍的量。 The amount of the curing agent in the liquid sealing material is not particularly limited, and can be selected in consideration of the equivalence ratio with the epoxy resin and the like. From the viewpoint of suppressing the unreacted portion of the epoxy resin or the hardener to be low, the amount of the hardener is preferably an epoxy resin relative to the epoxy resin. The ratio of the number of equivalents of functional groups of the curing agent (for example, in the case of an amine-based curing agent, the number of equivalents of active hydrogen) in terms of the number of equivalents of groups is an amount in the range of 0.7 to 1.6, more preferably 0.8 The amount in the range of ~1.4 is more preferably the amount in the range of 0.9 to 1.2.

<無機填充材> <Inorganic filler>

液狀密封材中所含的無機填充材的種類並無特別限制。例如可列舉：二氧化矽、碳酸鈣、黏土、氧化鋁、氮化矽、碳化矽、氮化硼、矽酸鈣、鈦酸鉀、氮化鋁、氧化鈹、氧化鋯、鋯石、鎂橄欖石、塊滑石、尖晶石、富鋁紅柱石、氧化鈦等的粉體、或者將該些加以球形化而成的珠粒(beads)、玻璃纖維等。進而，可使用具有阻燃效果的無機填充材，作為此種無機填充材，可列舉：氫氧化鋁、氫氧化鎂、硼酸鋅、鉬酸鋅等。無機填充材可單獨使用一種，亦可將兩種以上組合使用。 The type of the inorganic filler contained in the liquid sealing material is not particularly limited. Examples include: silica, calcium carbonate, clay, alumina, silicon nitride, silicon carbide, boron nitride, calcium silicate, potassium titanate, aluminum nitride, beryllium oxide, zirconia, zircon, forsterite Powders of stone, talc, spinel, mullite, titanium oxide, etc., or beads, glass fibers, etc. obtained by spheroidizing these. Furthermore, an inorganic filler having a flame retardant effect can be used, and examples of such an inorganic filler include aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, and the like. The inorganic filler may be used alone or in combination of two or more.

無機填充材中，就獲取的容易性、化學穩定性、材料成本的觀點而言，較佳為二氧化矽。作為二氧化矽，可列舉球狀二氧化矽、結晶二氧化矽等，就液狀密封材朝微細間隙的流動性及滲透性的觀點而言，較佳為球狀二氧化矽。作為球狀二氧化矽，可列舉藉由爆燃法所得的二氧化矽、熔融二氧化矽等。 Among the inorganic fillers, silicon dioxide is preferable from the viewpoints of availability, chemical stability, and material cost. Spherical silica, crystalline silica, etc. are mentioned as silica, and spherical silica is preferable from a viewpoint of the fluidity|liquidity and permeability to a fine gap of a liquid sealing material. As spherical silica, the silica obtained by a deflagration method, fused silica, etc. are mentioned.

亦可對無機填充材的表面進行表面處理。例如，亦可使用後述的偶合劑進行表面處理。 Surface treatment can also be performed on the surface of the inorganic filler. For example, surface treatment can also be performed using a coupling agent described later.

無機填充材的體積平均粒徑較佳為0.1μm~30μm，更佳為0.3μm~5μm，進而佳為0.5μm~3μm。特別是於球形二氧 化矽的情況下，較佳為體積平均粒徑為所述範圍內。若體積平均粒徑為0.1μm以上，則有於液狀密封材中的分散性優異、流動性優異的傾向。若體積平均粒徑為30μm以下，則有如下傾向：液狀密封材中的無機填充材的沈降減少，液狀密封材朝微細間隙的滲透性及流動性提升並抑制孔隙及未填充的發生。 The volume average particle diameter of the inorganic filler is preferably 0.1 μm to 30 μm, more preferably 0.3 μm to 5 μm, and still more preferably 0.5 μm to 3 μm. especially for spherical In the case of silicon carbide, it is preferable that the volume average particle size is within the above-mentioned range. When the volume average particle diameter is 0.1 μm or more, the dispersibility in the liquid sealing material tends to be excellent, and the fluidity tends to be excellent. When the volume average particle size is 30 μm or less, the sedimentation of the inorganic filler in the liquid sealing material is reduced, the permeability and fluidity of the liquid sealing material to the fine gaps are improved, and the occurrence of voids and unfilling is suppressed.

無機填充材的體積平均粒徑是指，於使用雷射繞射式粒度分佈測定裝置而獲得的體積基準的粒度分佈中，自小徑側起的累積成為50%時的粒徑(D50%)。 The volume average particle size of an inorganic filler refers to the particle size (D50%) when the accumulation from the small diameter side becomes 50% in the volume-based particle size distribution obtained by using a laser diffraction particle size distribution analyzer. .

無機填充材的最大粒徑較佳為75μm以下，更佳為50μm以下，進而佳為20μm以下。 The maximum particle diameter of the inorganic filler is preferably 75 μm or less, more preferably 50 μm or less, and still more preferably 20 μm or less.

本揭示中無機填充材的最大粒徑是指，於體積基準的粒度分佈中，自小徑側起的累積成為99%時的粒徑(D99%)。 In the present disclosure, the maximum particle diameter of the inorganic filler refers to the particle diameter (D99%) at which the accumulation from the small diameter side becomes 99% in the particle size distribution based on volume.

以液狀密封材的總質量為基準，無機填充材的含量較佳為50質量%以上。以液狀密封材的總質量為基準，若無機填充材的含量為50質量%以上，則有可充分確保線周邊的放熱性與強度的傾向。以液狀密封材的總質量為基準，無機填充材的含量更佳為60質量%以上，進而佳為70質量%以上。 The content of the inorganic filler is preferably 50% by mass or more based on the total mass of the liquid sealing material. When the content of the inorganic filler is 50 mass % or more based on the total mass of the liquid sealing material, the heat dissipation properties and strength around the wire tend to be sufficiently secured. The content of the inorganic filler is more preferably 60% by mass or more, and further preferably 70% by mass or more, based on the total mass of the liquid sealing material.

就抑制液狀密封材的黏度上升的觀點而言，以液狀密封材的總質量為基準，無機填充材的含量較佳為80質量%以下。 From the viewpoint of suppressing an increase in the viscosity of the liquid sealing material, the content of the inorganic filler is preferably 80% by mass or less based on the total mass of the liquid sealing material.

<溶劑> <Solvent>

液狀密封材亦可含有溶劑。藉由包含溶劑，可將液狀密封材的黏度調節為所期望的範圍。溶劑可單獨使用一種，亦可併用兩 種以上。 The liquid sealing material may contain a solvent. By including the solvent, the viscosity of the liquid sealing material can be adjusted to a desired range. One solvent can be used alone, or two can be used in combination more than one species.

溶劑的種類並無特別限制，可自於半導體裝置的安裝技術中使用的樹脂組成物中一般所使用的溶劑中選擇。具體而言，可列舉：丁基卡必醇乙酸酯、甲醇、乙醇、丙醇、丁醇等醇系溶劑，丙酮、甲基乙基酮等酮系溶劑，乙二醇***、乙二醇甲醚、乙二醇丁醚、丙二醇甲醚、二丙二醇甲醚、丙二醇***、丙二醇甲醚乙酸酯等二醇醚系溶劑，γ-丁內酯、δ-戊內酯、ε-己內酯等內酯系溶劑，二甲基乙醯胺、二甲基甲醯胺等醯胺系溶劑，及甲苯、二甲苯等芳香族系溶劑等。 The type of the solvent is not particularly limited, and can be selected from solvents generally used in resin compositions used in the mounting technology of semiconductor devices. Specifically, alcohol-based solvents such as butyl carbitol acetate, methanol, ethanol, propanol, and butanol; ketone-based solvents such as acetone and methyl ethyl ketone; ethylene glycol ethyl ether, ethylene glycol Methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol methyl ether acetate and other glycol ether solvents, γ-butyrolactone, δ-valerolactone, ε-caprolactone Lactone-based solvents such as esters, amide-based solvents such as dimethylacetamide and dimethylformamide, and aromatic solvents such as toluene and xylene.

就避免將液狀密封材硬化時的由急劇揮發所致的氣泡形成的觀點而言，較佳為使用沸點高(例如，常壓下的沸點為170℃以上)的溶劑。 From the viewpoint of avoiding bubble formation due to rapid volatilization when the liquid sealing material is hardened, it is preferable to use a solvent with a high boiling point (for example, a boiling point at normal pressure of 170° C. or higher).

於液狀密封材包含溶劑的情況下，所述溶劑的量並無特別限制，但較佳為液狀密封材整體的1質量%~70質量%。 When the liquid sealing material contains a solvent, the amount of the solvent is not particularly limited, but is preferably 1% by mass to 70% by mass of the entire liquid sealing material.

<硬化促進劑> <Hardening accelerator>

液狀密封材視需要亦可含有促進環氧樹脂與硬化劑的反應的硬化促進劑。 A liquid sealing material may contain a hardening accelerator which accelerates the reaction of an epoxy resin and a hardening|curing agent as needed.

硬化促進劑並無特別限制，可使用現有公知者。例如可列舉：1,8-二氮雜-雙環[5.4.0]十一烯-7、1,5-二氮雜-雙環[4.3.0]壬 烯、5,6-二丁基胺基-1,8-二氮雜-雙環[5.4.0]十一烯-7等環脒化合物，三乙二胺、苄基二甲基胺、三乙醇胺、二甲基胺基乙醇、三(二甲基胺基甲基)苯酚等三級胺化合物，2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-苯基咪唑、1-苄基-2-甲基咪唑、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑、2,4-二胺基-6-(2'-甲基咪唑基-(1'))-乙基-均三嗪、2-十七烷基咪唑等咪唑化合物，三烷基膦(三丁基膦等)、二烷基芳基膦(二甲基苯基膦等)、烷基二芳基膦(甲基二苯基膦等)、三苯基膦、烷基取代三苯基膦等有機膦化合物，及於該些有機膦化合物中加成順丁烯二酸酐、1,4-苯醌、2,5-甲醌、1,4-萘醌、2,3-二甲基苯醌、2,6-二甲基苯醌、2,3-二甲氧基-5-甲基-1,4-苯醌、2,3-二甲氧基-1,4-苯醌、及苯基-1,4-苯醌等醌化合物、以及重氮苯基甲烷、及酚樹脂等具有π鍵的化合物而成的具有分子內分極的化合物、與該些的衍生物。 The hardening accelerator is not particularly limited, and conventionally known ones can be used. For example: 1,8-diaza-bicyclo[5.4.0]undecene-7, 1,5-diaza-bicyclo[4.3.0]nonane Cyclic amidine compounds such as alkene, 5,6-dibutylamino-1,8-diaza-bicyclo[5.4.0]undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine , dimethylaminoethanol, tris(dimethylaminomethyl)phenol and other tertiary amine compounds, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2- Phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl -4-Methyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2'-methylimidazolyl-(1'))-ethyl-s-triazine, 2-heptadecane imidazole compounds such as imidazole, trialkylphosphine (tributylphosphine, etc.), dialkylarylphosphine (dimethylphenylphosphine, etc.), alkyldiarylphosphine (methyldiphenylphosphine, etc.), Organic phosphine compounds such as triphenylphosphine, alkyl-substituted triphenylphosphine, etc., and addition of maleic anhydride, 1,4-benzoquinone, 2,5-methanone, 1,4 to these organic phosphine compounds - naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxyquinone Compounds with intramolecular polarization including quinone compounds such as methoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, and compounds having π bonds such as diazophenylmethane and phenol resins , and derivatives of these.

進而可列舉：2-乙基-4-甲基咪唑四苯基硼酸鹽、N-甲基嗎啉四苯基硼酸鹽等苯基硼鹽。另外，作為具有潛伏性的硬化促進劑，可列舉以常溫固體的具有胺基的化合物為核並被覆常溫固體的環氧化合物的殼而成的核-殼粒子。硬化促進劑可單獨使用一種，亦可將兩種以上組合使用。 Further, phenyl boron salts such as 2-ethyl-4-methylimidazolium tetraphenyl borate and N-methylmorpholine tetraphenyl borate can be mentioned. Moreover, as a hardening accelerator which has a latent property, the core-shell particle which uses the compound which has a room temperature solid amine group as a core and coats the shell of the room temperature solid epoxy compound is mentioned. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more types.

於液狀密封材包含硬化促進劑的情況下，所述硬化促進 劑的量並無特別限制，但相對於環氧樹脂100質量份，較佳為0.1質量份~40質量份，更佳為1質量份~20質量份。 When the liquid sealing material contains a hardening accelerator, the hardening accelerator The amount of the agent is not particularly limited, but is preferably 0.1 parts by mass to 40 parts by mass, more preferably 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the epoxy resin.

<可撓劑> <flexible agent>

就提升耐熱衝擊性、減少對於半導體器件的應力等觀點而言，液狀密封材視需要亦可含有可撓劑。 From the viewpoints of improving thermal shock resistance and reducing stress to a semiconductor device, the liquid sealing material may contain a flexible agent if necessary.

可撓劑並無特別限制，可自樹脂組成物中一般所使用的可撓劑中選擇。其中，較佳為橡膠粒子。作為橡膠粒子，可列舉：苯乙烯-丁二烯橡膠(styrene butadiene rubber，SBR)、腈-丁二烯橡膠(nitrile-butadiene rubber，NBR)、丁二烯橡膠(butadiene rubber，BR)、胺基甲酸酯橡膠(urethane rubber，UR)、丙烯酸橡膠(acrylic rubber，AR)等粒子。該些中，就耐熱性及耐濕性的觀點而言，較佳為丙烯酸橡膠的粒子，更佳為具有核殼結構的丙烯酸系聚合體的粒子(即，核殼型丙烯酸橡膠粒子)。 The flexible agent is not particularly limited, and can be selected from flexible agents generally used in resin compositions. Among them, rubber particles are preferred. Examples of the rubber particles include styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), butadiene rubber (BR), amine groups Particles such as urethane rubber (UR) and acrylic rubber (AR). Among these, from the viewpoint of heat resistance and moisture resistance, particles of acrylic rubber are preferred, and particles of an acrylic polymer having a core-shell structure (ie, core-shell acrylic rubber particles) are more preferred.

另外，亦可較佳地使用矽酮橡膠粒子。作為矽酮橡膠粒子，可列舉：將直鏈狀的聚二甲基矽氧烷、聚甲基苯基矽氧烷、聚二苯基矽氧烷等聚有機矽氧烷交聯所得的矽酮橡膠粒子，利用矽酮樹脂將矽酮橡膠粒子的表面被覆而成者，藉由乳化聚合等所得的包含固體矽酮粒子的核與丙烯酸樹脂等有機聚合體的殼的核-殼聚合體粒子等。該些矽酮橡膠粒子的形狀可為非晶形，亦可為球形，但為了將液狀密封材的黏度抑制得低，較佳為球形者。該些矽酮橡膠粒子例如可自東麗道康寧矽酮(Toray Dow Corning Silicone)股份有限公司、信越化學工業股份有限公司等獲取市售 品。 In addition, silicone rubber particles can also be preferably used. Examples of silicone rubber particles include silicones obtained by crosslinking polyorganosiloxane such as linear polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. Rubber particles, obtained by covering the surface of silicone rubber particles with silicone resin, core-shell polymer particles obtained by emulsion polymerization, etc., including a core of solid silicone particles and a shell of an organic polymer such as acrylic resin, etc. . The shape of these silicone rubber particles may be amorphous or spherical, but in order to keep the viscosity of the liquid sealing material low, spherical ones are preferred. These silicone rubber particles are commercially available, for example, from Toray Dow Corning Silicone Co., Ltd., Shin-Etsu Chemical Co., Ltd., etc. Taste.

<偶合劑> <Coupling Agent>

出於提高樹脂成分與無機填充材、或者樹脂成分與線的界面中的接著性的目的，液狀密封材亦可含有偶合劑。偶合劑可用於無機填充材的表面處理中，亦可與無機填充材分開調配。 The liquid sealing material may contain a coupling agent for the purpose of improving the adhesiveness at the interface between the resin component and the inorganic filler, or between the resin component and the wire. The coupling agent can be used in the surface treatment of the inorganic filler, and can also be prepared separately from the inorganic filler.

偶合劑並無特別限制，可使用公知者。例如可列舉：具有胺基(1級、2級或3級)的矽烷化合物、環氧矽烷、巰基矽烷、烷基矽烷、脲基矽烷、乙烯基矽烷等各種矽烷化合物，鈦化合物，鋁螯合劑類，鋁/鋯系化合物等。偶合劑可單獨使用一種，亦可將兩種以上組合使用。 The coupling agent is not particularly limited, and known ones can be used. For example, various silane compounds such as silane compounds having an amine group (primary, secondary, or tertiary), epoxy silanes, mercapto silanes, alkyl silanes, ureido silanes, and vinyl silanes, titanium compounds, and aluminum chelating agents can be mentioned. class, aluminum/zirconium series compounds, etc. A coupling agent may be used individually by 1 type, and may be used in combination of 2 or more types.

作為矽烷偶合劑，具體而言，可列舉：乙烯基三氯矽烷、乙烯基三乙氧基矽烷、乙烯基三(β-甲氧基乙氧基)矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、β-(3,4-環氧環己基)乙基三甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基甲基二甲氧基矽烷、乙烯基三乙醯氧基矽烷、γ-巰基丙基三甲氧基矽烷、γ-胺基丙基三甲氧基矽烷、γ-胺基丙基甲基二甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-胺基丙基甲基二乙氧基矽烷、γ-苯胺基丙基三甲氧基矽烷、γ-苯胺基丙基三乙氧基矽烷、γ-(N,N-二甲基)胺基丙基三甲氧基矽烷、γ-(N,N-二乙基)胺基丙基三甲氧基矽烷、γ-(N,N-二丁基)胺基丙基三甲氧基矽烷、γ-(N-甲基)苯胺基丙基三甲氧基矽烷、γ-(N-乙基)苯胺基丙基三甲氧基矽烷、γ-(N,N-二甲基)胺基丙基三乙氧基矽烷、γ-(N,N-二乙基)胺基丙基三乙氧基矽烷、 γ-(N,N-二丁基)胺基丙基三乙氧基矽烷、γ-(N-甲基)苯胺基丙基三乙氧基矽烷、γ-(N-乙基)苯胺基丙基三乙氧基矽烷、γ-(N,N-二甲基)胺基丙基甲基二甲氧基矽烷、γ-(N,N-二乙基)胺基丙基甲基二甲氧基矽烷、γ-(N,N-二丁基)胺基丙基甲基二甲氧基矽烷、γ-(N-甲基)苯胺基丙基甲基二甲氧基矽烷、γ-(N-乙基)苯胺基丙基甲基二甲氧基矽烷、N-(三甲氧基矽烷基丙基)乙二胺、N-(二甲氧基甲基矽烷基異丙基)乙二胺、甲基三甲氧基矽烷、二甲基二甲氧基矽烷、甲基三乙氧基矽烷、γ-氯丙基三甲氧基矽烷、六甲基二矽烷、乙烯基三甲氧基矽烷、γ-巰基丙基甲基二甲氧基矽烷等。 Specific examples of the silane coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, and γ-methacryloyloxypropane. Trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethyl dimethyl Oxysilane, vinyltriacetoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma- Aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ-( N,N-Dimethyl)aminopropyltrimethoxysilane, γ-(N,N-diethyl)aminopropyltrimethoxysilane, γ-(N,N-dibutyl)amino Propyltrimethoxysilane, γ-(N-methyl)anilinopropyltrimethoxysilane, γ-(N-ethyl)anilinopropyltrimethoxysilane, γ-(N,N-dimethyl aminopropyltriethoxysilane, γ-(N,N-diethyl)aminopropyltriethoxysilane, γ-(N,N-Dibutyl)aminopropyltriethoxysilane, γ-(N-methyl)anilinopropyltriethoxysilane, γ-(N-ethyl)anilinopropyl triethoxysilane, γ-(N,N-dimethyl)aminopropylmethyldimethoxysilane, γ-(N,N-diethyl)aminopropylmethyldimethoxy Silane, γ-(N,N-dibutyl)aminopropylmethyldimethoxysilane, γ-(N-methyl)anilinopropylmethyldimethoxysilane, γ-(N -Ethyl)anilinopropylmethyldimethoxysilane, N-(trimethoxysilylpropyl)ethylenediamine, N-(dimethoxymethylsilylisopropyl)ethylenediamine, Methyltrimethoxysilane, Dimethyldimethoxysilane, Methyltriethoxysilane, γ-Chloropropyltrimethoxysilane, Hexamethyldisilane, Vinyltrimethoxysilane, γ-Mercapto Propylmethyldimethoxysilane, etc.

作為鈦偶合劑，具體而言，可列舉：異丙基三異硬脂醯基鈦酸酯、異丙基三(二辛基焦磷酸酯)鈦酸酯、異丙基三(N-胺基乙基-胺基乙基)鈦酸酯、四辛基雙(二-十三烷基亞磷酸酯)鈦酸酯、四(2,2-二烯丙基氧基甲基-1-丁基)雙(二-十三烷基)亞磷酸酯鈦酸酯、雙(二辛基焦磷酸酯)氧基乙酸酯鈦酸酯、雙(二辛基焦磷酸酯)伸乙基鈦酸酯、異丙基三辛醯基鈦酸酯、異丙基二甲基丙烯酸異硬脂醯基鈦酸酯、異丙基三-十二烷基苯磺醯基鈦酸酯、異丙基異硬脂醯基二丙烯酸鈦酸酯、異丙基三(二辛基磷酸酯)鈦酸酯、異丙基三枯基苯基鈦酸酯、四異丙基雙(二辛基亞磷酸酯)鈦酸酯等。 Specific examples of the titanium coupling agent include isopropyl triisostearyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl tris(N-amino) Ethyl-aminoethyl)titanate, tetraoctylbis(di-tridecylphosphite)titanate, tetrakis(2,2-diallyloxymethyl-1-butyl) ) bis(di-tridecyl) phosphite titanate, bis(dioctyl pyrophosphate) oxyacetate titanate, bis(dioctyl pyrophosphate) ethylidene titanate , Isopropyl trioctanoyl titanate, isopropyl dimethacrylate isostearyl titanate, isopropyl tri-dodecylbenzenesulfonyl titanate, isopropyl isostearyl titanate Diacrylate titanate, isopropyl tris(dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, tetraisopropyl bis(dioctyl phosphite) titanate Wait.

於液狀密封材包含偶合劑的情況下，所述偶合劑的量並無特別限制，較佳為相對於無機填充材100質量份而為1質量份~30質量份。 When the liquid sealing material contains a coupling agent, the amount of the coupling agent is not particularly limited, but is preferably 1 part by mass to 30 parts by mass relative to 100 parts by mass of the inorganic filler.

<離子捕捉劑> <Ion trapping agent>

就提升半導體封裝的耐遷移性、耐濕性、高溫放置特性等的觀點而言，液狀密封材亦可含有離子捕捉劑。離子捕捉劑可單獨使用一種，亦可將兩種以上組合使用。 The liquid sealing material may contain an ion trapping agent from the viewpoint of improving the migration resistance, moisture resistance, high temperature storage characteristics, etc. of the semiconductor package. An ion trapping agent may be used individually by 1 type, and may be used in combination of 2 or more types.

作為離子捕捉劑，可列舉下述組成式(V)及組成式(VI)所表示的陰離子交換體。 As an ion scavenger, the anion exchanger represented by the following compositional formula (V) and compositional formula (VI) is mentioned.

Mg1-aAla(OH)2(CO3)a/2．mH2O．．．(V) Mg 1-a Al a (OH) 2 (CO 3 ) a/2 . mH 2 O. . ． (V)

(0<a≦0.5，m為正數) (0<a≦0.5, m is a positive number)

BiOa(OH)b(NO3)c．．．(VI) BiO a (OH) b (NO 3 ) c . . ． (VI)

(0.9≦a≦1.1、0.6≦b≦0.8、0.2≦c≦0.4) (0.9≦a≦1.1, 0.6≦b≦0.8, 0.2≦c≦0.4)

所述式(V)的化合物可作為市售品(協和化學工業股份有限公司製造的商品名「DHT-4A」)而獲取。另外，所述式(VI)的化合物可作為市售品(東亞合成股份有限公司製造的商品名「IXE500」)而獲取。所述化合物以外的陰離子交換體亦可用作離子捕捉劑。例如可列舉選自鎂、鋁、鈦、鋯、銻等中的元素的含水氧化物等。 The compound of the formula (V) can be obtained as a commercial product (trade name "DHT-4A" manufactured by Kyowa Chemical Industry Co., Ltd.). In addition, the compound of the said formula (VI) can be obtained as a commercial item (trade name "IXE500" by Toagosei Co., Ltd.). Anion exchangers other than the compounds described above can also be used as ion scavengers. For example, hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium, antimony, and the like can be mentioned.

於液狀密封材包含離子捕捉劑的情況下，所述離子捕捉劑的量並無特別限制。例如較佳為液狀密封材整體的0.1質量%~3.0質量%，更佳為0.3質量%~1.5質量%。 When the liquid sealing material contains an ion scavenger, the amount of the ion scavenger is not particularly limited. For example, it is preferably 0.1% by mass to 3.0% by mass of the entire liquid sealing material, and more preferably 0.3% by mass to 1.5% by mass.

於離子捕捉劑為粒子狀的情況下，其體積平均粒徑(D50%)較佳為0.1μm~3.0μm。另外，最大粒徑較佳為10μm 以下。 When the ion trapping agent is in the form of particles, the volume average particle diameter (D50%) is preferably 0.1 μm to 3.0 μm. In addition, the maximum particle size is preferably 10 μm the following.

<其他成分> <Other ingredients>

液狀密封材視需要亦可含有所述成分以外的成分。例如視需要可調配染料、碳黑等著色劑、稀釋劑、調平劑、消泡劑等。 The liquid sealing material may contain components other than the above-mentioned components as necessary. For example, dyes, colorants such as carbon black, diluents, leveling agents, defoaming agents, etc. can be formulated as needed.

4b.第2密封層 4b. The second sealing layer

第2密封層4b包含絕緣性樹脂塗佈材的乾燥塗膜，並藉由第1密封層4a形成後塗佈所述絕緣性塗佈材而形成。所述第2密封層4b作為針對線而言的絕緣保護層發揮功能。 The 2nd sealing layer 4b consists of the dry coating film of an insulating resin coating material, and is formed by coating the said insulating coating material after the formation of the 1st sealing layer 4a. The second sealing layer 4b functions as an insulating protective layer for the wire.

所述絕緣性樹脂塗佈材具有以下記載的一個以上的特性。 The insulating resin coating material has one or more properties described below.

(i)至少成膜後的絕緣破壞電壓為150kV/mm以上。 (i) At least the dielectric breakdown voltage after film formation is 150 kV/mm or more.

(ii)含有平均粒徑0.1μm~5.0μm的樹脂填料。 (ii) A resin filler having an average particle diameter of 0.1 μm to 5.0 μm is contained.

(iii)25℃下的黏度為30Pa．s~500Pa．s。 (iii) The viscosity at 25°C is 30Pa. s~500Pa. s.

(iv)25℃下的觸變係數為2.0~10.0。 (iv) The thixotropic coefficient at 25°C is 2.0 to 10.0.

(v)加熱成膜後，絕緣性樹脂成分與樹脂填料變得均勻，不會產生絕緣性樹脂與填料的界面。因此，雖為薄膜，但可保證高絕緣性。 (v) After film-forming by heating, the insulating resin component and the resin filler become uniform, and the interface between the insulating resin and the filler does not occur. Therefore, although it is a thin film, high insulating properties can be ensured.

關於絕緣性樹脂塗佈材，於塗佈時根據作為塗佈對象的半導體元件的形狀而有產生空間之虞。例如，於保護半導體元件中的線上部的情況下，將線的端部堵住，藉此，於線下部形成空間，且於之後的密封步驟中，亦有密封材並不順利地侵入之虞。於半導體元件中存在空間的情況下，由於濕度的影響等大大影響 半導體元件的可靠性下降，因此，通常不容許半導體元件中的空間部分的產生。 Regarding the insulating resin coating material, at the time of coating, there is a possibility that a space may be generated depending on the shape of the semiconductor element to be coated. For example, in the case of protecting the upper part of the wire in the semiconductor element, the end of the wire is blocked to form a space under the wire, and there is a possibility that the sealing material may not penetrate smoothly in the subsequent sealing step. . When there is space in the semiconductor element, it is greatly affected by the influence of humidity, etc. The reliability of the semiconductor element is degraded, and therefore, the generation of a space portion in the semiconductor element is generally not tolerated.

為了避免此種半導體元件中、或線部的空間產生，而利用事先說明的液狀密封材預先將線下部密封，藉此，可抑制半導體元件中的孔隙的產生，從而改善半導體元件的可靠性。液狀密封材將線下部的空間部分填充，不僅有助於保證半導體的可靠，性，亦具有保護線自身的效果。線亦存在由於元件密封步驟中的壓力而塌陷的情況。但藉由利用液狀密封材預先密封，亦可避免線的塌陷。 In order to avoid the occurrence of space in the semiconductor element or the wire portion, the lower portion of the wire is sealed in advance with a liquid sealing material described in advance, whereby the generation of voids in the semiconductor element can be suppressed, and the reliability of the semiconductor element can be improved. . The liquid sealing material partially fills the space below the wire, which not only helps to ensure the reliability and performance of the semiconductor, but also has the effect of protecting the wire itself. There are also cases where the wire collapses due to the pressure during the element sealing step. However, the collapse of the wire can also be avoided by pre-sealing with a liquid sealing material.

一實施形態中，絕緣性樹脂塗佈材較佳為成膜後的絕緣破壞電壓為150kV/mm以上，並含有平均粒徑0.1μm~5.0μm的樹脂填料，25℃下的黏度為30Pa．s~500Pa．s，且觸變係數為2.0~10.0。 In one embodiment, the insulating resin coating material preferably has a dielectric breakdown voltage of 150kV/mm or more after film formation, contains a resin filler with an average particle size of 0.1 μm to 5.0 μm, and has a viscosity of 30Pa at 25°C. s~500Pa. s, and the thixotropic coefficient is 2.0~10.0.

成膜後的絕緣破壞電壓較佳為150kV/mm以上，進而佳為200kV/mm以上。一實施形態中，根據絕緣性樹脂塗佈材，可獲得200kV/mm以上的絕緣破壞電壓，可有助於半導體元件的薄型化。 The dielectric breakdown voltage after film formation is preferably 150 kV/mm or more, and more preferably 200 kV/mm or more. In one embodiment, according to the insulating resin coating material, a dielectric breakdown voltage of 200 kV/mm or more can be obtained, which can contribute to thinning of the semiconductor element.

絕緣性樹脂可自聚醯胺、聚醯胺醯亞胺、聚醯亞胺等高耐熱性樹脂中選擇。一實施形態中，絕緣性樹脂塗佈材較佳為包含選自由聚醯胺、聚醯胺醯亞胺、及聚醯亞胺所組成的群組中的至少一種絕緣性樹脂。特別是就半導體元件形成時無需醯亞胺化的高溫處理的方面而言，較佳為聚醯胺、聚醯胺醯亞胺，就高耐 熱性的方面而言，更佳為聚醯胺醯亞胺樹脂。關於樹脂，只要為與樹脂密封構件的密接力優異的高耐熱的樹脂，則可應用。只要聚醯亞胺具有即便於醯亞胺基形成後亦可溶於溶媒的樹脂結構，則就耐熱性的觀點而言，亦存在最佳為聚醯亞胺的情況。 The insulating resin can be selected from high heat-resistant resins such as polyamide, polyamide imide, and polyimide. In one embodiment, the insulating resin coating material preferably includes at least one insulating resin selected from the group consisting of polyamide, polyamide imide, and polyimide. In particular, from the viewpoint of not requiring high-temperature treatment for imidization when forming a semiconductor element, polyamide and polyamide imide are preferred. In terms of thermal properties, a polyamide imide resin is more preferred. The resin can be applied as long as it is a highly heat-resistant resin excellent in adhesion to the resin sealing member. As long as the polyimide has a resin structure that is soluble in the solvent even after the formation of the imide group, there are cases where the polyimide is optimal from the viewpoint of heat resistance.

以下，對構成絕緣性樹脂塗佈材的成分進行說明。絕緣性樹脂塗佈材包含：以質量比6：4~9：1包含第一極性溶媒(A1)與具有較第一極性溶媒(A1)的沸點低的沸點的第二極性溶媒(A2)的混合溶媒；於室溫下可溶於第一極性溶媒(A1)與第二極性溶媒(A2)的混合溶媒的絕緣耐熱性樹脂(B)；以及於室溫下可溶於第一極性溶媒(A1)、不溶於第二極性溶媒(A2)、且不溶於第一極性溶媒(A1)與第二極性溶媒(A2)的混合溶媒的絕緣耐熱性樹脂(C)。此處，本說明書中記載的所謂「室溫」為25℃。 Hereinafter, the components constituting the insulating resin coating material will be described. The insulating resin coating material includes a first polar solvent (A1) and a second polar solvent (A2) having a lower boiling point than the first polar solvent (A1) in a mass ratio of 6:4 to 9:1. mixed solvent; insulating heat-resistant resin (B) soluble in a mixed solvent of the first polar solvent (A1) and the second polar solvent (A2) at room temperature; and soluble in the first polar solvent (A2) at room temperature A1), an insulating heat-resistant resin (C) that is insoluble in the second polar solvent (A2) and insoluble in a mixed solvent of the first polar solvent (A1) and the second polar solvent (A2). Here, the so-called "room temperature" described in this specification is 25°C.

絕緣耐熱性樹脂(B)於室溫下可溶於第一極性溶媒(A1)與第二極性溶媒(A2)的混合溶媒，絕緣耐熱性樹脂(C)於室溫下不溶於第一極性溶媒(A1)與第二極性溶媒(A2)的混合溶媒。因此，絕緣性樹脂塗佈材中，絕緣耐熱性樹脂(C)分散於第一極性溶媒(A1)、第二極性溶媒(A2)及絕緣耐熱性樹脂(B)的混合溶媒中，並作為填料起作用。藉此，特別是可容易地調整為適於為了形成線上部的第2密封層而以分配器方式供給絕緣性樹脂塗佈材的觸變值。進而，若將絕緣性樹脂塗佈材加熱至絕緣耐熱性樹脂(C)溶解的溫度為止，則絕緣耐熱性樹脂(C)溶解，從 而填料消失。藉此，可賦予精密的解析度，並且提升樹脂膜的表而的平坦性。 The insulating heat-resistant resin (B) is soluble in the mixed solvent of the first polar solvent (A1) and the second polar solvent (A2) at room temperature, and the insulating heat-resistant resin (C) is insoluble in the first polar solvent at room temperature. (A1) A mixed solvent with the second polar solvent (A2). Therefore, in the insulating resin coating material, the insulating heat-resistant resin (C) is dispersed in a mixed solvent of the first polar solvent (A1), the second polar solvent (A2), and the insulating heat-resistant resin (B), and serves as a filler kick in. Thereby, it is possible to easily adjust the thixotropic value suitable for supplying the insulating resin coating material by the dispenser method in order to form the second sealing layer in the upper part of the line. Furthermore, when the insulating resin coating material is heated to a temperature at which the insulating heat-resistant resin (C) dissolves, the insulating and heat-resistant resin (C) is dissolved, and the And the filler disappears. Thereby, precise resolution can be imparted, and the surface flatness of the resin film can be improved.

作為第一極性溶媒(A1)及第二極性溶媒(A2)，例如可列舉：二乙二醇單甲醚、二乙二醇單***、三乙二醇單甲醚、三乙二醇單***、四乙二醇單甲醚、四乙二醇單***等聚醚醇系溶媒，二乙二醇二甲醚、二乙二醇二***、二乙二醇二丙醚、二乙二醇二丁醚、三乙二醇二甲醚、三乙二醇二***、三乙二醇二丙醚、三乙二醇二丁醚、四乙二醇二甲醚、四乙二醇二***、四乙二醇二丙醚、四乙二醇二丁醚等醚系溶媒，二甲基亞碸、二乙基亞碸、二甲基碸、環丁碸等含硫系溶媒，乙酸乙酯、乙酸丁酯、乙酸溶纖劑、乙基溶纖劑乙酸酯、丁基溶纖劑乙酸酯等酯系溶媒，甲基乙基酮、甲基異丁基酮、環己酮、苯乙酮等酮系溶媒，N-甲基吡咯啶酮、二甲基乙醯胺、二甲基甲醯胺、1,3-二甲基-3,4,5,6-四氫-2(1H)-嘧啶酮、1,3-二甲基-2-咪唑啶酮等含氮系溶媒，甲苯、二甲苯等芳香族烴系溶媒，γ-丁內酯、γ-戊內酯、γ-己內酯、γ-庚內酯、α-乙醯基-γ-丁內酯、ε-己內酯等內酯系溶媒，丁醇、辛醇、乙二醇、丙三醇(glycerine)等醇系溶媒，及苯酚、甲酚、二甲苯酚等酚系溶媒等。 Examples of the first polar solvent (A1) and the second polar solvent (A2) include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether. , tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether and other polyether alcohol solvents, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol diethyl ether Butyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dipropyl ether, triethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol Ether-based solvents such as ethylene glycol dipropyl ether and tetraethylene glycol dibutyl ether, sulfur-containing solvents such as dimethyl sulfite, diethyl sulfite, dimethyl sulfite, and cyclobutane, ethyl acetate, acetic acid Ester solvents such as butyl ester, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, etc., ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, etc. Solvents, N-methylpyrrolidone, dimethylacetamide, dimethylformamide, 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidine Nitrogen-containing solvents such as ketones and 1,3-dimethyl-2-imidazolidinone, aromatic hydrocarbon solvents such as toluene and xylene, γ-butyrolactone, γ-valerolactone, γ-caprolactone, Lactone-based solvents such as γ-enantholactone, α-acetyl-γ-butyrolactone, and ε-caprolactone, alcohol-based solvents such as butanol, octanol, ethylene glycol, and glycerine, And phenolic solvents such as phenol, cresol, xylenol, etc.

第一極性溶媒(A1)及第二極性溶媒(A2)的組合只要自該些溶媒中根據絕緣耐熱性樹脂(B)及絕緣耐熱性樹脂(C)的種類而適宜選擇並使用即可。 The combination of the first polar solvent (A1) and the second polar solvent (A2) may be appropriately selected and used according to the types of the insulating heat-resistant resin (B) and the insulating heat-resistant resin (C) from these solvents.

作為第一極性溶媒(A1)，較佳為可列舉：N-甲基吡咯啶酮、二甲基乙醯胺、二甲基甲醯胺、1,3-二甲基-3,4,5,6-四氫-2(1H)-嘧啶酮、1,3-二甲基-2-咪唑啶酮等含氮系溶媒，二甲基亞碸、二乙基亞碸、二甲基碸、環丁碸等含硫系溶媒，γ-丁內酯、γ-戊內酯、γ-己內酯、γ-庚內酯、α-乙醯基-γ-丁內酯、ε-己內酯等內酯系溶媒，甲基乙基酮、甲基異丁基酮、環己酮、苯乙酮等酮系溶媒，及丁醇、辛醇、乙二醇、丙三醇等醇系溶媒等。 Preferable examples of the first polar solvent (A1) include N-methylpyrrolidone, dimethylacetamide, dimethylformamide, 1,3-dimethyl-3,4,5 ,6-tetrahydro-2(1H)-pyrimidinone, 1,3-dimethyl-2-imidazolidinone and other nitrogen-containing solvents, dimethylsulfoxide, diethylsulfite, dimethylsulfite, Sulfur-containing solvents such as cyclobutane, γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-enantholactone, α-acetyl-γ-butyrolactone, ε-caprolactone Isolactone-based solvents, ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, and alcohol-based solvents such as butanol, octanol, ethylene glycol, and glycerol, etc. .

於後述絕緣耐熱性樹脂(B)及絕緣耐熱性樹脂(C)分別獨立地為選自聚醯胺樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、或聚醯亞胺樹脂及聚醯胺醯亞胺樹脂的前驅物中的至少一者的情況下，作為第一極性溶媒(A1)，特佳為γ-丁內酯。 The insulating heat-resistant resin (B) and the insulating heat-resistant resin (C) described later are independently selected from polyamide resins, polyimide resins, polyamide-imide resins, or polyimide resins and polyamide resins. In the case of at least one of the precursors of the imide imide resin, as the first polar solvent (A1), γ-butyrolactone is particularly preferred.

作為第二極性溶媒(A2)，較佳為可列舉：二乙二醇二甲醚、二乙二醇二***、二乙二醇二丙醚、二乙二醇二丁醚、三乙二醇二甲醚、三乙二醇二***、三乙二醇二丙醚、三乙二醇二丁醚、四乙二醇二甲醚、四乙二醇二***、四乙二醇二丙醚、四乙二醇二丁醚等醚系溶媒， 二乙二醇單甲醚、二乙二醇單***、三乙二醇單甲醚、三乙二醇單***、四乙二醇單甲醚、四乙二醇單***等聚醚醇系溶媒，及乙酸乙酯、乙酸丁酯、乙酸溶纖劑、乙基溶纖劑乙酸酯、丁基溶纖劑乙酸酯等酯系溶媒等。 Preferable examples of the second polar solvent (A2) include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and triethylene glycol. Dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dipropyl ether, triethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dipropyl ether, Ether-based solvents such as tetraethylene glycol dibutyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether and other polyether alcohol solvents , and ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate and other ester solvents.

於後述絕緣耐熱性樹脂(B)及絕緣耐熱性樹脂(C)分別獨立地為選自聚醯胺樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、或聚醯亞胺樹脂及聚醯胺醯亞胺樹脂的前驅物中的至少一者的情況下，作為第二極性溶媒(A2)，較佳為聚醚醇系溶媒、或酯系溶媒。 The insulating heat-resistant resin (B) and the insulating heat-resistant resin (C) described later are independently selected from polyamide resins, polyimide resins, polyamide-imide resins, or polyimide resins and polyamide resins. In the case of at least one of the precursors of the amide imide resin, the second polar solvent (A2) is preferably a polyether alcohol-based solvent or an ester-based solvent.

就提升絕緣性樹脂塗佈材的處理性的觀點而言，絕緣性樹脂塗佈材較佳為第一極性溶媒(A1)的沸點與第二極性溶媒(A2)的沸點之差為10℃~100℃，更佳為10℃~50℃，進而佳為10℃~30℃。另外，就可延長塗佈時的絕緣性樹脂塗佈材的可使用時間的觀點而言，第一極性溶媒(A1)與第二極性溶媒(A2)兩者的沸點較佳為100℃以上，更佳為150℃以上。 From the viewpoint of improving the handleability of the insulating resin coating material, the insulating resin coating material is preferably such that the difference between the boiling point of the first polar solvent (A1) and the boiling point of the second polar solvent (A2) is 10° C. to 100°C, more preferably 10°C to 50°C, still more preferably 10°C to 30°C. In addition, from the viewpoint of prolonging the usable time of the insulating resin coating material at the time of coating, the boiling points of both the first polar solvent (A1) and the second polar solvent (A2) are preferably 100° C. or higher, More preferably, it is 150 degreeC or more.

絕緣耐熱性樹脂(B)及絕緣耐熱性樹脂(C)較佳為分別獨立地為選自聚醯胺樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、或聚醯亞胺樹脂及聚醯胺醯亞胺樹脂的前驅物中的至少一者。作為聚醯胺樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、或聚醯亞胺樹脂及聚醯胺醯亞胺樹脂的前驅物，例如可列舉藉由芳香族、脂肪族、或脂環式二胺化合物與具有2個~4個羧基的多元羧酸的反應而獲得者。所謂聚醯亞胺樹脂及聚醯胺醯亞胺樹脂的前驅物， 是指進行脫水閉環而形成聚醯亞胺樹脂、或聚醯胺醯亞胺樹脂的、作為即將脫水閉環前的物質的聚醯胺酸。再者，絕緣耐熱性樹脂(C)較佳為例如以60℃以上(較佳為60℃~200℃、更佳為100℃~180℃)加熱的情況下，可溶於所述混合溶媒。 The insulating heat-resistant resin (B) and the insulating heat-resistant resin (C) are preferably independently selected from polyamide resins, polyimide resins, polyamide-imide resins, or polyimide resins and At least one of the precursors of the polyimide imide resin. Examples of precursors of polyimide resins, polyimide resins, polyimide resins, or polyimide resins and polyimide resins include aromatic, aliphatic, or Obtained by the reaction of an alicyclic diamine compound and a polyvalent carboxylic acid having 2 to 4 carboxyl groups. The so-called polyimide resin and the precursor of polyimide resin, It means a polyimide resin, which is a substance immediately before dehydration and ring closure, which is a polyimide resin or a polyimide resin by dehydration and ring closure. Furthermore, the insulating heat-resistant resin (C) is preferably soluble in the mixed solvent when heated at, for example, 60° C. or higher (preferably 60° C. to 200° C., more preferably 100° C. to 180° C.).

作為芳香族、脂肪族、或脂環式二胺化合物，可列舉：包含伸芳基、可具有不飽和鍵的伸烷基、或可具有不飽和鍵的伸環烷基、或者將該些組合而成的基的二胺化合物。該些基亦可經由碳原子、氧原子、硫原子、矽原子、或將該些原子組合而成的基而鍵結。另外，伸烷基的碳骨架上所鍵結的氫原子亦可經氟原子取代。就耐熱性及機械強度的觀點而言，較佳為芳香族二胺。 Examples of the aromatic, aliphatic, or alicyclic diamine compound include an arylidene group, an alkylene group which may have an unsaturated bond, a cycloalkylene group which may have an unsaturated bond, or a combination of these. The resulting diamine compound. These groups may also be bonded via carbon atoms, oxygen atoms, sulfur atoms, silicon atoms, or groups formed by combining these atoms. In addition, the hydrogen atom bonded to the carbon skeleton of the alkylene group may be substituted with a fluorine atom. From the viewpoint of heat resistance and mechanical strength, aromatic diamines are preferred.

作為具有2個~4個羧基的多元羧酸，可列舉：二羧酸或其反應性酸衍生物、三羧酸或其反應性酸衍生物、四羧酸二酐。該些化合物可為於芳基或環內可具有交聯結構或者不飽和鍵的環烷基上鍵結有羧基的二羧酸、三羧酸或該些的反應性酸衍生物、或者於芳基或環內可具有交聯結構或者不飽和鍵的環烷基上鍵結有羧基的四羧酸二酐，該二羧酸、三羧酸或該些的反應性酸衍生物、以及四羧酸二酐可經由單鍵、或者經由碳原子、氧原子、硫原子、矽原子、或將該些原子組合而成的基而鍵結。另外，伸烷基的碳骨架上所鍵結的氫原子亦可經氟原子取代。該些化合物中，就耐熱性及機械強度的觀點而言，較佳為四羧酸二酐。芳香族、脂肪族、或脂環式二胺化合物與具有2個~4個羧基的多元羧酸的組合可根據反應性等而適宜選擇。 As a polyhydric carboxylic acid which has 2-4 carboxyl groups, dicarboxylic acid or its reactive acid derivative, tricarboxylic acid or its reactive acid derivative, and tetracarboxylic dianhydride are mentioned. These compounds may be dicarboxylic acids, tricarboxylic acids, or reactive acid derivatives thereof, in which a carboxyl group is bonded to an aryl group or a cycloalkyl group that may have a cross-linked structure or an unsaturated bond in the ring, or an aryl group. Tetracarboxylic dianhydride in which a carboxyl group is bonded to a cycloalkyl group which may have a cross-linked structure or an unsaturated bond in the ring, the dicarboxylic acid, tricarboxylic acid or reactive acid derivatives thereof, and tetracarboxylic acid The acid dianhydride may be bonded via a single bond, or via a carbon atom, an oxygen atom, a sulfur atom, a silicon atom, or a group formed by combining these atoms. In addition, the hydrogen atom bonded to the carbon skeleton of the alkylene group may be substituted with a fluorine atom. Among these compounds, tetracarboxylic dianhydride is preferred from the viewpoint of heat resistance and mechanical strength. The combination of an aromatic, aliphatic, or alicyclic diamine compound and a polyvalent carboxylic acid having 2 to 4 carboxyl groups can be appropriately selected according to reactivity and the like.

反應可不使用溶媒或者於有機溶媒的存在下進行。反應溫度較佳為設為25℃~250℃，反應時間可根據批次(batch)的規模、所採用的反應條件等而適宜選擇。 The reaction can be carried out without a solvent or in the presence of an organic solvent. The reaction temperature is preferably set to 25°C to 250°C, and the reaction time can be appropriately selected according to the scale of the batch, the reaction conditions employed, and the like.

對聚醯亞胺樹脂前驅物或聚醯胺醯亞胺樹脂前驅物進行脫水閉環而製成聚醯亞胺樹脂或聚醯胺醯亞胺樹脂的方法亦無特別限制，可使用一般的方法。例如，可使用在常壓或減壓下藉由加熱而脫水閉環的熱閉環法、於觸媒的存在下或觸媒的不存在下使用乙酸酐等脫水劑的化學閉環法等。 The method for dehydrating and ring-closing the polyimide resin precursor or the polyimide resin precursor to obtain the polyimide resin or the polyimide resin is also not particularly limited, and general methods can be used. For example, a thermal ring closure method of dehydration and ring closure by heating under normal pressure or reduced pressure, a chemical ring closure method using a dehydrating agent such as acetic anhydride in the presence or absence of a catalyst, and the like can be used.

熱閉環法較佳為一面將脫水反應中產生的水去除至系統外一面進行。此時，藉由將反應液加熱為80℃~400℃、較佳為100℃~250℃而進行。此時，亦可併用苯、甲苯、二甲苯等之類的與水共沸般的溶劑而將水共沸去除。 The thermal closed loop method is preferably carried out while removing water generated in the dehydration reaction to the outside of the system. At this time, it is performed by heating the reaction liquid to 80°C to 400°C, preferably 100°C to 250°C. In this case, water may be azeotropically removed by using a solvent such as benzene, toluene, and xylene that azeotropes with water in combination.

化學閉環法較佳為於化學脫水劑的存在下，於0℃~120℃、較佳為10℃~80℃下使其反應。作為化學脫水劑，例如較佳為乙酸酐、丙酸酐、丁酸酐、苯甲酸酐等酸酐；二環己基碳二醯亞胺等碳二醯亞胺化合物等。此時，較佳為併用吡啶、異喹啉、三甲基胺、三乙基胺、胺基吡啶、咪唑等促進環化反應的物質。化學脫水劑相對於二胺化合物的總量而使用90莫耳%~600莫耳%，促進環化反應的物質相對於二胺化合物的總量而使用40莫耳%~300莫耳%。另外，亦可使用亞磷酸三苯酯、亞磷酸三環己酯、磷酸三苯酯、磷酸、五氧化磷等磷化合物、硼酸、硼酸酐等硼化合物等脫水觸媒。 In the chemical ring-closure method, the reaction is preferably carried out at 0°C to 120°C, preferably 10°C to 80°C, in the presence of a chemical dehydrating agent. As the chemical dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride, and benzoic anhydride; carbodiimide compounds such as dicyclohexylcarbodiimide, and the like are preferred. In this case, it is preferable to use together a substance that promotes the cyclization reaction, such as pyridine, isoquinoline, trimethylamine, triethylamine, aminopyridine, and imidazole. The chemical dehydrating agent is used in 90 mol % to 600 mol % with respect to the total amount of the diamine compound, and the substance that promotes the cyclization reaction is used in 40 mol % to 300 mol % with respect to the total amount of the diamine compound. In addition, dehydration catalysts such as phosphorus compounds such as triphenyl phosphite, tricyclohexyl phosphite, triphenyl phosphate, phosphoric acid, and phosphorus pentoxide, and boron compounds such as boric acid and boric anhydride can also be used.

將藉由脫水反應而使醯亞胺化結束的反應液注入至大量過剩的相對於所述第一極性溶媒(A1)及第二極性溶媒(A2)而具有相容性、且相對於絕緣耐熱性樹脂(B)及絕緣耐熱性樹脂(C)而為貧溶媒的甲醇等低級醇、水、或該些的混合物等溶媒中，獲得樹脂的沈澱物，並對其進行過濾，將溶媒乾燥，藉此可獲得聚醯亞胺樹脂或聚醯胺醯亞胺樹脂。就所殘存的離子性雜質的減少化等觀點而言，較佳為熱閉環法。 The reaction solution that has been imidized by the dehydration reaction is injected into a large excess of the first polar solvent (A1) and the second polar solvent (A2), which is compatible with the first polar solvent (A1) and the second polar solvent (A2). The resin (B) and the insulating heat-resistant resin (C) are used in a solvent such as a lower alcohol such as methanol, water, or a mixture thereof, which is a poor solvent, to obtain a precipitate of the resin, which is filtered, and the solvent is dried. Thereby, a polyimide resin or a polyimide resin can be obtained. From the viewpoint of reduction of remaining ionic impurities, etc., the thermal closed loop method is preferred.

可根據絕緣耐熱性樹脂(B)及絕緣耐熱性樹脂(C)的種類來決定較佳的第一極性溶媒(A1)及第二極性溶媒(A2)的種類。作為第一極性溶媒(A1)及第二極性溶媒(A2)的較佳組合(混合溶媒)，例如可列舉下述(a)、(b)兩種。 The kind of preferable 1st polar solvent (A1) and 2nd polar solvent (A2) can be determined according to the kind of insulating heat-resistant resin (B) and insulating heat-resistant resin (C). As a preferable combination (mixed solvent) of a 1st polar solvent (A1) and a 2nd polar solvent (A2), the following two (a) and (b) are mentioned, for example.

(a)第一極性溶媒(A1)：N-甲基吡咯啶酮、二甲基乙醯胺等所述含氮系溶媒；二甲基亞碸等所述含硫系溶媒；γ-丁內酯等所述內酯系溶媒；二甲苯酚等所述酚系溶媒、與第二極性溶媒(A2)：二乙二醇二甲醚等所述醚系溶媒；環己酮等所述酮系溶媒；丁基溶纖劑乙酸酯等所述酯系溶媒；丁醇等所述醇系溶媒；二甲苯等所述芳香族烴系溶媒的組合。 (a) First polar solvent (A1): nitrogen-containing solvents such as N-methylpyrrolidone, dimethylacetamide, etc.; sulfur-containing solvents such as dimethylsulfoxide; γ-butane Lactone-based solvents such as esters; phenol-based solvents such as xylenol; and second polar solvents (A2): ether-based solvents such as diethylene glycol dimethyl ether; ketone-based solvents such as cyclohexanone Solvents; combinations of the ester-based solvents such as butyl cellosolve acetate; the alcohol-based solvents such as butanol; and the aromatic hydrocarbon-based solvents such as xylene.

(b)第一極性溶媒(A1)：四乙二醇二甲醚等所述醚系溶媒；環己酮等所述酮系溶媒、與第二極性溶媒(A2)：丁基溶纖劑乙酸酯、乙酸乙酯等所述酯系溶媒；丁醇等所述醇系溶媒；二乙二醇單***等所述聚醚醇系溶媒；二甲苯等所述芳香族烴系溶媒的組合。 (b) First polar solvent (A1): ether-based solvent such as tetraethylene glycol dimethyl ether; ketone-based solvent such as cyclohexanone, and second polar solvent (A2): butyl cellosolve acetate A combination of the ester-based solvents such as ethyl acetate, the alcohol-based solvents such as butanol, the polyether alcohol-based solvents such as diethylene glycol monoethyl ether, and the aromatic hydrocarbon-based solvents such as xylene.

作為應用於(a)型的混合溶媒中的絕緣耐熱性樹脂(B)及絕緣耐熱性樹脂(C)，例如可列舉以下者。作為絕緣耐熱性樹脂(B)，例如可列舉具有下述式(1)~式(10)所表示的結構單元的樹脂。 As the insulating heat-resistant resin (B) and the insulating heat-resistant resin (C) to be used in the mixed solvent of the (a) type, for example, the following can be mentioned. As insulating heat-resistant resin (B), the resin which has the structural unit represented by following formula (1) - formula (10) is mentioned, for example.

Figure 107127711-A0305-02-0035-1
Figure 107127711-A0305-02-0035-1

式(1)中，X為-CH2-、-O-、-CO-、-SO2-、或下述式(a)~式(i)所表示的基，式(i)中，p為1~100的整數。 In formula (1), X is -CH 2 -, -O-, -CO-, -SO 2 -, or a group represented by the following formulae (a) to (i), and in formula (i), p is an integer from 1 to 100.

[化2]

Figure 107127711-A0305-02-0036-2
[hua 2]
Figure 107127711-A0305-02-0036-2

Figure 107127711-A0305-02-0036-3
Figure 107127711-A0305-02-0036-3

式(2)中，R1及R2分別為氫原子或碳數1~6的烴基，彼此可相同亦可不同。X與式(1)的X相同。 In formula (2), R 1 and R 2 are each a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and may be the same or different from each other. X is the same as X in formula (1).

Figure 107127711-A0305-02-0037-4
Figure 107127711-A0305-02-0037-4

式(3)中，M為下述式(c)、式(h)、式(i)或式(j)所表示的基，式(i)中，p為1~100的整數。 In formula (3), M is a group represented by the following formula (c), formula (h), formula (i) or formula (j), and in formula (i), p is an integer of 1 to 100.

Figure 107127711-A0305-02-0037-5
Figure 107127711-A0305-02-0037-5

[化6]

Figure 107127711-A0305-02-0038-6
[hua 6]
Figure 107127711-A0305-02-0038-6

式(4)中，X與式(1)的X相同。 In formula (4), X is the same as X in formula (1).

Figure 107127711-A0305-02-0038-7
Figure 107127711-A0305-02-0038-7

式(5)中，X與式(1)的X相同。 In formula (5), X is the same as X in formula (1).

Figure 107127711-A0305-02-0038-8
Figure 107127711-A0305-02-0038-8

式(6)中，R3及R4分別為甲基、乙基、丙基、或苯基，彼此可相同亦可不同，X與式(1)的X相同。 In formula (6), R 3 and R 4 are each a methyl group, an ethyl group, a propyl group, or a phenyl group, which may be the same or different from each other, and X is the same as X in the formula (1).

Figure 107127711-A0305-02-0038-9
Figure 107127711-A0305-02-0038-9

Figure 107127711-A0305-02-0039-10
Figure 107127711-A0305-02-0039-10

式(8)中，x1為0或2，X與式(1)的X相同。 In formula (8), x 1 is 0 or 2, and X is the same as X in formula (1).

Figure 107127711-A0305-02-0039-11
Figure 107127711-A0305-02-0039-11

Figure 107127711-A0305-02-0039-13
Figure 107127711-A0305-02-0039-13

作為絕緣耐熱性樹脂(C)，例如可列舉具有下述式(11)~式(20)所表示的結構單元的樹脂。 As insulating heat-resistant resin (C), the resin which has the structural unit represented by following formula (11) - formula (20) is mentioned, for example.

[化13]

Figure 107127711-A0305-02-0040-14
[Chemical 13]
Figure 107127711-A0305-02-0040-14

式(11)中，Y為下述式(a)、式(c)或式(h)所表示的基。 In formula (11), Y is a group represented by the following formula (a), formula (c) or formula (h).

Figure 107127711-A0305-02-0040-15
Figure 107127711-A0305-02-0040-15

Figure 107127711-A0305-02-0040-16
Figure 107127711-A0305-02-0040-16

式(12)中，Y與式(11)的Y相同。再者，*部分相互鍵 結(以下相同)。 In formula (12), Y is the same as Y in formula (11). Again, the * part of the mutual key knot (same below).

Figure 107127711-A0305-02-0041-17
Figure 107127711-A0305-02-0041-17

Figure 107127711-A0305-02-0041-18
Figure 107127711-A0305-02-0041-18

式(14)中，Z為-CH2-、-O-、-CO-、-SO2-、或者下述式(a)或式(d)所表示的基。 In formula (14), Z is -CH 2 -, -O-, -CO-, -SO 2 -, or a group represented by the following formula (a) or formula (d).

Figure 107127711-A0305-02-0041-20
Figure 107127711-A0305-02-0041-20

[化19]

Figure 107127711-A0305-02-0042-21
[Chemical 19]
Figure 107127711-A0305-02-0042-21

Figure 107127711-A0305-02-0042-22
Figure 107127711-A0305-02-0042-22

式(16)中，Z與式(14)的Z相同。 In formula (16), Z is the same as Z in formula (14).

Figure 107127711-A0305-02-0042-23
Figure 107127711-A0305-02-0042-23

Figure 107127711-A0305-02-0042-24
Figure 107127711-A0305-02-0042-24

Figure 107127711-A0305-02-0043-27
Figure 107127711-A0305-02-0043-27

Figure 107127711-A0305-02-0043-28
Figure 107127711-A0305-02-0043-28

式(20)中，X與式(1)的X相同，n及m分別獨立地表示1以上的整數。n與m之比(n/m)較佳為80/20~30/70，更佳為70/30~50/50。 In formula (20), X is the same as X in formula (1), and n and m each independently represent an integer of 1 or more. The ratio of n to m (n/m) is preferably 80/20 to 30/70, more preferably 70/30 to 50/50.

所述組合中，較佳為使用內酯系溶媒或含氮系溶媒作為第一極性溶媒(A1)，使用醚系溶媒或酯系溶媒作為第二極性溶媒(A2)，使用式(1)所表示的樹脂作為絕緣耐熱性樹脂(B)，且使用具有式(20)或式(16)所表示的結構單元的樹脂作為絕緣耐熱性樹脂(C)。 In the combination, preferably a lactone-based solvent or a nitrogen-containing solvent is used as the first polar solvent (A1), an ether-based solvent or an ester-based solvent is used as the second polar solvent (A2), and the formula (1) is used. The represented resin is used as the insulating heat-resistant resin (B), and the resin having the structural unit represented by the formula (20) or the formula (16) is used as the insulating heat-resistant resin (C).

作為應用於(b)型的混合溶媒中的絕緣耐熱性樹脂(B)及絕緣耐熱性樹脂(C)，例如可列舉以下者。 Examples of the insulating heat-resistant resin (B) and the insulating heat-resistant resin (C) to be used in the mixed solvent of the (b) type include the following.

作為絕緣耐熱性樹脂(B)，例如使用具有下述式(21)及式(22)所表示的結構單元的樹脂、或者具有所述式(6)所表示的 結構單元的聚矽氧烷醯亞胺。 As the insulating heat-resistant resin (B), for example, a resin having a structural unit represented by the following formulas (21) and (22), or a resin having the above-mentioned formula (6) is used. Structural unit of polysiloxane imide.

Figure 107127711-A0305-02-0044-29
Figure 107127711-A0305-02-0044-29

Figure 107127711-A0305-02-0044-30
Figure 107127711-A0305-02-0044-30

式(22)中，Z1為-O-、-CO-、或者下述式(d)、式(e)、式(k)或式(1)所表示的基。R5及R6分別為下述式(m)或式(n)所表示的基，彼此可相同亦可不同。p為1~100的整數。 In formula (22), Z 1 is -O-, -CO-, or a group represented by the following formula (d), formula (e), formula (k) or formula (1). R 5 and R 6 are groups represented by the following formula (m) or formula (n), respectively, and may be the same or different from each other. p is an integer from 1 to 100.

[化27]

Figure 107127711-A0305-02-0045-31
[Chemical 27]
Figure 107127711-A0305-02-0045-31

Figure 107127711-A0305-02-0045-32
Figure 107127711-A0305-02-0045-32

作為絕緣耐熱性樹脂(C)，例如可列舉：具有所述式(1)的X為下述式(a)、式(b)或式(i)所表示的基的情況下的結構單元的聚醚醯胺醯亞胺、或所述式(5)~式(9)所表示的聚醯亞胺(其中，所述式(5)、式(6)、式(8)中的X為下述式(a)的情況除外)。 As the insulating heat-resistant resin (C), for example, those having a structural unit in the case where X of the above formula (1) is a group represented by the following formula (a), formula (b) or formula (i) can be mentioned. Polyetherimide imide, or polyimide represented by the formula (5) to formula (9) (wherein, X in the formula (5), formula (6), and formula (8) is Except for the case of the following formula (a)).

[化29]

Figure 107127711-A0305-02-0046-33
[Chemical 29]
Figure 107127711-A0305-02-0046-33

Figure 107127711-A0305-02-0046-34
Figure 107127711-A0305-02-0046-34

式(i)中，p為1~100的整數。 In formula (i), p is an integer of 1-100.

製備絕緣性樹脂塗佈材時的原料的投入順序並無特別限制。例如，可將所述絕緣性樹脂塗佈材的原料彙總混合，另外，亦可首先將第一極性溶媒(A1)及第二極性溶媒(A2)混合，並向該混合溶液中混合絕緣耐熱性樹脂(B)，其後，對第一極性溶媒(A1)、第二極性溶媒(A2)、及絕緣耐熱性樹脂(B)的混合溶液添加絕緣耐熱性樹脂(C)。 There is no particular limitation on the order of inputting the raw materials when preparing the insulating resin coating material. For example, the raw materials of the insulating resin coating material may be mixed together, or the first polar solvent (A1) and the second polar solvent (A2) may be mixed first, and the insulating heat resistance may be mixed into the mixed solution. Resin (B), then, the insulating heat-resistant resin (C) is added to the mixed solution of the first polar solvent (A1), the second polar solvent (A2), and the insulating heat-resistant resin (B).

可一面對所述絕緣性樹脂塗佈材的原料混合物進行加熱、攪拌等，直至於第一極性溶媒(A1)、第二極性溶媒(A2)、及絕緣耐熱性樹脂(B)的混合溶液中絕緣耐熱性樹脂(C)充分溶解的溫度為止，一面使其充分混合。 The raw material mixture of the insulating resin coating material can be heated, stirred, etc., until the mixed solution of the first polar solvent (A1), the second polar solvent (A2), and the insulating heat-resistant resin (B) Mix well until the temperature at which the medium insulating heat resistant resin (C) is sufficiently dissolved.

關於以所述方式獲得的絕緣性樹脂塗佈材，於室溫下於包含第一極性溶媒(A1)、第二極性溶媒(A2)及絕緣耐熱性樹脂(B)的溶液中分散有絕緣耐熱性樹脂(C)。即，絕緣耐熱性樹脂(C)於絕緣性樹脂塗佈材中作為填料而存在，可對絕緣性樹脂塗佈材賦予朝線上部供給時較佳的觸變性。 Regarding the insulating resin coating material obtained as described above, the insulating heat-resistant resin is dispersed in a solution containing the first polar solvent (A1), the second polar solvent (A2), and the insulating heat-resistant resin (B) at room temperature. Sexual resin (C). That is, the insulating heat-resistant resin (C) exists as a filler in the insulating resin coating material, and can impart a preferable thixotropy to the insulating resin coating material when supplied toward the upper part of the wire.

分散於絕緣性樹脂塗佈材中的絕緣耐熱性樹脂(C)的平均粒徑可為50μm以下的粒子狀，較佳為0.01μm~10μm、更佳為0.1μm~5μm。另外，最大粒徑較佳為10μm、更佳為5μm。該絕緣耐熱性樹脂(C)的平均粒徑及最大粒徑可藉由使用島津製作所股份有限公司製造的粒度分佈測定裝置SALD-2200而測定。 The average particle diameter of the insulating heat-resistant resin (C) dispersed in the insulating resin coating material may be in the form of particles of 50 μm or less, preferably 0.01 μm to 10 μm, more preferably 0.1 μm to 5 μm. In addition, the maximum particle diameter is preferably 10 μm, more preferably 5 μm. The average particle diameter and the maximum particle diameter of the insulating heat-resistant resin (C) can be measured by using a particle size distribution analyzer SALD-2200 manufactured by Shimadzu Corporation.

第一極性溶媒(A1)與第二極性溶媒(A2)的混合比率雖依存於絕緣耐熱性樹脂(B)及絕緣耐熱性樹脂(C)的種類、相對於第一極性溶媒(A1)及第二極性溶媒(A2)而言的溶解度或使用量等，但就使絕緣性樹脂塗佈材的流動性、樹脂膜的解析度、形狀保持性、及表面的平坦性高度地平衡的觀點而言，混合比率(A1：A2)為6：4~9：1，更佳為6.5：3.5~8.5：1.5，特佳為7：3~8：2。 Although the mixing ratio of the first polar solvent (A1) and the second polar solvent (A2) depends on the type of the insulating heat-resistant resin (B) and the insulating heat-resistant resin (C), relative to the first polar solvent (A1) and the second polar solvent The solubility and usage amount of the bipolar solvent (A2), but from the viewpoint of highly balancing the fluidity of the insulating resin coating material, the resolution, shape retention, and surface flatness of the resin film , the mixing ratio (A1:A2) is 6:4~9:1, more preferably 6.5:3.5~8.5:1.5, especially 7:3~8:2.

絕緣性樹脂塗佈材中，相對於絕緣耐熱性樹脂(B)及絕緣耐熱性樹脂(C)的樹脂總量100質量份，較佳為調配100質量份~3500質量份的第一極性溶媒(A1)與第二極性溶媒(A2)的混合溶媒，更佳為調配150質量份~1000質量份。 In the insulating resin coating material, it is preferable to prepare 100 parts by mass to 3500 parts by mass of the first polar solvent ( A1) The mixed solvent of the second polar solvent (A2) is more preferably 150 parts by mass to 1000 parts by mass.

絕緣耐熱性樹脂(B)與絕緣耐熱性樹脂(C)的調配比 並無特別限制，可為任意的調配量，但絕緣耐熱性樹脂(C)相對於絕緣耐熱性樹脂(B)的總量100質量份，較佳為調配10質量份~300質量份，若為10質量份~200質量份則更佳。若絕緣耐熱性樹脂(C)的使用量少於10質量份，則有所獲得的絕緣性樹脂塗佈材的觸變性下降的傾向，若絕緣耐熱性樹脂(C)的使用量多於300質量份，則有所獲得的樹脂膜的物性下降的傾向。 Mixing ratio of insulating heat-resistant resin (B) and insulating heat-resistant resin (C) There is no particular limitation, and any amount can be prepared, but the total amount of the insulating heat-resistant resin (C) relative to the total 100 parts by mass of the insulating heat-resistant resin (B) is preferably 10 to 300 parts by mass. 10 parts by mass to 200 parts by mass are more preferable. When the usage-amount of the insulating heat-resistant resin (C) is less than 10 parts by mass, the thixotropy of the insulating resin coating material obtained tends to decrease, and when the usage-amount of the insulating heat-resistant resin (C) is more than 300 parts by mass parts, the physical properties of the obtained resin film tended to decrease.

就形狀保持性的觀點而言，絕緣性樹脂塗佈材的25℃下的黏度為30Pa．s~500Pa．s，較佳為50Pa．s~400Pa．s，更佳為70Pa．s~300Pa．s。若25℃下的黏度為30Pa．s以下，則容易變得難以於印刷時保持形狀。另外，若黏度為500Pa．s以上，則有操作性容易下降的傾向。黏度可藉由調整絕緣性樹脂塗佈材的不揮發成分濃度(以下設為NV)、第一極性溶媒(A1)、絕緣耐熱性樹脂(B)或絕緣耐熱性樹脂(C)的分子量等而加以控制。例如，使用凝膠滲透層析法對絕緣耐熱性樹脂(B)及絕緣耐熱性樹脂(C)的分子量以標準聚苯乙烯換算進行測定所得的重量平均分子量設為10000~100000、較佳為20000~80000、特佳為30000~60000即可。 From the viewpoint of shape retention, the viscosity at 25°C of the insulating resin coating material is 30Pa. s~500Pa. s, preferably 50Pa. s~400Pa. s, more preferably 70Pa. s~300Pa. s. If the viscosity at 25 ℃ is 30Pa. s or less, it becomes difficult to maintain the shape during printing. In addition, if the viscosity is 500Pa. s or more tends to decrease the operability easily. The viscosity can be adjusted by adjusting the non-volatile content concentration of the insulating resin coating material (hereinafter referred to as NV), the first polar solvent (A1), the molecular weight of the insulating heat-resistant resin (B) or the insulating heat-resistant resin (C), etc. be controlled. For example, the weight average molecular weight obtained by measuring the molecular weight of the insulating heat-resistant resin (B) and the insulating heat-resistant resin (C) in terms of standard polystyrene using gel permeation chromatography is 10,000 to 100,000, preferably 20,000. ~80000, especially good is 30000~60000.

絕緣性樹脂塗佈材的觸變係數為2.0~10.0，較佳為2.0~6.0，更佳為2.5~5.5，進而佳為3.0~5.0。若觸變係數未滿2.0，則印刷性下降，若觸變係數超過6.0，則操作性下降，從而難以製作絕緣性樹脂塗佈材。 The thixotropic coefficient of the insulating resin coating material is 2.0 to 10.0, preferably 2.0 to 6.0, more preferably 2.5 to 5.5, and still more preferably 3.0 to 5.0. If the thixotropy coefficient is less than 2.0, the printability will decrease, and if the thixotropy coefficient exceeds 6.0, the workability will decrease, and it will be difficult to produce an insulating resin coating material.

5.樹脂密封構件 5. Resin sealing member

樹脂密封構件是以至少覆蓋所述第2密封層的方式設置。樹脂密封構件較佳為以覆蓋半導體器件與所述第2密封層的上表面的方式設置於基板整個面上。由於已經將線密封，因此無需於樹脂密封構件形成時考慮線流動等問題的發生。樹脂密封構件並無特別限定，可使用本技術領域中眾所周知的材料而構成。 The resin sealing member is provided so as to cover at least the second sealing layer. The resin sealing member is preferably provided on the entire surface of the substrate so as to cover the semiconductor device and the upper surface of the second sealing layer. Since the wire is already sealed, there is no need to consider the occurrence of problems such as wire flow when the resin sealing member is formed. The resin sealing member is not particularly limited, and can be constituted by using materials well known in the technical field.

作為形成樹脂密封構件的材料，例如可列舉包含環氧樹脂與酚樹脂的硬化性組成物。酚樹脂作為針對環氧樹脂而言的硬化劑而使用。 As a material which forms a resin sealing member, the curable composition containing an epoxy resin and a phenol resin is mentioned, for example. Phenolic resins are used as hardeners for epoxy resins.

作為環氧樹脂的具體例，可列舉：聯苯型環氧樹脂、雙酚型(雙酚F型、雙酚A型等)環氧樹脂、三苯基甲烷型環氧樹脂、鄰甲酚酚醛清漆型環氧樹脂、萘型環氧樹脂等。另外，作為酚樹脂的具體例，可列舉：三苯基甲烷型酚樹脂、苯酚芳烷基型酚樹脂、新酚樹脂型酚樹脂、共聚合苯酚芳烷基型酚樹脂、萘酚芳烷基型酚樹脂、伸聯苯基芳烷基型酚樹脂等。可單獨使用該些中的每一種，亦可將兩種以上組合使用。 Specific examples of epoxy resins include biphenyl type epoxy resins, bisphenol type (bisphenol F type, bisphenol A type, etc.) epoxy resins, triphenylmethane type epoxy resins, o-cresol novolacs Varnish type epoxy resin, naphthalene type epoxy resin, etc. In addition, as specific examples of the phenol resin, triphenylmethane type phenol resin, phenol aralkyl type phenol resin, neophenol resin type phenol resin, copolymerized phenol aralkyl type phenol resin, naphthol aralkyl type can be mentioned. type phenol resin, biphenyl-extended aralkyl type phenol resin, etc. Each of these may be used alone, or two or more may be used in combination.

<半導體元件的製造方法> <Manufacturing method of semiconductor element>

圖3(a)~圖3(d)是對半導體元件的製造方法進行說明的概略剖面圖，圖3(a)~圖3(d)對應於各步驟。一實施形態中，所述製造方法較佳為至少包含以下的步驟(a)~步驟(c)，進而包含步驟(d)。 FIGS. 3( a ) to 3 ( d ) are schematic cross-sectional views illustrating a method of manufacturing a semiconductor element, and FIGS. 3 ( a ) to 3 ( d ) correspond to the respective steps. In one embodiment, the manufacturing method preferably includes at least the following steps (a) to (c), and further includes a step (d).

步驟(a)：如圖3(a)所示，藉由線3將基板1與配置於基板1上的半導體器件2電性連接。所謂「電性連接」，是指通 常於基板1及半導體器件2上分別設置有電極(未圖示)，並藉由線將各者的電極連接。利用線的連接可使用線接合裝置來實施。一實施形態中，自基板的表面至線的頂點3a為止的高度(圖中，參照符號h)可為0.5mm~1.5mm。例如，所述高度較佳為1mm左右。另外，於金線的情況下，線徑可為10μm~30μm的範圍。於面向功率半導體的用途而使用鋁線的情況下，鋁線的線徑可為80μm~600μm的範圍，有與金線的情況相比高度h亦變高的傾向。 Step (a): As shown in FIG. 3( a ), the substrate 1 and the semiconductor device 2 disposed on the substrate 1 are electrically connected by wires 3 . The so-called "electrical connection" refers to the Electrodes (not shown) are usually provided on the substrate 1 and the semiconductor device 2, respectively, and the electrodes are connected by wires. The connection using wire can be carried out using wire bonding means. In one embodiment, the height from the surface of the substrate to the vertex 3a of the line (in the figure, refer to symbol h) may be 0.5 mm to 1.5 mm. For example, the height is preferably about 1 mm. In addition, in the case of a gold wire, the wire diameter may be in the range of 10 μm to 30 μm. When an aluminum wire is used for power semiconductor applications, the wire diameter of the aluminum wire can be in the range of 80 μm to 600 μm, and the height h tends to be higher than that of the gold wire.

步驟(b)：如圖3(b)所示，對線的頂點3a的下部空間供給液狀密封材。液狀密封材的供給方法並無特別限定，可應用分配器方式、注模方式、印刷方式等。一實施形態中，較佳為應用分配器方式。其中，較佳為使用噴射分配器裝置自線的側部注入液狀密封材的方法。藉由使用噴射分配器裝置對線下部的空間注入液狀密封材，而容易將所述空間無間隙地填充。藉由使供給至所述空間的液狀密封材硬化，可形成第1密封層4a。液狀密封材的硬化可於步驟(c)中後述的絕緣性樹脂塗佈材的供給前實施，或者亦可於絕緣性樹脂塗佈材的供給後實施。例如，於液狀密封材為熱硬化性的情況下，較佳為於液狀密封材注入後，繼續使液狀密封材加熱硬化。加熱硬化時的溫度可根據所使用的液狀密封材的種類而適宜調整，但代表性地較佳為100℃~200℃的範圍。 Step (b): As shown in FIG.3(b), the liquid sealing material is supplied to the lower space of the vertex 3a of a line. The supply method of the liquid sealing material is not particularly limited, and a dispenser method, an injection molding method, a printing method, and the like can be applied. In one embodiment, a dispenser method is preferably used. Among them, a method of injecting the liquid sealing material from the side of the wire using a jet dispenser device is preferred. By injecting the liquid sealing material into the space below the wire using the jet distributor device, the space can be easily filled without gaps. The first sealing layer 4a can be formed by curing the liquid sealing material supplied to the space. The curing of the liquid sealing material may be performed before supply of the insulating resin coating material described later in the step (c), or may be performed after the supply of the insulating resin coating material. For example, when the liquid sealing material is thermosetting, it is preferable to continue heating and curing the liquid sealing material after the injection of the liquid sealing material. Although the temperature at the time of heat-hardening can be adjusted suitably according to the kind of liquid sealing material used, the range of 100 degreeC - 200 degreeC is typically preferable.

步驟(c)：如圖3(c)所示，經由線3而對第1密封層 4a的上部供給絕緣性樹脂塗佈材。步驟(b)中不實施液狀密封材的硬化的情況下，朝供給至所述空間中的液狀密封材的上方供給絕緣性樹脂塗佈材。絕緣性樹脂塗佈材的供給方法並無特別限定，可應用分配器方式、注模方式等。一實施形態中，較佳為應用分配器方式。絕緣性樹脂塗佈材較佳為被供給於包含液狀密封材的硬化物的第1密封層的上部。繼所述步驟(b)之後實施步驟(c)，藉此，不產生流掛等不良現象而於線上部將絕緣性樹脂塗佈材維持原樣，並藉由乾燥而可容易地形成第2密封層。 Step (c): As shown in FIG. 3( c ), through the line 3, the first sealing layer is The upper part of 4a is supplied with an insulating resin coating material. In the case where the curing of the liquid sealing material is not performed in the step (b), the insulating resin coating material is supplied above the liquid sealing material supplied into the space. The supply method of the insulating resin coating material is not particularly limited, and a dispenser method, an injection molding method, or the like can be applied. In one embodiment, a dispenser method is preferably used. The insulating resin coating material is preferably supplied to the upper part of the first sealing layer containing the cured product of the liquid sealing material. The step (c) is carried out after the step (b), whereby the insulating resin coating material is kept as it is on the upper part of the wire without causing problems such as sagging, and the second seal can be easily formed by drying Floor.

一實施形態中，就確保絕緣性的觀點而言，第2密封層的膜厚較佳為5μm以上，更佳為8μm以上，進而佳為10μm以上。另一方面，就薄型化的觀點而言，所述膜厚較佳為100μm以下，更佳為50μm以下，進而佳為30μm以下。一實施形態中，所述膜厚較佳為10μm~30μm的範圍。因此，較佳為以乾燥後的膜厚成為所述範圍內的方式調整絕緣性樹脂塗佈材的供給量。 In one embodiment, from the viewpoint of securing insulating properties, the film thickness of the second sealing layer is preferably 5 μm or more, more preferably 8 μm or more, and still more preferably 10 μm or more. On the other hand, from the viewpoint of thinning, the film thickness is preferably 100 μm or less, more preferably 50 μm or less, and still more preferably 30 μm or less. In one embodiment, the film thickness is preferably in the range of 10 μm to 30 μm. Therefore, it is preferable to adjust the supply amount of an insulating resin coating material so that the film thickness after drying may fall within the said range.

步驟(d)：如圖3(d)所示，以至少覆蓋第2密封層4b的方式形成樹脂密封構件。樹脂密封構件較佳為以包含第2密封層4b在內將半導體器件及基板的整個表面覆蓋的方式形成。根據本實施形態的製造方法，於樹脂密封構件形成之前，將線密封，因此不會產生線流動等不良現象。樹脂密封構件的形成方法並無特別限制，可應用本技術領域中眾所周知的技術。 Step (d): As shown in FIG. 3(d), a resin sealing member is formed so as to cover at least the second sealing layer 4b. The resin sealing member is preferably formed so as to cover the entire surface of the semiconductor device and the substrate including the second sealing layer 4b. According to the manufacturing method of this embodiment, since the wire is sealed before the resin sealing member is formed, problems such as wire flow do not occur. The method of forming the resin sealing member is not particularly limited, and a well-known technique in this technical field can be applied.

一實施形態中，樹脂密封構件的形成可藉由在具有規定形狀的模具內，使用之前所說明的包含環氧樹脂與酚樹脂的硬化性組 成物進行轉注成形(transfer molding)而實施。另外，樹脂密封構件的厚度雖無特別限定，但由於藉由第2密封層確保了絕緣性，因此亦可設計得薄。一實施形態中，樹脂密封構件形成後所獲得的半導體元件的膜厚較佳為可設為1.5mm以下，更佳為設為1.1mm以下。 In one embodiment, the resin sealing member can be formed by using, in a mold having a predetermined shape, a curable composition comprising an epoxy resin and a phenol resin as described above. The finished product is carried out by transfer molding. Moreover, although the thickness of a resin sealing member is not specifically limited, Since insulation is ensured by a 2nd sealing layer, it can also be designed to be thin. In one embodiment, the film thickness of the semiconductor element obtained after the resin sealing member is formed may preferably be 1.5 mm or less, and more preferably 1.1 mm or less.

一實施形態中，半導體元件的製造方法包括：藉由線將基板與配置於基板上的半導體器件電性連接的步驟；藉由對所述線的頂點的下部空間供給液狀密封材、繼而使液狀密封材硬化而形成第1密封層的步驟；以及藉由經由所述線對所述第1密封層的上部供給絕緣性樹脂塗佈材、繼而使其乾燥而形成第2密封層的步驟。於另一實施形態中，半導體元件的製造方法於所述實施形態的製造方法中，於形成第2密封層的步驟之後，進而包括以至少覆蓋第2密封層的方式形成樹脂密封構件的步驟。 In one embodiment, a method of manufacturing a semiconductor element includes the steps of: electrically connecting a substrate and a semiconductor device arranged on the substrate by a wire; A step of forming a first sealing layer by curing a liquid sealing material; and a step of forming a second sealing layer by supplying an insulating resin coating material to the upper portion of the first sealing layer through the wire, followed by drying . In another embodiment, the manufacturing method of a semiconductor element in the manufacturing method of the said embodiment further includes the process of forming a resin sealing member so that a 2nd sealing layer may be covered at least after the process of forming a 2nd sealing layer.

[實施例] [Example]

以下，按照實施例來說明本發明的實施形態，但本發明並不限定於以下實施例，關於施加有各種變形的實施形態，當然亦包括在內。 Hereinafter, embodiments of the present invention will be described based on examples, but the present invention is not limited to the following examples, and various modifications are also included as a matter of course.

1.液狀密封材的製備 1. Preparation of liquid sealing material

(製備例1) (Preparation Example 1)

調配以下所示的材料，並利用三根輥及真空擂潰機進行混煉分散，從而製備液狀密封材。 The materials shown below were prepared, kneaded and dispersed with three rolls and a vacuum crusher to prepare a liquid sealing material.

環氧樹脂1：對(2,3-環氧丙氧基)-N,N-雙(2,3-環氧丙基)苯胺 (艾迪科(ADEKA)股份有限公司製造的商品名「EP-3950S」、總氯量為1500ppm以下) 60份 Epoxy Resin 1: p-(2,3-glycidoxy)-N,N-bis(2,3-glycidoxy)aniline (trade name "EP-3950S" manufactured by ADEKA Co., Ltd., total chlorine content is 1500 ppm or less) 60 parts

環氧樹脂2：雙酚F型環氧樹脂(新日鐵住金化學股份有限公司製造的商品名「YDF-8170C」) 20份 Epoxy resin 2: bisphenol F type epoxy resin (trade name "YDF-8170C" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) 20 parts

環氧樹脂3：1,6-己二醇二縮水甘油醚(阪本藥品工業股份有限公司的商品名「SR-16HL」) 20份 Epoxy resin 3: 1,6-hexanediol diglycidyl ether (trade name "SR-16HL" of Sakamoto Pharmaceutical Co., Ltd.) 20 parts

硬化劑：二乙基甲苯二胺(三菱化學股份有限公司製造的商品名「jER固(cure)W」) 42份 Hardener: Diethyltoluenediamine (trade name "jER solid (cure) W" manufactured by Mitsubishi Chemical Corporation) 42 parts

離子捕捉劑：鉍系離子捕捉劑(東亞合成股份有限公司製造的商品名「IXE-500」) 3份 Ion scavenger: bismuth-based ion scavenger (trade name "IXE-500" manufactured by Toagosei Co., Ltd.) 3 parts

溶劑：丁基卡必醇乙酸酯 57份 Solvent: 57 parts of butyl carbitol acetate

無機填充材1：利用矽烷偶合劑進行了表面處理的球狀熔融二氧化矽(亞都瑪科技(Admatechs)股份有限公司製造的商品名「SE5050-SEJ」、體積平均粒徑1.5μm) 707份 Inorganic filler 1: 707 parts of spherical fused silica surface-treated with a silane coupling agent (trade name "SE5050-SEJ" manufactured by Admatechs Co., Ltd., volume average particle size 1.5 μm)

無機填充材2：利用矽烷偶合劑進行了表面處理的球狀熔融二氧化矽(亞都瑪科技(Admatechs)股份有限公司製造的商品名「SE2050-SEJ」、體積平均粒徑0.5μm) 235份 Inorganic filler 2: Spherical fused silica surface-treated with a silane coupling agent (trade name "SE2050-SEJ" manufactured by Admatechs Co., Ltd., volume average particle size 0.5 μm) 235 parts

對於以所述方式製備的液狀密封材，分別測定25℃、剪切速度10s-1下的黏度、與75℃、剪切速度5s-1下的黏度。另外，測定75℃、剪切速度50s-1下的黏度，求出75℃下的觸變係數。將該些結果示於以下。 For the liquid sealing material prepared in the above-described manner, the viscosity at 25°C and the shear rate of 10 s -1 and the viscosity at 75°C and the shear rate of 5 s -1 were measured, respectively. In addition, the viscosity at 75°C and a shear rate of 50 s −1 was measured, and the thixotropic coefficient at 75°C was obtained. These results are shown below.

25℃黏度：20(Pa．s)(剪切速度10s-1) Viscosity at 25℃: 20(Pa.s) (shear speed 10s -1 )

75℃黏度：2.0(Pa．s)(剪切速度5s-1) Viscosity at 75°C: 2.0 (Pa.s) (shear speed 5s -1 )

75℃下的觸變係數：1.7(剪切速度5s-1/50s-1的值) Thixotropic coefficient at 75°C: 1.7 (value of shear rate 5s -1 /50s -1 )

再者，25℃下的黏度測定是使用E型黏度計(東京計器股份有限公司製造的維斯柯尼(VISCONIC)EHD型)而實施。另外，75℃下的黏度測定是使用流變儀(TA儀器(TA Instruments)公司的商品名「AR2000」)而實施。 In addition, the viscosity measurement at 25 degreeC was implemented using the E-type viscometer (Visconi (VISCONIC) EHD type|mold by Tokyo Keiki Co., Ltd.). In addition, the viscosity measurement at 75 degreeC was implemented using a rheometer (trade name "AR2000" of TA Instruments).

另外，對所製備的液狀密封材的氯離子量(ppm)進行測定。關於測定，藉由離子層析法於121℃、20小時的條件下進行處理，並使用碳酸鈉溶液作為溶離液來進行測定。測定的結果為，液狀密封材中的氯離子量為10ppm。 Moreover, the chloride ion amount (ppm) of the prepared liquid sealing material was measured. The measurement was performed by ion chromatography under the conditions of 121° C. and 20 hours, and the measurement was performed using a sodium carbonate solution as an eluate. As a result of the measurement, the amount of chloride ions in the liquid sealing material was 10 ppm.

2.絕緣性樹脂塗佈材的製備 2. Preparation of insulating resin coating material

(製備例2) (Preparation Example 2)

<絕緣性樹脂塗佈材(P-1)的製備> <Preparation of insulating resin coating material (P-1)>

(1)耐熱性樹脂(B)的合成例 (1) Synthesis example of heat resistant resin (B)

於安裝有溫度計、攪拌機、氮氣導入管、帶油水分離機的冷卻管的5升的四口燒瓶中，於氮氣流下，放入650.90g(1.59莫耳)的2,2-雙[4-(4-胺基苯氧基)苯基]丙烷(2,2-bis[4-(4-aminophenoxy)phenyl]propane，以下設為BAPP)、及43.80g(0.18莫耳)的1,3-雙(3-胺基丙基)四甲基二矽氧烷(以下設為BY16-871(東麗道康寧(Toray Dow Corning)股份有限公司製造))，進而加入3609.86g的N-甲基-2-吡咯啶酮(N-methyl-2-pyrrolidone，以下設為NMP)並進行溶解。繼而， 一面將溶液冷卻為不超過20℃，一面加入384.36g(1.83莫耳)的偏苯三酸酐醯氯(trimellitic anhydride acid chloride，以下設為TAC)。 650.90 g (1.59 moles) of 2,2-bis[4-( 4-aminophenoxy)phenyl]propane (2,2-bis[4-(4-aminophenoxy)phenyl]propane, hereinafter referred to as BAPP), and 43.80 g (0.18 moles) of 1,3-bis (3-aminopropyl)tetramethyldisiloxane (hereinafter referred to as BY16-871 (manufactured by Toray Dow Corning Co., Ltd.)), and 3609.86 g of N-methyl-2- Pyrrolidone (N-methyl-2-pyrrolidone, hereinafter referred to as NMP) was dissolved. Then, While cooling the solution to not more than 20°C, 384.36 g (1.83 moles) of trimellitic anhydride acid chloride (hereinafter referred to as TAC) was added.

於室溫下攪拌1小時後，一面冷卻為不超過20℃，一面加入215.90g(2.14莫耳)的三乙胺(triethylamine，以下設為TEA)後，於室溫下使其反應1小時，從而製造聚醯胺酸清漆。對於所獲得的聚醯胺酸清漆，進而於180℃下進行6小時脫水反應，從而製造聚醯胺醯亞胺樹脂的清漆。對將所述聚醯胺醯亞胺樹脂的清漆注入於水中所得的沈澱物進行分離、粉碎及乾燥，而獲得聚醯胺醯亞胺樹脂粉末(PAI-1)。所獲得的聚醯胺醯亞胺樹脂(PAI-1)的Mw為77000。 After stirring at room temperature for 1 hour, 215.90 g (2.14 mol) of triethylamine (hereinafter referred to as TEA) was added while cooling to a temperature of not more than 20° C., and then allowed to react at room temperature for 1 hour, Thus, a polyamide varnish is produced. About the obtained polyamic acid varnish, the dehydration reaction was further performed at 180 degreeC for 6 hours, and the varnish of a polyamide imide resin was manufactured. The precipitate obtained by pouring the varnish of the polyamide imide resin into water was separated, pulverized, and dried to obtain a polyamide imide resin powder (PAI-1). The Mw of the obtained polyamideimide resin (PAI-1) was 77,000.

(2)耐熱性樹脂(C)的合成例 (2) Synthesis example of heat resistant resin (C)

於安裝有溫度計、攪拌機、氮氣導入管、帶油水分離機的冷卻管的1升的四口燒瓶中，於氮氣流下，放入69.72g(170.1毫莫耳)的BAPP、及4.69g(18.9毫莫耳)的BY16-871，進而加入693.52g的NMP並進行溶解。繼而，一面將溶液冷卻為不超過20℃，一面加入25.05g(119.0毫莫耳)的TAC、及25.47g(79.1毫莫耳)的3,4,3',4'-二苯甲酮四羧酸二酐(3,4,3',4'-benzophenone tetracarboxylic acid dianhydride，以下設為BTDA)。 In a 1-liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube with an oil-water separator, under nitrogen flow, 69.72 g (170.1 mmol) of BAPP and 4.69 g (18.9 mmol) were placed. Mol) BY16-871, and then 693.52 g of NMP was added and dissolved. Then, 25.05 g (119.0 mmol) of TAC and 25.47 g (79.1 mmol) of 3,4,3',4'-benzophenone tetra Carboxylic dianhydride (3,4,3',4'-benzophenone tetracarboxylic acid dianhydride, hereinafter referred to as BTDA).

於室溫下攪拌1小時後，一面冷卻為不超過20℃，一面加入14.42g(142.8毫莫耳)的TEA後，於室溫下使其反應1小時，從而製造聚醯胺酸清漆。對於所獲得的聚醯胺酸清漆，進而於180 ℃下進行6小時脫水反應，從而製造聚醯亞胺樹脂的清漆。對將所述聚醯亞胺樹脂的清漆注入於水中所得的沈澱物進行分離、粉碎及乾燥，而獲得聚醯亞胺樹脂粉末(PAIF-1)。所獲得的聚醯亞胺樹脂(PAIF-1)的Mw為42000。 After stirring at room temperature for 1 hour, 14.42 g (142.8 mmol) of TEA was added while cooling to 20°C or less, and the reaction was performed at room temperature for 1 hour to produce a polyamide varnish. For the obtained polyamide varnish, further at 180 A dehydration reaction was performed at °C for 6 hours to produce a varnish of a polyimide resin. The precipitate obtained by pouring the varnish of the polyimide resin into water was separated, pulverized, and dried to obtain a polyimide resin powder (PAIF-1). The Mw of the obtained polyimide resin (PAIF-1) was 42,000.

(3)絕緣性樹脂塗佈材的製備 (3) Preparation of insulating resin coating material

於安裝有溫度計、攪拌機、氮氣導入管及冷卻管的0.5升的四口燒瓶中，於氮氣流下，加入92.4g的作為第一極性溶媒(A1)的γ-丁內酯(γ-butyrolactone，以下設為γ-BL)、39.6g的作為第二極性溶媒(A2)的三乙二醇二甲醚(triethylene glycol dimethyl ether，以下設為DMTG)、30.8g的作為耐熱性樹脂(B)的之前所合成的聚醯胺醯亞胺樹脂粉末(PAI-1)、及13.2g的作為耐熱性樹脂(C)的之前所合成的聚醯亞胺樹脂粉末(PAIF-1)，一面攪拌一面升溫至180℃為止。於180℃下攪拌2小時後，使加熱停止，一面攪拌一面放置冷卻，於60℃下加入16.8g的γ-BL及7.2g的DMTG，攪拌1小時，冷卻後，獲得黃色組成物。填充於過濾器KST-47(愛多邦得科(Advantec)股份有限公司製造)中，並將矽酮橡膠製活塞***，以3.0kg/cm2的壓力進行加壓過濾，從而獲得絕緣性樹脂塗佈材(P-1)。 In a 0.5-liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube and a cooling tube, under a nitrogen stream, 92.4 g of γ-butyrolactone (γ-butyrolactone, the following) was added as the first polar solvent (A1). γ-BL), 39.6 g of triethylene glycol dimethyl ether (hereinafter referred to as DMTG) as the second polar solvent (A2), and 30.8 g of the heat-resistant resin (B) before The synthesized polyimide resin powder (PAI-1) and 13.2 g of the previously synthesized polyimide resin powder (PAIF-1) as the heat-resistant resin (C) were heated to 13.2 g while stirring. up to 180°C. After stirring at 180° C. for 2 hours, heating was stopped, and the mixture was left to cool while stirring. 16.8 g of γ-BL and 7.2 g of DMTG were added at 60° C., stirred for 1 hour, and cooled to obtain a yellow composition. A filter KST-47 (manufactured by Advantec Co., Ltd.) was filled, and a silicone rubber piston was inserted, and pressure filtration was performed at a pressure of 3.0 kg/cm 2 to obtain an insulating resin. Coating material (P-1).

(製備例3) (Preparation Example 3)

<包含無機填料的絕緣性樹脂塗佈材(P-2)的製備> <Preparation of Insulating Resin Coating Material (P-2) Containing Inorganic Filler>

與製備例2(1)同樣地，獲得PAI-1後，添加5wt%的日本艾羅西爾(AEROSIL)股份有限公司製造的艾羅西爾(AEROSIL) 200，從而製備比較例用的絕緣性樹脂塗佈材。 After obtaining PAI-1 in the same manner as in Preparation Example 2 (1), 5 wt % of AEROSIL (AEROSIL) manufactured by Japan Aerosil Co., Ltd. was added. 200 to prepare the insulating resin coating material for the comparative example.

具體而言，於安裝有溫度計、攪拌機、氮氣導入管及冷卻管的0.5升的四口燒瓶中，於氮氣流下，加入92.4g的作為第一極性溶媒(A1)的γ-BL，39.6g的作為第二極性溶媒(A2)的三乙二醇二甲醚(以下設為DMTG)、30.8g的作為耐熱性樹脂(B)的之前所合成的聚醯胺醯亞胺樹脂粉末(PAI-1)、及9.8g的艾羅西爾(AEROSIL)200，一面攪拌一面升溫至180℃為止。於180℃下攪拌2小時後，使加熱停止，一面攪拌一面放置冷卻，於60℃下加入16.8g的γ-BL及7.2g的DMTG，攪拌1小時，冷卻後，獲得黃色組成物。填充於過濾器KST-47(愛多邦得科(Advantec)股份有限公司製造)中，並將矽酮橡膠製活塞***，以3.0kg/cm2的壓力進行加壓過濾，從而獲得比較例用的絕緣性樹脂塗佈材(P-2)。 Specifically, 92.4 g of γ-BL as the first polar solvent (A1), 39.6 g of γ-BL and 39.6 g of Triethylene glycol dimethyl ether (hereinafter referred to as DMTG) as the second polar solvent (A2), 30.8 g of the previously synthesized polyimide resin powder (PAI-1) as the heat-resistant resin (B) ) and 9.8 g of AEROSIL 200, and the temperature was raised to 180°C while stirring. After stirring at 180° C. for 2 hours, heating was stopped, and the mixture was left to cool while stirring. 16.8 g of γ-BL and 7.2 g of DMTG were added at 60° C., stirred for 1 hour, and cooled to obtain a yellow composition. A filter KST-47 (manufactured by Advantec Co., Ltd.) was filled, a silicone rubber piston was inserted, and pressure filtration was performed at a pressure of 3.0 kg/cm 2 to obtain a comparative example. The insulating resin coating material (P-2).

3.半導體元件的製造 3. Manufacture of semiconductor components

(實施例1) (Example 1)

準備利用焊料將半導體器件安裝於玻璃環氧基板上，並利用金線將安裝於基板上的半導體器件與基板電性連接而成的結構體。對半導體器件的四邊形成4×20根(合計80根)金線接合。自基板至線頂點的高度為0.9mm。 A structure in which a semiconductor device is mounted on a glass epoxy substrate with solder, and the semiconductor device mounted on the substrate and the substrate are electrically connected with a gold wire is prepared. 4×20 (80 in total) gold wire bonds were formed on the four sides of the semiconductor device. The height from the substrate to the top of the line was 0.9 mm.

繼而，使用噴射分配器裝置(諾信先進技術(Nordson Advanced Technology)股份有限公司製造的裝置名「S2-910」)將製備例1中所獲得的液狀密封材供給於所述結構體的線的頂點的 下部空間。繼而，於175℃下對所供給的液狀密封材加熱2小時，藉此使其硬化，從而形成第1密封層(線密封層)。 Next, the liquid sealing material obtained in Preparation Example 1 was supplied to the line of the structure using a jet dispenser device (device name "S2-910" manufactured by Nordson Advanced Technology Co., Ltd.). the apex of lower space. Next, the supplied liquid sealing material was heated at 175° C. for 2 hours to be hardened, thereby forming a first sealing layer (line sealing layer).

使用分配器裝置(三英(SAN-EI TECH)股份有限公司製造的裝置名「SDP500」)將製備例2中所獲得的絕緣性樹脂塗佈材經由線供給於第1密封層的上方。繼而，於以100℃進行30分鐘、進而以200℃進行1小時的溫度條件下使所述塗佈材的塗膜乾燥，藉此形成膜厚為12μm的第2密封層(絕緣保護層)。 The insulating resin coating material obtained in Preparation Example 2 was supplied above the first sealing layer via a wire using a dispenser device (device name "SDP500" manufactured by SAN-EI TECH). Next, the coating film of the said coating material was dried under the temperature conditions of 100 degreeC for 30 minutes and 200 degreeC for 1 hour, and the 2nd sealing layer (insulation protective layer) with a film thickness of 12 micrometers was formed.

(比較例1) (Comparative Example 1)

與實施例1同樣地，準備藉由線將安裝於基板上的半導體器件電性連接而成的結構體。繼而，使用分配器裝置(三英(SAN-EI TECH)股份有限公司製造的裝置名「SDP500」)將製備例2中所獲得的絕緣性樹脂塗佈材僅供給於結構體的線上部。對於線下部而言，線成為障礙，未能順利地填充絕緣性樹脂塗佈材。繼而，於以100℃進行30分鐘、進而以200℃進行1小時的溫度條件下使塗膜乾燥，藉此形成密封層(絕緣保護層)。再者，對絕緣性樹脂塗佈材的供給量進行調整，以使得位於線上部的密封層的乾燥膜厚與實施例1相同而成為12μm。 As in Example 1, a structure in which semiconductor devices mounted on a substrate were electrically connected by wires was prepared. Next, the insulating resin coating material obtained in Preparation Example 2 was supplied only to the wire portion of the structure using a dispenser device (device name "SDP500" manufactured by SAN-EI TECH Co., Ltd.). In the lower part of the wire, the wire became an obstacle, and the insulating resin coating material could not be filled smoothly. Next, the coating film was dried under temperature conditions of 100° C. for 30 minutes and 200° C. for 1 hour to form a sealing layer (insulation protective layer). In addition, the supply amount of the insulating resin coating material was adjusted so that the dry film thickness of the sealing layer located in the line part might become 12 micrometers similarly to Example 1.

(比較例2) (Comparative Example 2)

與實施例1同樣地，準備藉由線將安裝於基板上的半導體器件電性連接而成的結構體。繼而，使用噴射分配器裝置(諾信先進技術(Nordson Advanced Technology)股份有限公司製造的裝置名「S2-910」)將製備例1中所獲得的液狀密封材供給於所述結構 體的線下部及上部。繼而，於以175℃進行2小時的溫度條件下使塗膜硬化，藉此形成密封層(線密封層)。再者，對液狀密封材的供給量進行調整，以使得位於線上部的密封層的膜厚與實施例1相同而成為12μm。 As in Example 1, a structure in which semiconductor devices mounted on a substrate were electrically connected by wires was prepared. Next, the liquid sealing material obtained in Preparation Example 1 was supplied to the structure using a jet dispenser device (device name "S2-910" manufactured by Nordson Advanced Technology Co., Ltd.). The lower and upper parts of the body line. Next, the coating film was hardened under a temperature condition of 175° C. for 2 hours to form a sealing layer (line sealing layer). In addition, the supply amount of the liquid sealing material was adjusted so that the film thickness of the sealing layer located in the line part might become 12 micrometers similarly to Example 1.

(比較例3) (Comparative Example 3)

與實施例1同樣地，準備藉由線將安裝於基板上的半導體器件電性連接而成的結構體。繼而，與實施例1同樣地，於所述結構體的線下部形成第1密封層後，將製備例3中所獲得的包含無機填料的絕緣性樹脂塗佈材經由線供給於所述第1密封層的上方。再者，對包含無機填料的絕緣性樹脂塗佈材的供給量進行調整，以使得位於線上部的密封層的乾燥膜厚與實施例1相同而成為12μm。 As in Example 1, a structure in which semiconductor devices mounted on a substrate were electrically connected by wires was prepared. Next, in the same manner as in Example 1, after forming the first sealing layer on the lower part of the wire of the structure, the insulating resin coating material containing the inorganic filler obtained in Preparation Example 3 was supplied to the first through the wire. above the sealing layer. In addition, the supply amount of the insulating resin coating material containing an inorganic filler was adjusted so that the dry film thickness of the sealing layer located in the upper part of a line might become 12 micrometers similarly to Example 1.

4.半導體元件的評價 4. Evaluation of semiconductor elements

<半導體元件的可靠性> <Reliability of semiconductor elements>

對於實施例1及比較例1~比較例3中所獲得的半導體元件，根據超音波顯微鏡測定來判斷針對線而言的密封層中的孔隙的有無，並評價元件的可靠性。 For the semiconductor elements obtained in Example 1 and Comparative Examples 1 to 3, the presence or absence of voids in the sealing layer for the wire was determined by ultrasonic microscope measurement, and the reliability of the element was evaluated.

超音波顯微鏡測定藉由使用索諾斯堪(SONOSCAN)公司製造的裝置名「D9000」而實施。於藉由超音波顯微鏡測定未能確認到半導體元件中的孔隙的存在的情況下，判斷為可靠性良好。另一方面，於藉由超音波顯微鏡測定可確認到孔隙的存在的情況下，判斷為可靠性不良。將結果示於表1。 The ultrasonic microscope measurement was performed by using the device name "D9000" manufactured by SONOSCAN. When the presence of voids in the semiconductor element was not confirmed by the ultrasonic microscope measurement, it was judged that the reliability was good. On the other hand, when the existence of voids was confirmed by ultrasonic microscope measurement, it was judged that the reliability was poor. The results are shown in Table 1.

<絕緣破壞電壓> <Insulation breakdown voltage>

對於實施例1及比較例1~比較例3中所獲得的半導體元件，為了對形成於線上部的密封層的絕緣破壞電壓進行評價，而以如下方式製作測定用樣品。 For the semiconductor elements obtained in Example 1 and Comparative Examples 1 to 3, in order to evaluate the dielectric breakdown voltage of the sealing layer formed on the wire portion, samples for measurement were prepared as follows.

作為與實施例1(比較例1)對應的測定用樣品1，利用輔料器將製備例2中所得的絕緣性樹脂塗佈材P-1塗佈於鋁基板上。繼而，於100℃下於烘箱中加熱30分鐘，進而於200℃下於烘箱中加熱1小時，藉此獲得膜厚10μm的乾燥塗膜。 As the sample 1 for measurement corresponding to Example 1 (Comparative Example 1), the insulating resin coating material P-1 obtained in Preparation Example 2 was applied on an aluminum substrate using an auxiliary device. Then, it heated in an oven at 100 degreeC for 30 minutes, and also heated in an oven at 200 degreeC for 1 hour, thereby obtaining the dry coating film with a film thickness of 10 micrometers.

作為針對比較例2而言的測定樣品2，利用輔料器將製備例1中所得的液狀密封材塗佈於鋁基板上。繼而，於175℃、2小時的條件下使塗膜加熱硬化，藉此獲得膜厚10μm的硬化膜。 As the measurement sample 2 with respect to the comparative example 2, the liquid sealing material obtained in the preparation example 1 was apply|coated on the aluminum substrate using the applicator. Next, the coating film was heat-hardened on the conditions of 175 degreeC and 2 hours, and the cured film with a film thickness of 10 micrometers was obtained.

作為針對比較例3而言的測定樣品3，利用輔料器將製備例3中所得的包含無機填料的絕緣性樹脂塗佈材P-2塗佈於鋁基板上。繼而，於100℃下於烘箱中加熱30分鐘，進而於200℃下於烘箱中加熱1小時，藉此獲得膜厚10μm的乾燥塗膜。 As a measurement sample 3 with respect to Comparative Example 3, the insulating resin coating material P-2 containing an inorganic filler obtained in Preparation Example 3 was applied on an aluminum substrate using an auxiliary device. Then, it heated in an oven at 100 degreeC for 30 minutes, and also heated in an oven at 200 degreeC for 1 hour, thereby obtaining the dry coating film with a film thickness of 10 micrometers.

將以所述方式製作的測定用樣品1~測定用樣品3分別利用一對電極夾持，並測定絕緣破壞電壓值。關於測定，以日本工業標準(Japanese Industrial Standards，JIS)C2110為參考，於油中，於將升壓速度設為0.5kV/秒、將測定溫度設為室溫、將電極形狀設為Φ20mm的球的條件下實施。將結果示於表1。 The measurement sample 1 to the measurement sample 3 produced as described above were respectively sandwiched by a pair of electrodes, and the dielectric breakdown voltage value was measured. Regarding the measurement, with reference to Japanese Industrial Standards (JIS) C2110, in oil, the pressure increase rate was set to 0.5 kV/sec, the measurement temperature was set to room temperature, and the electrode shape was set to a ball of Φ20 mm. conditions are implemented. The results are shown in Table 1.

<ESD耐性> <ESD resistance>

對於實施例1及比較例1~比較例3中所得的半導體元件， 實際上代替測定ESD耐性而根據另行測定的乾燥塗膜(硬化膜)的絕緣破壞電壓的值來評價ESD耐性。例如，之前所製作的測定樣品1的絕緣破壞電壓為230kV/mm，其與230V/μm為相同含義。因此，只要藉由成膜所得的密封層(膜)的膜厚為10μm，則密封層(膜)具有2300V(2.3kV)的絕緣性。通常，只要密封層(膜)可對超過2kV的電壓保持絕緣性，則於半導體元件中能夠獲得充分的ESD耐性。 For the semiconductor elements obtained in Example 1 and Comparative Examples 1 to 3, Actually, instead of measuring the ESD resistance, the ESD resistance was evaluated based on the value of the dielectric breakdown voltage of the dry coating film (cured film) measured separately. For example, the dielectric breakdown voltage of the previously prepared measurement sample 1 is 230 kV/mm, which means the same as 230 V/μm. Therefore, as long as the film thickness of the sealing layer (film) obtained by film formation is 10 μm, the sealing layer (film) has an insulating property of 2300 V (2.3 kV). In general, as long as the sealing layer (film) can maintain insulating properties against a voltage exceeding 2 kV, sufficient ESD resistance can be obtained in a semiconductor element.

一般而言，藉由增大膜厚而提高絕緣性，藉此可提高ESD耐性。例如，於以獲得100μm以上的膜厚的方式塗佈材料的情況下，容易保證絕緣性。但難以以原本獲得100μm的膜厚的方式均勻地塗佈絕緣性塗佈材。另外，就與要求薄型的半導體元件的市場趨勢逆行的方面而言，亦欠佳。因此，如以下般，以2kV為基準值，根據由膜厚10μm的測定樣品1~測定樣品3的絕緣破壞電壓的測定值所算出的絕緣性來評價ESD耐性。將結果示於表1。(ESD的評價基準) In general, by increasing the film thickness, the insulating properties can be improved, thereby improving the ESD resistance. For example, when the material is applied so as to obtain a film thickness of 100 μm or more, it is easy to ensure insulating properties. However, it is difficult to apply the insulating coating material uniformly so as to obtain a film thickness of 100 μm originally. In addition, it is also unfavorable in terms of going against the market trend that requires thin semiconductor elements. Therefore, the ESD resistance was evaluated based on the insulating properties calculated from the measured values of the dielectric breakdown voltages of the measurement samples 1 to 3 with a film thickness of 10 μm using 2 kV as a reference value as follows. The results are shown in Table 1. (Evaluation Criteria for ESD)

良好：絕緣性為2kV以上。 Good: The insulation is 2kV or more.

不良：絕緣性未滿2kV。 Defect: Insulation is less than 2kV.

[表1]

Figure 107127711-A0305-02-0062-35
[Table 1]
Figure 107127711-A0305-02-0062-35

(註解) (annotation)

實施例1及比較例1的絕緣破壞電壓及ESD耐性與針對測定樣品1而言的測定值及評價結果對應。比較例2及比較例3的絕緣破壞電壓及ESD耐性的評價與針對測定樣品2及測定樣品3而言的測定值及評價結果對應。 The dielectric breakdown voltage and ESD resistance of Example 1 and Comparative Example 1 correspond to the measured values and evaluation results of the measurement sample 1. The evaluation of the dielectric breakdown voltage and the ESD resistance of the comparative example 2 and the comparative example 3 corresponds to the measurement value and the evaluation result with respect to the measurement sample 2 and the measurement sample 3.

ESD耐性中的絕緣性為根據膜厚10μm的測定樣品1~測定樣品3的絕緣破壞電壓的測定值而算出的值。 The insulating properties in the ESD resistance are values calculated from the measured values of the dielectric breakdown voltages of the measurement samples 1 to 3 having a film thickness of 10 μm.

由實施例1與比較例1~比較例3的對比而明確到，根據本發明的實施形態(實施例1)，孔隙的產生得到抑制，且獲得高的絕緣破壞電壓。因此，根據本發明，可提供一種絕緣性、ESD耐性優異、且可靠性優異的薄型的半導體元件。 As is clear from the comparison of Example 1 with Comparative Examples 1 to 3, according to the embodiment of the present invention (Example 1), generation of voids is suppressed and a high dielectric breakdown voltage is obtained. Therefore, according to the present invention, it is possible to provide a thin semiconductor element which is excellent in insulation and ESD resistance, and which is excellent in reliability.

1:基板 1: Substrate

2:半導體器件 2: Semiconductor devices

3:線 3: Line

3a:線頂點(頂點) 3a: line vertex (vertex)

4a:第1密封層 4a: 1st sealing layer

4b:第2密封層 4b: 2nd sealing layer

5:樹脂密封構件 5: Resin sealing member

h:自基板起的線高度(高度) h: Line height from the substrate (height)

Claims (20)

一種半導體元件，包括：基板；配置於所述基板上的半導體器件；將所述基板與所述半導體器件電性連接的線；將所述線的頂點的下部空間密封的第1密封層；以及經由所述線設置於所述第1密封層的上部的第2密封層，且所述第1密封層包含液狀密封材的硬化膜，所述第2密封層包含絕緣性樹脂塗佈材的乾燥塗膜，所述絕緣性樹脂塗佈材的25℃下的觸變係數為2.0~10.0。 A semiconductor element comprising: a substrate; a semiconductor device disposed on the substrate; a wire electrically connecting the substrate and the semiconductor device; a first sealing layer for sealing a lower space at an apex of the wire; and A second sealing layer provided on the upper part of the first sealing layer via the wire, the first sealing layer including a cured film of a liquid sealing material, and the second sealing layer including an insulating resin coating material The coating film is dried, and the thixotropic coefficient at 25° C. of the insulating resin coating material is 2.0 to 10.0. 一種半導體元件，包括：基板；配置於所述基板上的半導體器件；將所述基板與所述半導體器件電性連接的線；將所述線的頂點的下部空間密封的第1密封層；以及經由所述線設置於所述第1密封層的上部的第2密封層，且所述第1密封層包含液狀密封材的硬化膜，所述第2密封層包含絕緣性樹脂塗佈材的乾燥塗膜，所述絕緣性樹脂塗佈材包含平均粒徑0.1μm~5.0μm的樹脂填料。 A semiconductor element comprising: a substrate; a semiconductor device disposed on the substrate; a wire electrically connecting the substrate and the semiconductor device; a first sealing layer for sealing a lower space at an apex of the wire; and A second sealing layer provided on the upper part of the first sealing layer via the wire, the first sealing layer including a cured film of a liquid sealing material, and the second sealing layer including an insulating resin coating material The coating film is dried, and the insulating resin coating material contains a resin filler with an average particle diameter of 0.1 μm to 5.0 μm. 如申請專利範圍第1項或第2項所述的半導體元件，其進而包括以至少覆蓋所述第2密封層的方式設置的樹脂密封構件。 The semiconductor element according to claim 1 or claim 2, further comprising a resin sealing member provided so as to cover at least the second sealing layer. 如申請專利範圍第1項或第2項所述的半導體元件，其中，所述絕緣性樹脂塗佈材的乾燥塗膜的絕緣破壞電壓為150kV/mm以上。 The semiconductor element according to claim 1 or claim 2, wherein the dielectric breakdown voltage of the dry coating film of the insulating resin coating material is 150 kV/mm or more. 如申請專利範圍第1項或第2項所述的半導體元件， 其中，所述絕緣性樹脂塗佈材的25℃下的黏度為30Pa．s~500Pa．s。 According to the semiconductor device described in item 1 or item 2 of the scope of the application, Wherein, the viscosity of the insulating resin coating material at 25 ℃ is 30Pa. s~500Pa. s. 如申請專利範圍第1項或第2項所述的半導體元件，其中，所述絕緣性樹脂塗佈材包含選自由聚醯胺、聚醯胺醯亞胺、及聚醯亞胺所組成的群組中的至少一種絕緣性樹脂。 The semiconductor device according to claim 1 or claim 2, wherein the insulating resin coating material comprises a group selected from the group consisting of polyamide, polyamide imide, and polyimide At least one insulating resin from the group. 如申請專利範圍第1項或第2項所述的半導體元件，其中，所述第2密封層的膜厚為100μm以下。 The semiconductor element according to claim 1 or claim 2, wherein the film thickness of the second sealing layer is 100 μm or less. 如申請專利範圍第1項或第2項所述的半導體元件，其中，所述第2密封層的膜厚為50μm以下。 The semiconductor element according to claim 1 or claim 2, wherein the film thickness of the second sealing layer is 50 μm or less. 如申請專利範圍第6項所述的半導體元件，其中，所述絕緣性樹脂的Tg為150℃以上。 The semiconductor element according to claim 6, wherein Tg of the insulating resin is 150° C. or higher. 如申請專利範圍第1項或第2項所述的半導體元件，其中，所述液狀密封材包含熱硬化性樹脂成分與無機填充劑，且當將於75℃、剪切速度5s-1的條件下所測定的黏度(Pa．s)設為黏度A，並將於75℃、剪切速度50s-1的條件下所測定的黏度(Pa．s)設為黏度B時，以黏度A/黏度B的值獲得的75℃下的觸變係數為0.1~2.5。 The semiconductor element according to claim 1 or claim 2, wherein the liquid sealing material contains a thermosetting resin component and an inorganic filler, and is heated to a temperature of 75° C. and a shear rate of 5 s −1 When the viscosity (Pa.s) measured under the conditions is defined as viscosity A, and the viscosity (Pa.s) measured under the conditions of 75°C and shear rate of 50s -1 is defined as viscosity B, the viscosity A/ The thixotropic coefficient at 75°C obtained from the value of viscosity B is 0.1 to 2.5. 如申請專利範圍第1項或第2項所述的半導體元件，其中，所述液狀密封材中的氯離子量為100ppm以下。 The semiconductor element according to claim 1 or claim 2, wherein the amount of chloride ions in the liquid sealing material is 100 ppm or less. 如申請專利範圍第10項所述的半導體元件，其中，所述液狀密封材中的所述無機填充劑的最大粒徑為75μm以下。 The semiconductor element according to claim 10, wherein the inorganic filler in the liquid sealing material has a maximum particle size of 75 μm or less. 如申請專利範圍第1項或第2項所述的半導體元件， 其中，所述液狀密封材的於75℃、剪切速度5s-1的條件下所測定的黏度為3.0Pa．s以下。 The semiconductor element according to claim 1 or claim 2, wherein the viscosity of the liquid sealing material measured under the conditions of 75° C. and a shear rate of 5s −1 is 3.0Pa. s or less. 如申請專利範圍第1項或第2項所述的半導體元件，其中，所述液狀密封材的於25℃、剪切速度10s-1的條件下所測定的黏度為30Pa．s以下。 The semiconductor element according to claim 1 or claim 2, wherein the viscosity of the liquid sealing material measured under the conditions of 25° C. and a shear rate of 10s −1 is 30Pa. s or less. 如申請專利範圍第10項所述的半導體元件，其中，以所述液狀密封材的總質量為基準，所述無機填充劑的含量為50質量%以上。 The semiconductor element according to claim 10, wherein the content of the inorganic filler is 50% by mass or more based on the total mass of the liquid sealing material. 如申請專利範圍第10項所述的半導體元件，其中，所述液狀密封材中的所述熱硬化性樹脂成分包含芳香族環氧樹脂與脂肪族環氧樹脂。 The semiconductor element according to claim 10, wherein the thermosetting resin component in the liquid sealing material contains an aromatic epoxy resin and an aliphatic epoxy resin. 如申請專利範圍第16項所述的半導體元件，其中，所述芳香族環氧樹脂包含選自由液狀的雙酚型環氧樹脂及液狀的縮水甘油胺型環氧樹脂所組成的群組中的至少一種，所述脂肪族環氧樹脂包含線狀脂肪族環氧樹脂。 The semiconductor device according to claim 16, wherein the aromatic epoxy resin is selected from the group consisting of a liquid bisphenol-type epoxy resin and a liquid glycidylamine-type epoxy resin At least one of the aliphatic epoxy resins includes linear aliphatic epoxy resins. 如申請專利範圍第1項或第2項所述的半導體元件，其被用於指紋認證感測器中。 The semiconductor device according to claim 1 or claim 2, which is used in a fingerprint authentication sensor. 一種半導體元件的製造方法，其為製造如下的半導體元件的方法，所述半導體元件包括：基板；配置於所述基板上的半導體器件；將所述基板與所述半導體器件電性連接的線；將所述線的頂點的下部空間密封的第1密封層；以及經由所述線設置於所述第1密封層的上部的第2密封層，且所述半導體元件的製 造方法包括：藉由所述線將所述基板與配置於所述基板上的所述半導體器件電性連接的步驟；對所述線的頂點的下部空間供給液狀密封材並形成第1密封層的步驟；以及經由所述線對所述第1密封層的上部供給絕緣性樹脂塗佈材並形成第2密封層的步驟，所述絕緣性樹脂塗佈材的25℃下的觸變係數為2.0~10.0。 A method of manufacturing a semiconductor element, which is a method of manufacturing a semiconductor element comprising: a substrate; a semiconductor device arranged on the substrate; a wire electrically connecting the substrate and the semiconductor device; a first sealing layer for sealing the lower space at the apex of the line; and a second sealing layer provided on the upper part of the first sealing layer through the line, and the semiconductor element is manufactured The manufacturing method includes the steps of electrically connecting the substrate and the semiconductor device arranged on the substrate through the wire; supplying a liquid sealing material to the space below the apex of the wire to form a first seal layer; and a step of supplying an insulating resin coating material to the upper part of the first sealing layer through the wire to form a second sealing layer, the thixotropic coefficient of the insulating resin coating material at 25°C is 2.0~10.0. 一種半導體元件的製造方法，其為製造如下的半導體元件的方法，所述半導體元件包括：基板；配置於所述基板上的半導體器件；將所述基板與所述半導體器件電性連接的線；將所述線的頂點的下部空間密封的第1密封層；以及經由所述線設置於所述第1密封層的上部的第2密封層，且所述半導體元件的製造方法包括：藉由所述線將所述基板與配置於所述基板上的所述半導體器件電性連接的步驟；對所述線的頂點的下部空間供給液狀密封材並形成第1密封層的步驟；以及經由所述線對所述第1密封層的上部供給絕緣性樹脂塗佈材並形成第2密封層的步驟，所述絕緣性樹脂塗佈材包含平均粒徑0.1μm~5.0μm的樹脂填料。 A method of manufacturing a semiconductor element, which is a method of manufacturing a semiconductor element comprising: a substrate; a semiconductor device arranged on the substrate; a wire electrically connecting the substrate and the semiconductor device; a first sealing layer for sealing the lower space of the vertex of the wire; and a second sealing layer provided on the upper part of the first sealing layer through the wire, and the manufacturing method of the semiconductor element includes: a step of electrically connecting the substrate and the semiconductor device arranged on the substrate by the wire; a step of supplying a liquid sealing material to a space below a vertex of the wire to form a first sealing layer; and the step of forming a first sealing layer through the wire The wire supplies an insulating resin coating material containing a resin filler having an average particle diameter of 0.1 μm to 5.0 μm to the upper portion of the first sealing layer to form a second sealing layer.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10261741A (en) * 1997-03-19 1998-09-29 Oki Electric Ind Co Ltd Semiconductor device and manufacture of semiconductor device
WO2014128899A1 (en) * 2013-02-22 2014-08-28 株式会社 日立製作所 Resin-sealed electronic control device
US20160372339A1 (en) * 2013-01-30 2016-12-22 Freescale Semiconductor, Inc. Semiconducitive catechol group encapsulant adhesion promoter for a packaged electronic device
US20170141020A1 (en) * 2015-11-18 2017-05-18 Invensas Corporation Stiffened wires for offset bva

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2697215B2 (en) * 1988-12-29 1998-01-14 日立化成工業株式会社 Heat resistant resin paste and IC using the same
US5300459A (en) * 1989-12-28 1994-04-05 Sanken Electric Co., Ltd. Method for reducing thermal stress in an encapsulated integrated circuit package
JPH0574831A (en) * 1991-09-11 1993-03-26 Nec Corp Semiconductor device
JP3729225B2 (en) * 1996-08-29 2005-12-21 信越化学工業株式会社 Semiconductor device
KR100575086B1 (en) * 2004-11-11 2006-05-03 삼성전자주식회사 Semiconductor package with conductive molding compound and manufacturing method thereof
JP4939184B2 (en) * 2005-12-15 2012-05-23 キヤノン株式会社 Method for manufacturing liquid discharge head
JP5586185B2 (en) * 2009-08-06 2014-09-10 パナソニック株式会社 Semiconductor device
WO2013008437A1 (en) * 2011-07-08 2013-01-17 三井化学株式会社 Polyimide resin composition and laminate including same
TW201335261A (en) * 2012-01-17 2013-09-01 Hitachi Chemical Co Ltd Resin paste and method for fabricating photovoltaic cell
JP6710065B2 (en) 2016-03-03 2020-06-17 大阪瓦斯株式会社 Pipe insertion tool
JP6292334B1 (en) * 2017-03-31 2018-03-14 日立化成株式会社 Electronic circuit protective material, electronic circuit protective material sealing material, sealing method, and semiconductor device manufacturing method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10261741A (en) * 1997-03-19 1998-09-29 Oki Electric Ind Co Ltd Semiconductor device and manufacture of semiconductor device
US20160372339A1 (en) * 2013-01-30 2016-12-22 Freescale Semiconductor, Inc. Semiconducitive catechol group encapsulant adhesion promoter for a packaged electronic device
WO2014128899A1 (en) * 2013-02-22 2014-08-28 株式会社 日立製作所 Resin-sealed electronic control device
US20170141020A1 (en) * 2015-11-18 2017-05-18 Invensas Corporation Stiffened wires for offset bva

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