TW201631674A - Conductive film-like adhesive, dicing tape attached with film-like adhesive, and manufacturing method of semiconductor device - Google Patents

Conductive film-like adhesive, dicing tape attached with film-like adhesive, and manufacturing method of semiconductor device Download PDF

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TW201631674A
TW201631674A TW104138997A TW104138997A TW201631674A TW 201631674 A TW201631674 A TW 201631674A TW 104138997 A TW104138997 A TW 104138997A TW 104138997 A TW104138997 A TW 104138997A TW 201631674 A TW201631674 A TW 201631674A
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adhesive
film
resin
wafer
conductive film
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TW104138997A
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TWI714540B (en
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Yuki Sugo
Yuta Kimura
Mitsuaki Fusumada
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Nitto Denko Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
    • H01L2224/45099—Material
    • H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/45144—Gold (Au) as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73251—Location after the connecting process on different surfaces
    • H01L2224/73265—Layer and wire connectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation

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  • Chemical & Material Sciences (AREA)
  • Adhesive Tapes (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Dicing (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Conductive Materials (AREA)
  • Dispersion Chemistry (AREA)
  • Non-Insulated Conductors (AREA)
  • Die Bonding (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)

Abstract

The present invention provides a conductive film-like adhesive with better heat-dissipation after hardening, and dicing tape attached with film-like adhesive. The present invention relates to a conductive film-like adhesive, which is heated and hardened to obtain a hardened object. The ratio of first thermal conductivity of the hardened object to the second thermal conductivity before hardening (the first thermal conductivity/ the second thermal conductivity) is more than 2.0. (claim 2) The first thermal conductivity is more than 1.7W/m*K. (claim 3) The conductive film-like adhesive contains conductive particles, said conductive particles contain sheet-like metal particles and sintering metal particles which, at least one portion of them, will be sintered at 200 DEG C.

Description

導電性膜狀接著劑、附有膜狀接著劑之切晶帶及半導體裝置之製造方法 Conductive film-like adhesive, etched tape with film-like adhesive, and method of manufacturing semiconductor device

本發明係關於一種導電性膜狀接著劑、附有膜狀接著劑之切晶帶及半導體裝置之製造方法。 The present invention relates to a conductive film-like adhesive, a dicing tape with a film-like adhesive, and a method of manufacturing a semiconductor device.

於半導體裝置之製造中，將半導體元件接著於金屬引線框架等被接著體之方法(所謂之晶片接著法)自以往之金-矽共晶開始逐漸過渡至利用焊料、樹脂糊之方法。現在，有時使用導電性之樹脂糊。 In the manufacture of a semiconductor device, a method in which a semiconductor element is subsequently bonded to a substrate such as a metal lead frame (so-called wafer bonding method) is gradually transitioned from a conventional gold-germanium eutectic to a method using solder or a resin paste. Nowadays, a conductive resin paste is sometimes used.

然而，於使用樹脂糊之方法中，存在孔隙導致導電性下降、或樹脂糊之厚度不均、或樹脂糊溢出導致焊盤被污染之問題。為了解決該等問題，有時使用含有聚醯亞胺樹脂之膜狀接著劑代替樹脂糊(例如，參見專利文獻1)。 However, in the method of using a resin paste, there is a problem that pores cause a decrease in conductivity, or a thickness of a resin paste is uneven, or a resin paste overflows to cause contamination of a pad. In order to solve such problems, a film-like adhesive containing a polyimide resin is sometimes used instead of the resin paste (for example, see Patent Document 1).

亦已知包含丙烯酸系樹脂之膜狀接著劑。例如，於專利文獻2中記載有藉由使用玻璃轉移溫度-10℃~50℃之丙烯酸共聚物而提高可撓性、降低引線框架等之熱損傷的技術。 A film-like adhesive containing an acrylic resin is also known. For example, Patent Document 2 describes a technique for improving flexibility and reducing thermal damage of a lead frame by using an acrylic copolymer having a glass transition temperature of -10 ° C to 50 ° C.

近年來，進行電力之控制及供給之功率半導體裝置正明顯普及。功率半導體裝置中始終有電流流通，因此發熱量大。因此，期望於功率半導體裝置中使用之導電性接著劑具有高散熱性及低電阻率。 In recent years, power semiconductor devices that control and supply power have become widespread. Since the current flows in the power semiconductor device, the amount of heat generation is large. Therefore, it is desirable that the conductive adhesive used in the power semiconductor device has high heat dissipation and low resistivity.

關於使用膜狀接著劑之晶片接著法，已知包括如圖10所示將具備膜狀接著劑503及半導體晶片505之晶片接著用晶片541壓接至約100℃~約150℃之被接著體506之步驟的方法。 Regarding the wafer bonding method using a film-like adhesive, it is known to include a wafer having a film-like adhesive 503 and a semiconductor wafer 505, followed by crimping the wafer 541 to a bonding body of about 100 ° C to about 150 ° C as shown in FIG. The method of step 506.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利特開平6-145639號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 6-145639

[專利文獻2]日本專利4137827號公報 [Patent Document 2] Japanese Patent No. 4137827

然而，本發明人進行了深入研究，結果發現，若膜狀接著劑503之散熱性高，則有時難以使膜狀接著劑503軟化至能夠接著於被接著體506之程度。 However, as a result of intensive studies, the present inventors have found that if the heat dissipation property of the film-like adhesive 503 is high, it may be difficult to soften the film-like adhesive 503 to the extent that it can be adhered to the adherend 506.

本發明之目的在於解決上述課題，提供硬化後散熱性高於硬化前散熱性之導電性膜狀接著劑及附有膜狀接著劑之切晶帶。 An object of the present invention is to solve the above problems and to provide a conductive film-like adhesive agent having heat dissipation properties after curing which is higher than heat dissipation before curing and a dicing tape having a film-like adhesive.

本發明係關於第1熱導率相對於第2熱導率之比之值(第1熱導率/第2熱導率)為2.0以上之導電性膜狀接著劑。第1熱導率為藉由加熱使本發明之導電性膜狀接著劑硬化而得到之硬化物之熱導率。第2熱導率為加熱前之熱導率。 The present invention relates to a conductive film-like adhesive in which the ratio of the first thermal conductivity to the second thermal conductivity (the first thermal conductivity / the second thermal conductivity) is 2.0 or more. The first thermal conductivity is a thermal conductivity of the cured product obtained by curing the conductive film-like adhesive of the present invention by heating. The second thermal conductivity is the thermal conductivity before heating.

第1熱導率較佳為1.7W/m‧K以上。 The first thermal conductivity is preferably 1.7 W/m‧K or more.

本發明之導電性膜狀接著劑較佳為包含導電性粒子。導電性粒子較佳為包含薄片狀金屬粒子及於200℃至少一部分會燒結之燒結性金屬粒子。因此，藉由使本發明之膜狀接著劑硬化，能夠使熱傳導路徑變寬，能夠提高散熱性。導電性粒子100重量%中之燒結性金屬粒子之含量較佳為5重量%~50重量%。 The conductive film-like adhesive of the present invention preferably contains conductive particles. The conductive particles preferably include flaky metal particles and sinter metal particles which are sintered at least at 200 ° C. Therefore, by curing the film-like adhesive of the present invention, the heat conduction path can be widened, and heat dissipation can be improved. The content of the sinter metal particles in 100% by weight of the conductive particles is preferably 5% by weight to 50% by weight.

本發明之導電性膜狀接著劑包含樹脂成分。樹脂成分較佳為包含熱塑性樹脂、熱硬化性樹脂。本發明之導電性膜狀接著劑較佳為進而包含硬化劑。 The conductive film-like adhesive of the present invention contains a resin component. The resin component preferably contains a thermoplastic resin or a thermosetting resin. The conductive film-like adhesive of the present invention preferably further contains a curing agent.

本發明之導電性膜狀接著劑之用途較佳為晶片接著用途。 The use of the conductive film-like adhesive of the present invention is preferably a wafer for subsequent use.

本發明亦關於具備切晶帶及配置於切晶帶上之導電性膜狀接著劑的附有膜狀接著劑之切晶帶。切晶帶具備基材及配置於基材上之黏著劑層。 The present invention also relates to a dicing tape having a film-like adhesive provided with a dicing tape and a conductive film-like adhesive disposed on the dicing tape. The dicing tape has a substrate and an adhesive layer disposed on the substrate.

本發明又關於半導體裝置之製造方法，該方法包括如下步驟：將具備導電性膜狀接著劑及配置於導電性膜狀接著劑上之半導體晶片的晶片接著用晶片壓接於被接著體。 Further, the present invention relates to a method of manufacturing a semiconductor device, which comprises the step of pressure-bonding a wafer including a conductive film-like adhesive and a semiconductor wafer disposed on a conductive film-like adhesive to a member to be bonded.

1‧‧‧切晶帶 1‧‧‧Cutting Tape

3‧‧‧膜狀接著劑 3‧‧‧membranous adhesive

3a 3a

3b 3b

4‧‧‧半導體晶圓 4‧‧‧Semiconductor wafer

5‧‧‧半導體晶片 5‧‧‧Semiconductor wafer

6‧‧‧被接著體 6‧‧‧Exposed body

7‧‧‧接合線 7‧‧‧bonding line

8‧‧‧密封樹脂 8‧‧‧ Sealing resin

10‧‧‧附有膜狀接著劑之切晶帶 10‧‧‧Cutting tape with film-like adhesive

11‧‧‧基材 11‧‧‧Substrate

12‧‧‧黏著劑層 12‧‧‧Adhesive layer

12a‧‧‧黏著劑層12之工件貼附部分所對應之部分 12a‧‧‧Parts corresponding to the attachment part of the workpiece of the adhesive layer 12

12b‧‧‧黏著劑層12之其他部分 12b‧‧‧Other parts of the adhesive layer 12

41‧‧‧晶片接著用晶片 41‧‧‧ wafer followed by wafer

61‧‧‧附有半導體晶片之被接著體 61‧‧‧ Attached body with semiconductor wafer

100‧‧‧評價基板 100‧‧‧ Evaluation substrate

101‧‧‧基板 101‧‧‧Substrate

102a‧‧‧銅佈線 102a‧‧‧ copper wiring

102b‧‧‧銅佈線 102b‧‧‧ copper wiring

102c‧‧‧銅佈線 102c‧‧‧ copper wiring

102d‧‧‧銅佈線 102d‧‧‧ copper wiring

200‧‧‧試驗膜 200‧‧‧ test film

300‧‧‧試驗基板 300‧‧‧Test substrate

503‧‧‧膜狀接著劑 503‧‧‧membranous adhesive

505‧‧‧半導體晶片 505‧‧‧Semiconductor wafer

506‧‧‧被接著體 506‧‧‧Exposed body

541‧‧‧晶片接著用晶片 541‧‧‧ wafer followed by wafer

圖1係膜狀接著劑之概略剖視圖。 Fig. 1 is a schematic cross-sectional view of a film-like adhesive.

圖2係附有膜狀接著劑之切晶帶之概略剖視圖。 Fig. 2 is a schematic cross-sectional view showing a dicing tape with a film-like adhesive.

圖3係變化例之附有膜狀接著劑之切晶帶之概略剖視圖。 Fig. 3 is a schematic cross-sectional view showing a dicing tape with a film-like adhesive attached to a modification.

圖4係概略表示於附有膜狀接著劑之切晶帶上配置有半導體晶圓之狀態之剖視圖。 4 is a cross-sectional view schematically showing a state in which a semiconductor wafer is placed on a dicing tape to which a film-like adhesive is attached.

圖5係晶片接著用晶片等之概略剖視圖。 Fig. 5 is a schematic cross-sectional view showing a wafer followed by a wafer or the like.

圖6係附有半導體晶片之被接著體之概略剖視圖。 Fig. 6 is a schematic cross-sectional view of a member to which a semiconductor wafer is attached.

圖7係半導體裝置之概略剖視圖。 Fig. 7 is a schematic cross-sectional view showing a semiconductor device.

圖8係評價基板之俯視圖。 Fig. 8 is a plan view of the evaluation substrate.

圖9係試驗基板之俯視圖。 Figure 9 is a plan view of the test substrate.

圖10係晶片接著步驟之概略剖視圖。 Figure 10 is a schematic cross-sectional view showing the next step of the wafer.

以下列舉實施形態，詳細說明本發明，但本發明並不僅限於該等實施形態。 The present invention will be described in detail below with reference to the embodiments, but the present invention is not limited to the embodiments.

[膜狀接著劑3] [membrane adhesive 3]

如圖1所示，膜狀接著劑3呈膜狀。膜狀接著劑3具備導電性及熱硬化性。 As shown in Fig. 1, the film-like adhesive 3 has a film shape. The film-like adhesive 3 has electrical conductivity and thermosetting properties.

膜狀接著劑3進而具備如下性質。即，藉由加熱進行硬化而得到之硬化物之第1熱導率相對於加熱前之第2熱導率之比之值(第1熱導率 /第2熱導率)為2.0以上。較佳為2.5以上。第1熱導率相對於第2熱導率之比之值之上限沒有特別限定，例如為5.0等。 The film-like adhesive 3 further has the following properties. That is, the ratio of the first thermal conductivity of the cured product obtained by curing by heating to the second thermal conductivity before heating (first thermal conductivity) / 2nd thermal conductivity) is 2.0 or more. It is preferably 2.5 or more. The upper limit of the value of the ratio of the first thermal conductivity to the second thermal conductivity is not particularly limited, and is, for example, 5.0 or the like.

第1熱導率較佳為1.7W/m‧K以上，更佳為2.0W/m‧K以上，進而較佳為2.5W/m‧K以上，尤佳為3.0W/m‧K以上。第1熱導率之上限例如為20W/m‧K、30W/m‧K等。 The first thermal conductivity is preferably 1.7 W/m‧K or more, more preferably 2.0 W/m ‧ K or more, further preferably 2.5 W/m ‧ K or more, and particularly preferably 3.0 W/m ‧ K or more The upper limit of the first thermal conductivity is, for example, 20 W/m‧K, 30 W/m‧K, or the like.

第2熱導率較佳為0.3W/m‧K以上，更佳為0.5W/m‧K以上。另一方面，第2熱導率較佳為15W/m‧K以下，更佳為10W/m‧K以下。 The second thermal conductivity is preferably 0.3 W/m‧K or more, more preferably 0.5 W/m‧K or more. On the other hand, the second thermal conductivity is preferably 15 W/m‧K or less, more preferably 10 W/m‧K or less.

第1熱導率、第2熱導率係使用實施例記載之方法進行測定。 The first thermal conductivity and the second thermal conductivity were measured by the method described in the examples.

較佳為，膜狀接著劑3進而具備如下性質。即，藉由加熱進行硬化而得到之硬化物之第1電阻率相對於加熱前之第2電阻率之比之值(第1電阻率/第2電阻率)較佳為0.01以上，更佳為0.015以上。第1電阻率相對於第2電阻率之比之值之上限例如為0.95、0.9等。 Preferably, the film-like adhesive 3 further has the following properties. In other words, the ratio of the first resistivity of the cured product obtained by curing by heating to the second resistivity before heating (first resistivity/second resistivity) is preferably 0.01 or more, more preferably 0.015 or more. The upper limit of the value of the ratio of the first resistivity to the second resistivity is, for example, 0.95, 0.9, or the like.

第1電阻率較佳為5×10-5Ω‧m以下，更佳為3×10-5Ω‧m以下。第1電阻率之下限例如為1×10-7Ω‧m等。 The first electrical resistivity is preferably 5 × 10 -5 Ω ‧ m or less, more preferably 3 × 10 -5 Ω ‧ m or less. The lower limit of the first electrical resistivity is, for example, 1 × 10 -7 Ω ‧ m or the like.

第2電阻率較佳為5×10-5Ω‧m以下，更佳為4×10-5Ω‧m以下。第2電阻率之下限例如為3×10-7Ω‧m等。 The second electrical resistivity is preferably 5 × 10 -5 Ω ‧ m or less, more preferably 4 × 10 -5 Ω ‧ m or less. The lower limit of the second electrical resistivity is, for example, 3 × 10 -7 Ω ‧ m or the like.

第1電阻率、第2電阻率係使用實施例記載之方法進行測定。 The first resistivity and the second resistivity were measured by the method described in the examples.

較佳為，膜狀接著劑3進而具備如下性質。即，硬化物之175℃之儲存模數較佳為50MPa以上。另一方面，硬化物之175℃之儲存模數較佳為1500MPa以下。 Preferably, the film-like adhesive 3 further has the following properties. That is, the storage modulus of the cured product at 175 ° C is preferably 50 MPa or more. On the other hand, the storage modulus of the cured product at 175 ° C is preferably 1,500 MPa or less.

較佳為，膜狀接著劑3進而具備如下性質。於40℃下將膜狀接著劑3貼附於鏡面矽晶圓後，於25℃下測定之密接力較佳為1N/10mm以上，更佳為4N/10mm以上。若為1N/10mm以上，則膜狀接著劑3可於40℃左右之低溫下貼附至半導體晶圓。密接力之上限沒有特別限定，例如為10N/10mm。 Preferably, the film-like adhesive 3 further has the following properties. After attaching the film-like adhesive 3 to the mirror-finished wafer at 40 ° C, the adhesion measured at 25 ° C is preferably 1 N/10 mm or more, and more preferably 4 N/10 mm or more. When it is 1 N/10 mm or more, the film-like adhesive 3 can be attached to a semiconductor wafer at a low temperature of about 40 °C. The upper limit of the adhesion is not particularly limited and is, for example, 10 N/10 mm.

本說明書中，密接力係指自鏡面矽晶圓剝離膜狀接著劑3時之剝離力，用如下方法測定。 In the present specification, the adhesion force refers to the peeling force when the film-like adhesive 3 is peeled off from the mirror-finished wafer, and is measured by the following method.

使用2kg輥將40℃之鏡面矽晶圓貼附至膜狀接著劑3後，於40℃下放置2分鐘。此後，於常溫(25℃)下放置20分鐘，得到具備膜狀接著劑3及貼附於膜狀接著劑3之鏡面矽晶圓之樣品。對於樣品，使用拉伸試驗機(島津製作所股份有限公司製之AGS-J)於剝離角度180度、剝離溫度25℃、剝離速度300mm/分鐘之條件下測定自鏡面矽晶圓剝離膜狀接著劑3時之剝離力。 A mirrored wafer of 40 ° C was attached to the film-like adhesive 3 using a 2 kg roller, and left at 40 ° C for 2 minutes. Thereafter, the film was allowed to stand at room temperature (25 ° C) for 20 minutes to obtain a sample having a film-like adhesive 3 and a mirror-finished wafer attached to the film-like adhesive 3. For the sample, a tensile tester (AGS-J manufactured by Shimadzu Corporation) was used to measure the peeling film-like adhesive from the mirror-finished wafer at a peeling angle of 180 degrees, a peeling temperature of 25 ° C, and a peeling speed of 300 mm/min. 3 o'clock peeling force.

膜狀接著劑3包含樹脂成分。作為樹脂成分，可列舉例如熱塑性樹脂、熱硬化性樹脂等。 The film-like adhesive 3 contains a resin component. Examples of the resin component include a thermoplastic resin and a thermosetting resin.

作為熱塑性樹脂，可列舉：天然橡膠、丁基橡膠、異戊二烯橡膠、氯丁二烯橡膠、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸酯共聚物、聚丁二烯樹脂、聚碳酸酯樹脂、熱塑性聚醯亞胺樹脂；6-尼龍、6,6-尼龍等聚醯胺樹脂；苯氧基樹脂、丙烯酸系樹脂；PET、PBT等飽和聚酯樹脂；聚醯胺醯亞胺樹脂、或者氟樹脂等。該等熱塑性樹脂之中，尤佳為離子性雜質少、耐熱性高、可確保半導體元件之可靠性之丙烯酸系樹脂。 Examples of the thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, and polybutylene. Polyene resin, polycarbonate resin, thermoplastic polyimide resin; 6-nylon, 6,6-nylon and other polyamide resin; phenoxy resin, acrylic resin; saturated polyester resin such as PET, PBT; An amine imine resin, or a fluororesin or the like. Among these thermoplastic resins, an acrylic resin having less ionic impurities, high heat resistance, and reliability of a semiconductor element can be preferably used.

作為丙烯酸系樹脂，沒有特別限定，可列舉以具備碳數為30以下、特別是碳數為4~18之直鏈或支鏈之烷基的丙烯酸或甲基丙烯酸之酯之1種或2種以上作為成分之聚合物(丙烯酸系共聚物)等。作為上述烷基，可列舉例如：甲基、乙基、丙基、異丙基、正丁基、第三丁基、異丁基、戊基、異戊基、己基、庚基、環己基、2-乙基己基、辛基、異辛基、壬基、異壬基、癸基、異癸基、十一烷基、月桂基、十三烷基、十四烷基、硬脂基、十八烷基、或十二烷基等。 The acrylic resin is not particularly limited, and one or two kinds of esters of acrylic acid or methacrylic acid having a linear or branched alkyl group having a carbon number of 30 or less, particularly a carbon number of 4 to 18, may be mentioned. The above-mentioned polymer (acrylic copolymer) as a component. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, and a cyclohexyl group. 2-ethylhexyl, octyl, isooctyl, decyl, isodecyl, decyl, isodecyl, undecyl, lauryl, tridecyl, tetradecyl, stearyl, ten Octaalkyl, or dodecyl, and the like.

又，作為形成聚合物(丙烯酸系共聚物)之其他單體，沒有特別限定，可列舉例如：丙烯酸、甲基丙烯酸、丙烯酸羧基乙酯、丙烯酸羧 基戊酯、衣康酸、馬來酸、富馬酸或巴豆酸等各種含羧基單體；馬來酸酐或衣康酸酐等各種酸酐單體；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯或丙烯酸(4-羥甲基環己基)甲酯等各種含羥基單體；苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺丙酯或(甲基)丙烯醯氧基萘磺酸等各種含磺酸基單體；或者2-羥基乙基丙烯醯基磷酸酯等各種含磷酸基單體。 Further, the other monomer forming the polymer (acrylic copolymer) is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, carboxyethyl acrylate, and acrylic acid carboxylate. Various carboxyl group-containing monomers such as pentamethyl ester, itaconic acid, maleic acid, fumaric acid or crotonic acid; various acid anhydride monomers such as maleic anhydride or itaconic anhydride; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, (meth) acrylate 10 - Various hydroxyl group-containing monomers such as hydroxydecyl ester, 12-hydroxylauryl (meth)acrylate or (4-hydroxymethylcyclohexyl)methyl acrylate; styrenesulfonic acid, allylsulfonic acid, 2-(methyl a variety of sulfonic acid groups such as acrylamide-2-methylpropanesulfonic acid, (meth)acrylamide, propanesulfonic acid, sulfopropyl (meth)acrylate or (meth)acryloxynaphthalenesulfonic acid a monomer; or a various phosphate group-containing monomer such as 2-hydroxyethyl acryloyl phosphate.

丙烯酸系樹脂之中，較佳為重量平均分子量為10萬以上者，更佳為重量平均分子量為30萬~300萬者，進而較佳為重量平均分子量為50萬~200萬者。其原因在於：若為上述數值範圍內，則接著性及耐熱性優異。再者，重量平均分子量係藉由GPC(凝膠滲透層析法)測定並根據聚苯乙烯換算而算出之值。 Among the acrylic resins, those having a weight average molecular weight of 100,000 or more, more preferably a weight average molecular weight of 300,000 to 3,000,000, more preferably a weight average molecular weight of 500,000 to 2,000,000 are preferable. The reason for this is that when it is in the above numerical range, it is excellent in adhesiveness and heat resistance. Further, the weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated based on polystyrene.

丙烯酸系樹脂較佳為包含可與環氧基反應之官能基。藉此，可使丙烯酸系樹脂與環氧樹脂交聯。 The acrylic resin preferably contains a functional group reactive with an epoxy group. Thereby, the acrylic resin can be crosslinked with the epoxy resin.

作為可與環氧基反應之官能基，可列舉例如羧基、羥基等。其中，出於與環氧基之反應性高之理由，較佳為羧基。 Examples of the functional group reactive with the epoxy group include a carboxyl group, a hydroxyl group and the like. Among them, a carboxyl group is preferred because of its high reactivity with an epoxy group.

丙烯酸系樹脂之酸值較佳為1mgKOH/g以上，更佳為3mgKOH/g以上。若為1mgKOH/g以上，可得到良好之凝聚力。另一方面，丙烯酸系樹脂之酸值較佳為20mgKOH/g以下，更佳為10mgKOH/g以下。 The acid value of the acrylic resin is preferably 1 mgKOH/g or more, more preferably 3 mgKOH/g or more. If it is 1 mgKOH/g or more, good cohesive force can be obtained. On the other hand, the acid value of the acrylic resin is preferably 20 mgKOH/g or less, more preferably 10 mgKOH/g or less.

再者，酸值可用JIS K 0070-1992中規定之中和滴定法進行測定。 Further, the acid value can be measured by the titration method specified in JIS K 0070-1992.

熱塑性樹脂之玻璃轉移溫度較佳為-40℃以上，更佳為-35℃以上，進而較佳為-25℃以上。若未達-40℃，則膜狀接著劑3有變得發黏而拾取性變差之傾向。又，熱塑性樹脂之玻璃轉移溫度較佳為-5℃以下，更佳為-10℃以下，進而較佳為-11℃以下。 The glass transition temperature of the thermoplastic resin is preferably -40 ° C or higher, more preferably -35 ° C or higher, and still more preferably -25 ° C or higher. If it is less than -40 ° C, the film-like adhesive 3 tends to become sticky and the pick-up property tends to be deteriorated. Further, the glass transition temperature of the thermoplastic resin is preferably -5 ° C or lower, more preferably -10 ° C or lower, further preferably -11 ° C or lower.

樹脂成分100重量%中之熱塑性樹脂之含量較佳為5重量%以上，更佳為10重量%以上。又，樹脂成分100重量%中之熱塑性樹脂之含量較佳為70重量%以下，更佳為50重量%以下，進而較佳為25重量%以下。 The content of the thermoplastic resin in 100% by weight of the resin component is preferably 5% by weight or more, more preferably 10% by weight or more. Further, the content of the thermoplastic resin in 100% by weight of the resin component is preferably 70% by weight or less, more preferably 50% by weight or less, still more preferably 25% by weight or less.

作為熱硬化性樹脂，可列舉：酚樹脂、胺基樹脂、不飽和聚酯樹脂、環氧樹脂、聚胺基甲酸酯樹脂、聚矽氧樹脂、或熱硬化性聚醯亞胺樹脂等。尤其，較佳為使半導體元件腐蝕之離子性雜質等之含量少之環氧樹脂。又，作為環氧樹脂之硬化劑，較佳為酚樹脂。 Examples of the thermosetting resin include a phenol resin, an amine resin, an unsaturated polyester resin, an epoxy resin, a polyurethane resin, a polyoxyxylene resin, or a thermosetting polyimide resin. In particular, an epoxy resin having a small content of ionic impurities or the like which causes corrosion of the semiconductor element is preferable. Further, as the curing agent for the epoxy resin, a phenol resin is preferred.

作為環氧樹脂，沒有特別限定，可使用例如：雙酚A型、雙酚F型、雙酚S型、溴化雙酚A型、氫化雙酚A型、雙酚AF型、聯苯型、萘型、芴型、苯酚酚醛清漆型、鄰甲酚酚醛清漆型、三羥苯基甲烷型、四酚基乙烷型等二官能環氧樹脂或多官能環氧樹脂；或者乙內醯脲型、三縮水甘油基異氰脲酸酯型或縮水甘油胺型等環氧樹脂。該等環氧樹脂之中，尤佳為酚醛清漆型環氧樹脂、聯苯型環氧樹脂、三羥苯基甲烷型樹脂或四酚基乙烷型環氧樹脂。其原因在於，該等環氧樹脂富有與作為硬化劑之酚樹脂之反應性，且耐熱性等優異。 The epoxy resin is not particularly limited, and for example, bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol AF type, biphenyl type, or the like can be used. Naphthalene type, bismuth type, phenol novolak type, o-cresol novolak type, trihydroxyphenylmethane type, tetraphenol ethane type and other difunctional epoxy resin or polyfunctional epoxy resin; or beta uregua form An epoxy resin such as a triglycidyl isocyanurate type or a glycidylamine type. Among these epoxy resins, a novolac type epoxy resin, a biphenyl type epoxy resin, a trishydroxyphenylmethane type resin or a tetraphenol ethane type epoxy resin is particularly preferable. The reason for this is that these epoxy resins are rich in reactivity with a phenol resin as a curing agent, and are excellent in heat resistance and the like.

作為環氧樹脂，可使用於25℃為固體之環氧樹脂、於25℃為液態之環氧樹脂等。 As the epoxy resin, an epoxy resin which is solid at 25 ° C and an epoxy resin which is liquid at 25 ° C can be used.

本說明書中，於25℃為液態係指於25℃時黏度未達5000Pa‧s。另一方面，於25℃為固體係指於25℃時黏度為5000Pa‧s以上。黏度可使用Thermo Scientific公司製之型號HAAKE Roto VISCO1進行測定。 In the present specification, the liquid state at 25 ° C means that the viscosity is less than 5000 Pa ‧ at 25 ° C. On the other hand, a solid at 25 ° C means a viscosity of 5,000 Pa s or more at 25 ° C. The viscosity can be measured using a model HAAKE Roto VISCO1 manufactured by Thermo Scientific.

環氧樹脂100重量%中，於25℃為固體之環氧樹脂之含量較佳為10重量%以上，更佳為30重量%以上。若未達10重量%，則膜狀接著劑3有變得發黏而拾取性變差之傾向。環氧樹脂100重量%中，於25℃為固體之環氧樹脂之含量較佳為80重量%以下，更佳為70重量%以 下。 The content of the epoxy resin which is solid at 25 ° C in 100% by weight of the epoxy resin is preferably 10% by weight or more, and more preferably 30% by weight or more. If it is less than 10% by weight, the film-like adhesive 3 tends to become sticky and the pick-up property tends to be deteriorated. The content of the epoxy resin which is solid at 25 ° C in 100% by weight of the epoxy resin is preferably 80% by weight or less, more preferably 70% by weight or less. under.

於25℃為固體之環氧樹脂之環氧當量較佳為100g/eq.以上，更佳為110g/eq.以上。另一方面，於25℃為固體之環氧樹脂之環氧當量較佳為2000g/eq.以下，更佳為1500g/eq.以下。 The epoxy equivalent of the epoxy resin which is solid at 25 ° C is preferably 100 g / eq. or more, more preferably 110 g / eq. or more. On the other hand, the epoxy equivalent of the epoxy resin which is solid at 25 ° C is preferably 2000 g / eq. or less, more preferably 1500 g / eq. or less.

環氧樹脂之環氧當量可用JIS K 7236-2009中規定方法進行測定。 The epoxy equivalent of the epoxy resin can be measured by the method specified in JIS K 7236-2009.

於25℃為液態之環氧樹脂之環氧當量較佳為100g/eq.以上，更佳為110g/eq.以上。另一方面，於25℃為液態之環氧樹脂之環氧當量較佳為2000g/eq.以下，更佳為1500g/eq.以下。 The epoxy equivalent of the epoxy resin which is liquid at 25 ° C is preferably 100 g / eq. or more, more preferably 110 g / eq. or more. On the other hand, the epoxy equivalent of the epoxy resin which is liquid at 25 ° C is preferably 2,000 g/eq. or less, more preferably 1,500 g/eq. or less.

酚樹脂係作為環氧樹脂之硬化劑而發揮作用，可列舉例如：苯酚酚醛清漆樹脂、苯酚芳烷基樹脂、甲酚酚醛清漆樹脂、第三丁基苯酚酚醛清漆樹脂、壬基苯酚酚醛清漆樹脂等酚醛清漆型酚樹脂、可溶酚醛型酚樹脂、聚對羥基苯乙烯等聚羥基苯乙烯等。該等酚樹脂之中，尤佳為苯酚酚醛清漆樹脂、苯酚芳烷基樹脂。其原因在於：可提高半導體裝置之連接可靠性。 The phenol resin functions as a curing agent for the epoxy resin, and examples thereof include a phenol novolak resin, a phenol aralkyl resin, a cresol novolak resin, a third butyl phenol novolak resin, and a nonylphenol novolak resin. Such as a novolac type phenol resin, a resol type phenol resin, polyhydroxy styrene such as polyhydroxy styrene, and the like. Among these phenol resins, a phenol novolak resin and a phenol aralkyl resin are particularly preferable. The reason for this is that the connection reliability of the semiconductor device can be improved.

酚樹脂之羥基當量較佳為80g/eq.以上，更佳為85g/eq.以上。另一方面，酚樹脂之羥基當量較佳為1000g/eq.以下，更佳為900g/eq.以下。 The hydroxyl equivalent of the phenol resin is preferably 80 g/eq. or more, more preferably 85 g/eq. or more. On the other hand, the hydroxyl equivalent of the phenol resin is preferably 1000 g/eq. or less, more preferably 900 g/eq. or less.

環氧樹脂與酚樹脂之調配比率例如適合按照相對於環氧樹脂成分中之環氧基每1當量而酚樹脂中之羥基為0.5~2.0當量之方式進行調配。更適合為0.8~1.2當量。即，其原因在於，若兩者之調配比率偏離上述範圍，則無法進行充分之硬化反應，而硬化物之特性容易劣化。 The blending ratio of the epoxy resin and the phenol resin is, for example, suitably adjusted so that the hydroxyl group in the phenol resin is 0.5 to 2.0 equivalents per equivalent of the epoxy group in the epoxy resin component. More suitable for 0.8~1.2 equivalents. That is, the reason is that if the blending ratio of the two is out of the above range, a sufficient curing reaction cannot be performed, and the properties of the cured product are likely to deteriorate.

樹脂成分100重量%中，熱硬化性樹脂之含量較佳為30重量%以上，更佳為50重量%以上，進而較佳為75重量%以上。樹脂成分100重量%中，熱硬化性樹脂之含量較佳為95重量%以下，更佳為90重量%以下。 The content of the thermosetting resin in 100% by weight of the resin component is preferably 30% by weight or more, more preferably 50% by weight or more, still more preferably 75% by weight or more. The content of the thermosetting resin in 100% by weight of the resin component is preferably 95% by weight or less, more preferably 90% by weight or less.

膜狀接著劑3包含導電性粒子。 The film-like adhesive 3 contains conductive particles.

作為導電性粒子，可適當使用燒結性金屬粒子、薄片狀金屬粒子等。 As the conductive particles, sinter metal particles, flaky metal particles, or the like can be suitably used.

燒結性金屬粒子具有於200℃至少一部分會燒結之性質。因此，於標準之硬化條件下燒結性金屬粒子會發生燒結。因此，藉由使膜狀接著劑3硬化，能夠使熱傳導路徑變寬，可提高散熱性。又，可降低電阻率。 The sinter metal particles have a property of being sintered at least in part at 200 °C. Therefore, the sinter metal particles are sintered under standard hardening conditions. Therefore, by curing the film-like adhesive 3, the heat conduction path can be widened, and heat dissipation can be improved. Also, the resistivity can be lowered.

作為燒結性金屬粒子，可適當使用金屬微粒之凝聚體。作為金屬微粒，可列舉包含金屬之微粒、被覆微粒等。被覆微粒具備核微粒及被覆核微粒之被覆膜。作為核微粒之材料，可列舉玻璃等。作為被覆膜之材料，可列舉金屬。作為金屬，可列舉金、銀、銅等。 As the sinter metal particles, an aggregate of metal fine particles can be suitably used. Examples of the metal fine particles include fine particles containing metal, coated fine particles, and the like. The coated fine particles include a core fine particle and a coating film covering the core fine particles. Examples of the material of the core fine particles include glass. As a material of a coating film, a metal is mentioned. Examples of the metal include gold, silver, copper, and the like.

燒結性金屬粒子之平均粒徑較佳為0.005μm以上，更佳為0.01μm以上。作為平均粒徑之下限，亦可例示0.1μm、0.5μm、1μm。另一方面，燒結性金屬粒子之平均粒徑較佳為30μm以下，更佳為25μm以下。作為平均粒徑之上限，亦可例示20μm、15μm、10μm、5μm。 The average particle diameter of the sinter metal particles is preferably 0.005 μm or more, and more preferably 0.01 μm or more. The lower limit of the average particle diameter is also exemplified by 0.1 μm, 0.5 μm, and 1 μm. On the other hand, the average particle diameter of the sinter metal particles is preferably 30 μm or less, and more preferably 25 μm or less. The upper limit of the average particle diameter is also exemplified by 20 μm, 15 μm, 10 μm, and 5 μm.

燒結性金屬粒子之平均粒徑用如下方法測定。即，使用粒度分佈測定裝置(日機裝製之MICROTRAC HRA)以標準模式進行測定，並將藉此所求出之D50資料作為粒徑。 The average particle diameter of the sinter metal particles was measured by the following method. That is, the measurement was performed in a standard mode using a particle size distribution measuring apparatus (MICROTRAC HRA manufactured by Nikkiso), and the D50 data thus obtained was used as the particle diameter.

燒結性金屬粒子之形狀沒有特別限定，例如為無定形。 The shape of the sinter metal particles is not particularly limited and is, for example, amorphous.

薄片狀金屬粒子之平均長徑較佳為0.5μm以上，更佳為1.0μm以上。若為0.5μm以上，則可有效地降低電阻率。另一方面，薄片狀金屬粒子之平均長徑較佳為50μm以下，更佳為30μm以下。 The average long diameter of the flaky metal particles is preferably 0.5 μm or more, and more preferably 1.0 μm or more. When it is 0.5 μm or more, the electrical resistivity can be effectively lowered. On the other hand, the average long diameter of the flaky metal particles is preferably 50 μm or less, more preferably 30 μm or less.

薄片狀金屬粒子之縱橫比較佳為5以上，較佳為8以上，更佳為10以上。若為5以上，可有效地降低電阻率。另一方面，薄片狀金屬粒子之縱橫比較佳為10000以下，更佳為100以下，進而較佳為70以 下，尤佳為50以下。 The aspect ratio of the flaky metal particles is preferably 5 or more, preferably 8 or more, more preferably 10 or more. If it is 5 or more, the electrical resistivity can be effectively reduced. On the other hand, the aspect ratio of the flaky metal particles is preferably 10,000 or less, more preferably 100 or less, still more preferably 70 or less. Next, especially good is 50 or less.

薄片狀金屬粒子之縱橫比為平均長徑相對於平均厚度之比之值(平均長徑/平均厚度)。本說明書中，薄片狀粒子之平均長徑係利用掃描型電子顯微鏡(SEM)觀察膜狀接著劑3之剖面並測定隨機選出之100個薄片狀金屬粒子之長徑而得到的平均值。薄片狀金屬粒子之平均厚度係利用掃描型電子顯微鏡(SEM)觀察膜狀接著劑3之剖面並測定隨機選出之100個薄片狀金屬粒子之厚度而得到之平均值。 The aspect ratio of the flaky metal particles is a ratio (average long diameter/average thickness) of the ratio of the average major axis to the average thickness. In the present specification, the average long diameter of the flaky particles is an average value obtained by observing the cross section of the film-like adhesive 3 by a scanning electron microscope (SEM) and measuring the long diameter of 100 randomly selected flaky metal particles. The average thickness of the flaky metal particles was observed by a scanning electron microscope (SEM) to observe the cross section of the film-like adhesive 3, and the average thickness of 100 randomly selected flaky metal particles was measured.

作為薄片狀金屬粒子之材料，可列舉金、銀、銅等。作為薄片狀金屬粒子，可列舉包含金屬之薄片狀之粒子、薄片狀之被覆粒子等。被覆粒子具備核粒子及被覆核粒子之被覆膜。作為核粒子之材料，可列舉玻璃等。作為被覆膜之材料，可列舉金屬。作為金屬，可列舉金、銀、銅等。 Examples of the material of the flaky metal particles include gold, silver, copper, and the like. Examples of the flaky metal particles include flaky particles of a metal, coated particles of a flaky shape, and the like. The coated particles include a coating film of core particles and coated core particles. Examples of the material of the core particles include glass and the like. As a material of a coating film, a metal is mentioned. Examples of the metal include gold, silver, copper, and the like.

導電性粒子100重量%中，燒結性金屬粒子之含量較佳為5重量%以上，更佳為10重量%以上，進而較佳為15重量%以上。導電性粒子100重量%中，燒結性金屬粒子之含量較佳為50重量%以下，更佳為40重量%以下，進而較佳為35重量%以下。若超過50重量%，則有不易膜化之傾向。 The content of the sinter metal particles in 100% by weight of the conductive particles is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 15% by weight or more. The content of the sinter metal particles in 100% by weight of the conductive particles is preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 35% by weight or less. If it exceeds 50% by weight, there is a tendency that it is not easily formed into a film.

膜狀接著劑3中之導電性粒子之含量較佳為50重量%以上，更佳為60重量%以上，進而較佳為70重量%以上，尤佳為75重量%以上。膜狀接著劑3中之導電性粒子之含量較佳為95重量%以下，更佳為90重量%以下。若超過95重量%，則有不易膜化之傾向。 The content of the conductive particles in the film-like adhesive 3 is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 70% by weight or more, and particularly preferably 75% by weight or more. The content of the conductive particles in the film-like adhesive 3 is preferably 95% by weight or less, more preferably 90% by weight or less. If it exceeds 95% by weight, there is a tendency that it is not easily formed into a film.

膜狀接著劑3於上述成分以外，亦可適當含有通常用於膜製造之調配劑、例如交聯劑等。 The film-like adhesive 3 may contain, in addition to the above components, a preparation agent generally used for film production, for example, a crosslinking agent.

膜狀接著劑3可用通常之方法製造。例如，製造含有上述各成分之接著劑組合物溶液，將接著劑組合物溶液以達到特定厚度之方式塗佈於基材隔離膜上而形成塗膜後，使該塗膜乾燥，藉此可製造膜狀接 著劑3。 The film-like adhesive 3 can be produced by a usual method. For example, a solution of an adhesive composition containing the above respective components is produced, and a solution of the adhesive composition is applied onto a substrate separator to form a coating film, and then the coating film is dried, whereby the coating film can be dried. Membrane connection Agent 3.

作為用於接著劑組合物溶液之溶劑，沒有特別限定，較佳為可將上述各成分均勻溶解、混煉或分散之有機溶劑。可列舉例如：二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯烷酮、丙酮、甲基乙基酮、環己酮等酮系溶劑；甲苯、二甲苯等。塗佈方法沒有特別限定。作為溶劑塗敷之方法，可列舉例如：模嘴塗佈機、凹版塗佈機、輥塗機、反向塗佈機、缺角輪塗佈機、管刀塗佈機、網版印刷等。其中，就塗佈厚度之均勻性高方面而言，較佳為模嘴塗佈機。 The solvent used for the adhesive composition solution is not particularly limited, and an organic solvent which can uniformly dissolve, knead or disperse the above components is preferable. For example, a ketone solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, acetone, methyl ethyl ketone or cyclohexanone; toluene, xylene or the like can be mentioned. The coating method is not particularly limited. Examples of the method of solvent coating include a die coater, a gravure coater, a roll coater, a reverse coater, a riprap coater, a tube knife coater, and screen printing. Among them, a die coater is preferred in terms of high uniformity of coating thickness.

作為基材隔離膜，可使用聚對苯二甲酸乙二酯(PET)、聚乙烯、聚丙烯、或利用氟系剝離劑、丙烯酸長鏈烷基酯系剝離劑等剝離劑進行表面塗佈而得之塑膠膜或紙等。作為接著劑組合物溶液之塗佈方法，可列舉例如：輥塗、網版塗敷、凹版塗敷等。又，塗膜之乾燥條件沒有特別限定，例如可以乾燥溫度70~160℃、乾燥時間1~5分鐘之條件進行。 As the substrate separator, polyethylene terephthalate (PET), polyethylene, polypropylene, or a release agent such as a fluorine-based release agent or an acrylic long-chain alkyl ester release agent can be used for surface coating. Get plastic film or paper. Examples of the coating method of the adhesive composition solution include roll coating, screen coating, gravure coating, and the like. Further, the drying conditions of the coating film are not particularly limited, and for example, it can be carried out under the conditions of a drying temperature of 70 to 160 ° C and a drying time of 1 to 5 minutes.

作為膜狀接著劑3之製造方法，例如亦較佳為如下方法等：將上述各成分用攪拌機混合，對所得到之混合物進行壓製成形而製造膜狀接著劑3。作為攪拌機，可列舉行星式攪拌機等。 For example, a method of producing the film-like adhesive 3 is preferably a method in which the above components are mixed by a stirrer, and the obtained mixture is press-molded to produce a film-like adhesive 3. As a stirrer, a planetary mixer etc. are mentioned.

膜狀接著劑3之厚度沒有特別限定，較佳為5μm以上，更佳為15μm以上。若未達5μm，則有與半導體晶圓、半導體晶片接觸之面積不穩定之情形。又，膜狀接著劑3之厚度較佳為100μm以下，更佳為50μm以下。若超過100μm，則有由於晶片黏著之負荷而使膜狀接著劑3過度溢出之虞。 The thickness of the film-like adhesive 3 is not particularly limited, but is preferably 5 μm or more, and more preferably 15 μm or more. If it is less than 5 μm, the area in contact with the semiconductor wafer or the semiconductor wafer may be unstable. Further, the thickness of the film-like adhesive 3 is preferably 100 μm or less, and more preferably 50 μm or less. When it exceeds 100 μm, there is a possibility that the film-like adhesive 3 excessively overflows due to the load of the wafer adhesion.

膜狀接著劑3用於製造半導體裝置。其中，可適合地用於製造功率半導體裝置。具體來說，用作將引線框架等被接著體與半導體晶片接著(進行晶片黏著)之晶片黏著膜。作為被接著體，可列舉引線框架、內插器、半導體晶片等。 The film-like adhesive 3 is used to manufacture a semiconductor device. Among them, it can be suitably used for manufacturing a power semiconductor device. Specifically, it is used as a wafer adhesive film in which a substrate such as a lead frame is bonded to a semiconductor wafer (attached to the wafer). Examples of the adherend include a lead frame, an interposer, and a semiconductor wafer.

膜狀接著劑3較佳為以附有膜狀接著劑之切晶帶之形態使用。[附有膜狀接著劑之切晶帶10] The film-like adhesive 3 is preferably used in the form of a dicing tape with a film-like adhesive. [Cutting tape 10 with film-like adhesive]

如圖2所示，附有膜狀接著劑之切晶帶10具備切晶帶1、及配置於切晶帶1上之膜狀接著劑3。切晶帶1具備基材11及配置於基材11上之黏著劑層12。膜狀接著劑3被配置於黏著劑層12上。 As shown in FIG. 2, the dicing tape 10 with a film-like adhesive agent has the dicing tape 1, and the film-form adhesive 3 arrange|positioned on the dicing tape 1. The dicing tape 1 includes a substrate 11 and an adhesive layer 12 disposed on the substrate 11. The film-like adhesive 3 is disposed on the adhesive layer 12.

如圖3所示，附有膜狀接著劑之切晶帶10亦可為僅於工件(半導體晶圓4等)貼附部分形成有膜狀接著劑3之構成。 As shown in FIG. 3, the dicing tape 10 with a film-like adhesive may be formed by forming a film-like adhesive 3 only on a workpiece (semiconductor wafer 4 or the like).

基材11成為附有膜狀接著劑之切晶帶10之強度母體，較佳為具有紫外線透射性者。作為基材11，可列舉例如：低密度聚乙烯、直鏈狀聚乙烯、中密度聚乙烯、高密度聚乙烯、超低密度聚乙烯、無規共聚聚丙烯、嵌段共聚聚丙烯、均聚丙烯、聚丁烯、聚甲基戊烯等聚烯烴；乙烯-乙酸乙烯酯共聚物、離聚物樹脂、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯(無規、交替)共聚物、乙烯-丁烯共聚物、乙烯-己烯共聚物、聚胺基甲酸酯、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等聚酯；聚碳酸酯、聚醯亞胺、聚醚醚酮、聚醯亞胺、聚醚醯亞胺、聚醯胺、全芳香族聚醯胺、聚苯硫醚、芳族聚醯胺(紙)、玻璃、玻璃布、氟樹脂、聚氯乙烯、聚偏二氯乙烯、纖維素系樹脂、聚矽氧樹脂、金屬(箔)、紙等。 The base material 11 is a strength matrix of the dicing tape 10 to which a film-like adhesive is attached, and is preferably one having ultraviolet ray transmittance. Examples of the substrate 11 include low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, random copolymer polypropylene, block copolymer polypropylene, and homopolymerization. Polyolefins such as propylene, polybutene, polymethylpentene; ethylene-vinyl acetate copolymer, ionomer resin, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate (random, Alternate) polyesters such as copolymers, ethylene-butene copolymers, ethylene-hexene copolymers, polyurethanes, polyethylene terephthalate, polyethylene naphthalate, etc.; polycarbonate, Polyimine, polyetheretherketone, polyimine, polyetherimide, polyamine, wholly aromatic polyamine, polyphenylene sulfide, aromatic polyamide (paper), glass, glass cloth , fluororesin, polyvinyl chloride, polyvinylidene chloride, cellulose resin, polyoxyxylene resin, metal (foil), paper, and the like.

為了提高與相鄰之層之密接性、保持性等，基材11之表面可實施慣用之表面處理，例如：鉻酸處理、臭氧暴露、火焰暴露、高壓電擊暴露、離子化放射線處理等化學性或物理性處理、利用底塗劑(例如後述之黏著物質)之塗佈處理。 In order to improve adhesion to adjacent layers, retention, etc., the surface of the substrate 11 can be subjected to conventional surface treatment such as chromic acid treatment, ozone exposure, flame exposure, high voltage shock exposure, ionizing radiation treatment, etc. Or physical treatment, coating treatment using a primer (for example, an adhesive substance described later).

基材11之厚度沒有特別限制，可適當確定，一般為5~200μm左右。 The thickness of the substrate 11 is not particularly limited and can be appropriately determined, and is generally about 5 to 200 μm.

作為用於形成黏著劑層12之黏著劑，沒有特別限制，可使用例如丙烯酸系黏著劑、橡膠系黏著劑等通常之感壓性接著劑。就半導體 晶圓或玻璃等忌諱污染之電子零件利用超純水或醇等有機溶劑之清潔清洗性等方面而言，作為感壓性接著劑，較佳為以丙烯酸系聚合物為基礎聚合物之丙烯酸系黏著劑。 The adhesive for forming the adhesive layer 12 is not particularly limited, and a general pressure-sensitive adhesive such as an acrylic adhesive or a rubber-based adhesive can be used. Semiconductor In the case of an electronic component such as a wafer or glass, which is contaminated with impurities, such as an ultra-pure water or an organic solvent such as an alcohol, the pressure-sensitive adhesive is preferably an acrylic polymer based on an acrylic polymer. Adhesive.

作為丙烯酸系聚合物，可列舉例如將(甲基)丙烯酸烷基酯(例如甲酯、乙酯、丙酯、異丙酯、丁酯、異丁酯、第二丁酯、第三丁酯、戊酯、異戊酯、己酯、庚酯、辛酯、2-乙基己酯、異辛酯、壬酯、癸酯、異癸酯、十一烷基酯、十二烷基酯、十三烷基酯、十四烷基酯、十六烷基酯、十八烷基酯、二十烷基酯等烷基之碳數為1~30、特別是碳數為4~18之直鏈狀或支鏈狀之烷基酯等)及(甲基)丙烯酸環烷基酯(例如環戊酯、環己酯等)中之1種或2種以上用作單體成分之丙烯酸系聚合物等。再者，所謂(甲基)丙烯酸酯係指丙烯酸酯及/或甲基丙烯酸酯，本發明之所謂(甲基)均為同樣之意思。 Examples of the acrylic polymer include alkyl (meth)acrylate (for example, methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, second butyl ester, and third butyl ester, Amyl, isoamyl, hexyl, heptyl, octyl, 2-ethylhexyl, isooctyl, decyl, decyl, isodecyl, undecyl, dodecyl, ten The alkyl group such as a trialkyl ester, a tetradecyl ester, a hexadecyl ester, an octadecyl ester or an eicosyl ester has a carbon number of 1 to 30, particularly a linear chain having a carbon number of 4 to 18. One or more of a cycloalkyl (meth) acrylate or the like (for example, a cyclopentyl ester or a cyclohexyl ester), and an acrylic polymer used as a monomer component Wait. In addition, the (meth)acrylate means an acrylate and/or a methacrylate, and what is called (meth) in this invention is the same.

以凝聚力、耐熱性等之改善為目的，丙烯酸系聚合物根據需要亦可含有能夠與上述(甲基)丙烯酸烷基酯或環烷基酯共聚之其他單體成分所對應之單元。作為此種單體成分，可列舉例如：丙烯酸、甲基丙烯酸、(甲基)丙烯酸羧乙酯、(甲基)丙烯酸羧戊酯、衣康酸、馬來酸、富馬酸、巴豆酸等含羧基之單體；馬來酸酐、衣康酸酐等酸酐單體；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯、(甲基)丙烯酸(4-羥甲基環己基)甲酯等含羥基之單體；苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯醯氧基萘磺酸等含磺酸基之單體；2-羥基乙基丙烯醯基磷酸酯等含磷酸基之單體；丙烯醯胺、丙烯腈等。該等可共聚之單體成分可使用1種或2種以上。該等可共聚之單體之使用量較佳為全部單體成分之40重量%以下。 For the purpose of improving the cohesive force, the heat resistance, and the like, the acrylic polymer may contain a unit corresponding to another monomer component copolymerizable with the alkyl (meth)acrylate or the cycloalkyl ester, if necessary. Examples of such a monomer component include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like. Carboxyl group-containing monomer; anhydride monomer such as maleic anhydride or itaconic anhydride; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate , 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (meth)acrylic acid a hydroxyl group-containing monomer such as (4-hydroxymethylcyclohexyl)methyl ester; styrenesulfonic acid, allylsulfonic acid, 2-(methyl)propenylamine-2-methylpropanesulfonic acid, (methyl a sulfonic acid group-containing monomer such as acrylamide propyl sulfonic acid, sulfopropyl (meth) acrylate, (meth) propylene phthaloxy naphthalene sulfonic acid; Base monomer; acrylamide, acrylonitrile, and the like. One or two or more kinds of these copolymerizable monomer components can be used. The amount of the copolymerizable monomers used is preferably 40% by weight or less based on the total of the monomer components.

進而，為了發生交聯，丙烯酸系聚合物根據需要可含有多官能性單體等作為共聚用單體成分。作為此種多官能性單體，可列舉例如：己二醇二(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、聚胺基甲酸酯(甲基)丙烯酸酯等。該等多官能性單體亦可使用1種或2種以上。就黏著特性等方面而言，多官能性單體之使用量較佳為全部單體成分之30重量%以下。 Further, in order to cause crosslinking, the acrylic polymer may contain a polyfunctional monomer or the like as a monomer component for copolymerization as needed. Examples of such a polyfunctional monomer include hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, and (poly)propylene glycol di(meth)acrylate. Neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(methyl) Acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, polyurethane (meth) acrylate, and the like. These polyfunctional monomers may be used alone or in combination of two or more. The amount of the polyfunctional monomer used is preferably 30% by weight or less based on the total of the monomer components in terms of adhesion characteristics and the like.

丙烯酸系聚合物係藉由將單一單體或2種以上單體之混合物進行聚合而獲得。聚合可以溶液聚合、乳化聚合、塊狀聚合、懸浮聚合等任一方式進行。就防止對清潔之被接著體之污染等方面而言，較佳為低分子量物質之含量小。就此方面而言，丙烯酸系聚合物之數量平均分子量較佳為30萬以上，進而較佳為40萬~300萬左右。 The acrylic polymer is obtained by polymerizing a single monomer or a mixture of two or more kinds of monomers. The polymerization can be carried out by any one of solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and the like. It is preferable that the content of the low molecular weight substance is small in terms of prevention of contamination of the cleaned adherend or the like. In this regard, the number average molecular weight of the acrylic polymer is preferably 300,000 or more, and more preferably about 400,000 to 3,000,000.

又，為了提高作為基礎聚合物之丙烯酸系聚合物等之數量平均分子量，上述黏著劑亦可適當採用外部交聯劑。作為外部交聯方法之具體手段，可列舉添加聚異氰酸酯化合物、環氧化合物、氮丙啶化合物、三聚氰胺系交聯劑等所謂交聯劑進行反應之方法。使用外部交聯劑之情形時，其使用量可根據與要進行交聯之基礎聚合物之平衡、以及根據作為黏著劑之使用用途來適當確定。通常，相對於上述基礎聚合物100重量份，外部交聯劑較佳為調配5重量份左右以下，進而較佳為調配0.1~5重量份。此外，黏著劑中除了上述成分以外，根據需要亦可使用先前公知之各種黏著賦予劑、抗老化劑等添加劑。 Moreover, in order to increase the number average molecular weight of the acrylic polymer or the like as the base polymer, an external crosslinking agent may be suitably used as the above-mentioned adhesive. Specific examples of the external crosslinking method include a method of adding a so-called crosslinking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound or a melamine crosslinking agent. In the case of using an external crosslinking agent, the amount thereof can be appropriately determined depending on the balance with the base polymer to be crosslinked, and the use as the adhesive. Usually, the external crosslinking agent is preferably formulated in an amount of about 5 parts by weight or less, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the base polymer. Further, in addition to the above components, additives such as various conventionally known adhesion-imparting agents and anti-aging agents may be used as needed.

黏著劑層12可利用放射線硬化型黏著劑來形成。放射線硬化型黏著劑可利用紫外線等放射線之照射來增大交聯度而容易地使其黏著力下降。 The adhesive layer 12 can be formed using a radiation hardening type adhesive. The radiation-curable adhesive can be irradiated with radiation such as ultraviolet rays to increase the degree of crosslinking and easily reduce the adhesion.

藉由僅對圖2所示之黏著劑層12之工件貼附部分所對應之部分12a進行放射線照射，能夠設置與其他部分12b之黏著力差。於該情形時，利用未硬化之放射線硬化型黏著劑形成之上述部分12b與膜狀接著劑3黏著，能夠確保切割時之保持力。 The radiation adhesion to the other portion 12b can be set by irradiating only the portion 12a corresponding to the workpiece attachment portion of the adhesive layer 12 shown in Fig. 2 . In this case, the portion 12b formed of the unhardened radiation-curable adhesive adheres to the film-like adhesive 3, and the holding force at the time of cutting can be ensured.

又，藉由與圖3所示之膜狀接著劑3對應地使放射線硬化型之黏著劑層12發生硬化，能夠形成黏著力顯著下降之上述部分12a。於該情形時，能夠將晶圓環固定於利用未硬化之放射線硬化型黏著劑形成之上述部分12b。 Moreover, the radiation-curable adhesive layer 12 is cured in accordance with the film-like adhesive 3 shown in FIG. 3, whereby the portion 12a in which the adhesive force is remarkably lowered can be formed. In this case, the wafer ring can be fixed to the above-described portion 12b formed of an uncured radiation-curable adhesive.

即，利用放射線硬化型黏著劑形成黏著劑層12之情形時，較佳為對上述部分12a進行放射線照射以使黏著劑層12中之上述部分12a之黏著力<其他部分12b之黏著力。 In other words, when the adhesive layer 12 is formed by the radiation-curable adhesive, it is preferable that the portion 12a is irradiated with radiation so that the adhesive force of the portion 12a in the adhesive layer 12 is <the adhesion of the other portion 12b.

放射線硬化型黏著劑可沒有特別限定地使用具有碳-碳雙鍵等放射線硬化性之官能基且示出黏著性之物質。作為放射線硬化型黏著劑，可示例例如於上述丙烯酸系黏著劑、橡膠系黏著劑等通常之感壓性黏著劑中調配有放射線硬化性之單體成分或低聚物成分之添加型放射線硬化型黏著劑。 The radiation-curable adhesive can be a material having a radiation curable functional group such as a carbon-carbon double bond and exhibiting adhesiveness without any particular limitation. The radiation-curable adhesive agent may, for example, be a radiation-curable type in which a radiation-curable monomer component or an oligomer component is blended in a usual pressure-sensitive adhesive such as the above-described acrylic pressure-sensitive adhesive or rubber-based pressure-sensitive adhesive. Adhesive.

作為所調配之放射線硬化性之單體成分，可列舉例如：胺基甲酸酯低聚物、(甲基)丙烯酸胺基甲酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇單羥基五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯等。又，放射線硬化性之低聚物成分可列舉胺基甲酸酯系、聚醚系、聚酯系、聚碳酸酯系、聚丁二烯系等各種低聚物，其分子量為100~30000左右之範圍之低聚物較適當。放射線硬化性之單體成分或低聚物成分之調配量可根據上述黏著劑層之種類而適當確定能夠使黏著劑層之黏著力降低之量。通常，相對於構成黏著劑之丙烯酸系聚合物等基礎聚 合物100重量份，為例如5~500重量份，較佳為40~150重量份左右。 Examples of the radiation curable monomer component to be blended include a urethane oligomer, a (meth) acrylate urethane, a trimethylolpropane tri(meth) acrylate, and the like. Methyl hydroxymethane tetra(meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxy penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Ester, 1,4-butanediol di(meth)acrylate, and the like. Further, examples of the radiation curable oligomer component include various oligomers such as a urethane type, a polyether type, a polyester type, a polycarbonate type, and a polybutadiene type, and the molecular weight thereof is about 100 to 30,000. The range of oligomers is more appropriate. The blending amount of the radiation-hardening monomer component or the oligomer component can be appropriately determined according to the kind of the above-mentioned adhesive layer to reduce the adhesive strength of the adhesive layer. Usually, it is based on a basic polymer such as an acrylic polymer constituting an adhesive. The compound is, for example, 5 to 500 parts by weight, preferably 40 to 150 parts by weight, based on 100 parts by weight of the compound.

又，作為放射線硬化型黏著劑，除上述說明之添加型放射線硬化型黏著劑之外，可列舉使用於聚合物側鏈或者主鏈中或主鏈末端具有碳-碳雙鍵者作為基礎聚合物之內在型放射線硬化型黏著劑。由於內在型放射線硬化型黏著劑無需含有作為低分子成分之低聚物成分等、或者不大量含有作為低分子成分之低聚物成分等，故而低聚物成分等不會隨著時間之推移於黏著劑層中發生移動，而能夠形成穩定之層結構之黏著劑層，因此較佳。 Further, as the radiation-curable adhesive, in addition to the above-described additive-type radiation-curable adhesive, a base polymer having a carbon-carbon double bond in a polymer side chain or a main chain or a main chain terminal may be mentioned. An intrinsic type radiation hardening adhesive. Since the intrinsic type radiation curable adhesive does not need to contain an oligomer component as a low molecular component or does not contain a large amount of an oligomer component as a low molecular component, the oligomer component or the like does not change over time. It is preferred that the adhesive layer moves in the adhesive layer to form a stable layer structure of the adhesive layer.

上述具有碳-碳雙鍵之基礎聚合物可沒有特別限定地使用具有碳-碳雙鍵且具有黏著性者。作為此種基礎聚合物，較佳為以丙烯酸系聚合物作為基本骨架者。作為丙烯酸系聚合物之基本骨架，可列舉上述示例之丙烯酸系聚合物。 The base polymer having a carbon-carbon double bond described above can be used without any particular limitation, and has a carbon-carbon double bond and has adhesiveness. As such a base polymer, an acrylic polymer is preferably used as a basic skeleton. The basic skeleton of the acrylic polymer may, for example, be an acrylic polymer exemplified above.

對於將碳-碳雙鍵導入上述丙烯酸系聚合物中之導入方法沒有特別限制，可採用各種方法，但碳-碳雙鍵導入聚合物側鏈中時容易進行分子設計。例如可列舉如下方法：預先使丙烯酸系聚合物與具有官能基之單體共聚後，於維持碳-碳雙鍵之放射線硬化性之狀態下使具有能夠與該官能基發生反應之官能基及碳-碳雙鍵之化合物進行縮合或加成反應。 The introduction method for introducing the carbon-carbon double bond into the above acrylic polymer is not particularly limited, and various methods can be employed. However, when a carbon-carbon double bond is introduced into the polymer side chain, molecular design is easily performed. For example, a method in which an acrylic polymer and a monomer having a functional group are copolymerized in advance, and a functional group capable of reacting with the functional group and carbon is maintained while maintaining the radiation curability of the carbon-carbon double bond The compound of the carbon double bond is subjected to a condensation or addition reaction.

作為該等官能基之組合之例子，可列舉：羧酸基與環氧基、羧酸基與氮丙啶基、羥基與異氰酸酯基等。就反應追蹤之容易性而言，該等官能基之組合中，羥基與異氰酸酯基之組合較適宜。又，只要為可利用該等官能基之組合生成上述具有碳-碳雙鍵之丙烯酸系聚合物之組合，則官能基可位於丙烯酸系聚合物及上述化合物中之任一側，但於上述較佳之組合中，較佳為丙烯酸系聚合物具有羥基、上述化合物具有異氰酸酯基之情形。於該情形時，作為具有碳-碳雙鍵之異氰酸酯化合物，可列舉例如：甲基丙烯醯基異氰酸酯、2-甲基丙烯醯氧 基乙基異氰酸酯、間異丙烯基-α,α-二甲基苄基異氰酸酯等。又，作為丙烯酸系聚合物，可使用共聚有上述示例之含羥基之單體或2-羥基乙基乙烯基醚、4-羥基丁基乙烯基醚、二乙二醇單乙烯基醚之醚系化合物等者。 Examples of the combination of such functional groups include a carboxylic acid group and an epoxy group, a carboxylic acid group and an aziridine group, a hydroxyl group and an isocyanate group. In the combination of such functional groups, a combination of a hydroxyl group and an isocyanate group is preferred in terms of ease of reaction tracking. Further, as long as a combination of the above-mentioned functional groups is used to form the above-mentioned acrylic polymer having a carbon-carbon double bond, the functional group may be located on either of the acrylic polymer and the above compound, but In a preferred combination, it is preferred that the acrylic polymer has a hydroxyl group and the above compound has an isocyanate group. In this case, examples of the isocyanate compound having a carbon-carbon double bond include methacryl oxime isocyanate and 2-methyl propylene oxime. Ethyl ethyl isocyanate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, and the like. Further, as the acrylic polymer, an ether group copolymerized with the above-described hydroxyl group-containing monomer or 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether or diethylene glycol monovinyl ether can be used. Compounds, etc.

上述內在型之放射線硬化型黏著劑可單獨使用上述具有碳-碳雙鍵之基礎聚合物(特別是丙烯酸系聚合物)，亦可於不使特性惡化之程度上調配上述放射線硬化性之單體成分或低聚物成分。相對於基礎聚合物100重量份，放射線硬化性之低聚物成分等通常為30重量份之範圍內，較佳為0~10重量份之範圍。 The above-mentioned intrinsic type radiation-curable adhesive can be used alone as the base polymer (especially an acrylic polymer) having a carbon-carbon double bond, or can be blended with the radiation curable monomer to the extent that the properties are not deteriorated. Ingredients or oligomer components. The radiation curable oligomer component or the like is usually in the range of 30 parts by weight, preferably 0 to 10 parts by weight, based on 100 parts by weight of the base polymer.

對於上述放射線硬化型黏著劑，利用紫外線等使其發生硬化之情形時，使其含有光聚合起始劑。作為光聚合起始劑，可列舉例如：4-(2-羥基乙氧基)苯基(2-羥基-2-丙基)酮、α-羥基-α,α'-二甲基苯乙酮、2-甲基-2-羥基苯丙酮、1-羥基環己基苯基酮等α-酮醇系化合物；甲氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基苯乙酮、2-甲基-1-[4-(甲硫基)-苯基]-2-嗎啉基丙烷-1等苯乙酮系化合物；安息香***、安息香異丙醚、大茴香偶姻甲醚等安息香醚系化合物；苯偶醯二甲基縮酮等縮酮系化合物；2-萘磺醯氯等芳香族磺醯氯系化合物；1-苯酮-1,1-丙二酮-2-(O-乙氧基羰基)肟等光活性肟系化合物；二苯甲酮、苯甲醯苯甲酸、3,3'-二甲基-4-甲氧基二苯甲酮等二苯甲酮系化合物；噻噸酮、2-氯噻噸酮、2-甲基噻噸酮、2,4-二甲基噻噸酮、異丙基噻噸酮、2,4-二氯噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮等噻噸酮系化合物；樟腦醌；鹵代酮；醯基氧化膦；醯基膦酸酯等。相對於構成黏著劑之丙烯酸系聚合物等基礎聚合物100重量份，光聚合起始劑之調配量為例如0.05~20重量份左右。 When the radiation curable adhesive is cured by ultraviolet rays or the like, it contains a photopolymerization initiator. The photopolymerization initiator may, for example, be 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)one or α-hydroxy-α,α'-dimethylacetophenone. , an α-keto alcohol compound such as 2-methyl-2-hydroxypropiophenone or 1-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylbenzene Ketone, 2,2-diethoxyacetophenone, 2-methyl-1-[4-(methylthio)-phenyl]-2-morpholinylpropane-1 and other acetophenone-based compounds; benzoin a benzoin ether compound such as diethyl ether, benzoin isopropyl ether, fennel aceton methyl ether; a ketal compound such as benzoin dimethyl ketal; an aromatic sulfonium chloride compound such as 2-naphthalene sulfonium chloride; Photoactive lanthanide compounds such as benzophenone-1,1-propanedione-2-(O-ethoxycarbonyl)anthracene; benzophenone, benzamidine benzoic acid, 3,3'-dimethyl-4 a benzophenone compound such as methoxybenzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthiophene a thioxanthone compound such as ketone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone or 2,4-diisopropylthioxanthone; camphorquinone; halogenated ketone; Phosphine oxide Ester and the like. The amount of the photopolymerization initiator to be added is, for example, about 0.05 to 20 parts by weight based on 100 parts by weight of the base polymer such as the acrylic polymer constituting the pressure-sensitive adhesive.

又，作為放射線硬化型黏著劑，可列舉例如日本專利特開昭60-196956號公報中揭示之含有具有2個以上不飽和鍵之加成聚合性化合 物、具有環氧基之烷氧基矽烷等光聚合性化合物、及羰基化合物、有機硫化合物、過氧化物、胺、鎓鹽系化合物等光聚合起始劑的橡膠系黏著劑或丙烯酸系黏著劑等。 In addition, as the radiation-curable adhesive, an addition polymerization property having two or more unsaturated bonds as disclosed in JP-A-60-196956, for example, is mentioned. A photopolymerizable compound such as an alkoxysilane having an epoxy group; and a rubber-based adhesive or acrylic adhesive which is a photopolymerization initiator such as a carbonyl compound, an organic sulfur compound, a peroxide, an amine or a phosphonium salt compound; Agents, etc.

上述放射線硬化型之黏著劑層12中，根據需要亦可含有利用放射線照射發生著色之化合物。藉由使黏著劑層12中含有利用放射線照射發生著色之化合物，能夠僅對經放射線照射之部分進行著色。利用放射線照射發生著色之化合物為於放射線照射前為無色或淡色、利用放射線照射變為有色之化合物，可列舉例如隱色染料等。利用放射線照射發生著色之化合物之使用比率可適當設定。 The radiation-curable adhesive layer 12 may contain a compound which is colored by radiation irradiation, if necessary. By including the compound colored by radiation irradiation in the adhesive layer 12, it is possible to color only the portion irradiated with radiation. The compound which is colored by radiation irradiation is a colorless or pale color before irradiation with radiation, and a compound which becomes colored by radiation irradiation, and examples thereof include a leuco dye. The ratio of use of the compound which is colored by radiation irradiation can be appropriately set.

黏著劑層12之厚度沒有特別限定，就兼顧晶片切割面缺口之防止及膜狀接著劑3之固定保持等方面而言，較佳為1~50μm之程度。較佳為2~30μm，進而較佳為5~25μm。 The thickness of the adhesive layer 12 is not particularly limited, and is preferably about 1 to 50 μm in terms of prevention of the chip cut surface notch and fixing of the film-like adhesive 3. It is preferably 2 to 30 μm, and more preferably 5 to 25 μm.

附有膜狀接著劑之切晶帶10之膜狀接著劑3較佳為由隔離膜進行保護(未圖示)。隔離膜具有於供於實用之前作為保護膜狀接著劑3之保護材料之功能。隔離膜於向膜狀接著劑3上貼合工件時被剝離。作為隔離膜，亦可使用聚對苯二甲酸乙二酯(PET)、聚乙烯、聚丙烯、或利用氟系剝離劑、丙烯酸長鏈烷基酯系剝離劑等剝離劑進行過表面塗佈之塑膠膜或紙等。 The film-like adhesive 3 of the dicing tape 10 with a film-like adhesive is preferably protected by a separator (not shown). The separator has a function as a protective material for protecting the film-like adhesive 3 before being put to practical use. The separator is peeled off when the workpiece is attached to the film-like adhesive 3. As the separator, polyethylene terephthalate (PET), polyethylene, polypropylene, or a surface release coating using a release agent such as a fluorine-based release agent or a long-chain alkyl acrylate release agent may be used. Plastic film or paper.

附有膜狀接著劑之切晶帶10可用通常之方法製造。例如，藉由將切晶帶1之黏著劑層12與膜狀接著劑3貼合，可製造附有膜狀接著劑之切晶帶10。 The dicing tape 10 with a film-like adhesive can be produced by a usual method. For example, by bonding the adhesive layer 12 of the dicing tape 1 to the film-like adhesive 3, a dicing tape 10 with a film-like adhesive can be produced.

於剝離溫度25℃、剝離速度300mm/分鐘之條件下將膜狀接著劑3自切晶帶1剝離時之剝離力較佳為0.01~3.00N/20mm。若未達0.01N/20mm，則有於切割時發生晶片飛散之虞。另一方面，若超過3.00N/20mm，則有拾取變得困難之傾向。 The peeling force of the film-like adhesive 3 from the dicing tape 1 at a peeling temperature of 25 ° C and a peeling speed of 300 mm/min is preferably 0.01 to 3.00 N / 20 mm. If it is less than 0.01 N/20 mm, there is a problem that the wafer scatters during dicing. On the other hand, when it exceeds 3.00 N/20 mm, picking becomes difficult.

[半導體裝置之製造方法] [Method of Manufacturing Semiconductor Device]

對半導體裝置之製造方法進行說明。 A method of manufacturing a semiconductor device will be described.

如圖4所示，將附有膜狀接著劑之切晶帶10壓接於半導體晶圓4。作為半導體晶圓4，可列舉矽晶圓、碳化矽晶圓、化合物半導體晶圓等。作為化合物半導體晶圓，可列舉氮化鎵晶圓等。 As shown in FIG. 4, the dicing tape 10 with a film-like adhesive is pressure-bonded to the semiconductor wafer 4. Examples of the semiconductor wafer 4 include a germanium wafer, a tantalum carbide wafer, and a compound semiconductor wafer. As the compound semiconductor wafer, a gallium nitride wafer or the like can be cited.

作為壓接方法，可列舉例如利用壓接輥等按壓裝置進行按壓之方法等。 Examples of the pressure bonding method include a method of pressing by a pressing device such as a pressure roller, and the like.

壓接溫度(貼附溫度)較佳為35℃以上，更佳為37℃以上。壓接溫度之上限較佳為低，較佳為50℃以下，更佳為45℃以下。藉由於低溫下進行壓接，可抑制半導體晶圓4之翹曲。 The crimping temperature (attachment temperature) is preferably 35 ° C or higher, more preferably 37 ° C or higher. The upper limit of the crimping temperature is preferably low, preferably 50 ° C or lower, more preferably 45 ° C or lower. The warpage of the semiconductor wafer 4 can be suppressed by crimping at a low temperature.

又，壓力較佳為1×105Pa~1×107Pa，更佳為2×105Pa~8×106Pa。 Further, the pressure is preferably from 1 × 10 5 Pa to 1 × 10 7 Pa, more preferably from 2 × 10 5 Pa to 8 × 10 6 Pa.

如圖5所示，藉由切割半導體晶圓4，而形成晶片接著用晶片41。晶片接著用晶片41具備膜狀接著劑3及配置於膜狀接著劑3上之半導體晶片5。於本步驟中，例如可採用切入至附有膜狀接著劑之切晶帶10之被稱作全切之切割方式等。作為本步驟中使用之切割裝置，沒有特別限定，可使用先前公知之裝置。又，半導體晶圓4係利用附有膜狀接著劑之切晶帶10進行接著固定，因而可抑制晶片缺口或晶片飛散，並且亦可抑制半導體晶圓4之破損。 As shown in FIG. 5, a wafer subsequent wafer 41 is formed by dicing the semiconductor wafer 4. The wafer subsequent wafer 41 includes a film-like adhesive 3 and a semiconductor wafer 5 disposed on the film-like adhesive 3. In this step, for example, a cutting method called a full cut which cuts into the dicing tape 10 with a film-like adhesive can be used. The cutting device used in this step is not particularly limited, and a conventionally known device can be used. Further, since the semiconductor wafer 4 is subsequently fixed by the dicing tape 10 with the film-like adhesive, the wafer notch or the wafer scattering can be suppressed, and the semiconductor wafer 4 can be prevented from being damaged.

對晶片接著用晶片41進行拾取。作為拾取之方法，沒有特別限定，可採用先前公知之各種方法。可列舉例如以下方法等：將晶片接著用晶片41自切晶帶1側利用針上頂，並利用拾取裝置對被頂起之晶片接著用晶片41進行拾取。 The wafer is then picked up with wafer 41. The method of picking up is not particularly limited, and various methods known in the prior art can be employed. For example, the following method or the like is used: the wafer subsequent wafer 41 is lifted from the side of the dicing tape 1 by the needle, and the wafer to be lifted is then picked up by the wafer 41 by the pick-up device.

黏著劑層12為紫外線硬化型之情形時，於對黏著劑層12進行紫外線照射後進行拾取。藉此，黏著劑層12對晶片接著用晶片41之黏著力下降，因而可容易地拾取晶片接著用晶片41。對於紫外線照射時之照射強度、照射時間等條件沒有特別限定，根據需要適當設定即可。 When the adhesive layer 12 is an ultraviolet curing type, it is picked up after ultraviolet irradiation of the adhesive layer 12. Thereby, the adhesion of the adhesive layer 12 to the wafer following the wafer 41 is lowered, so that the wafer can be easily picked up by the wafer 41. The conditions such as the irradiation intensity and the irradiation time at the time of ultraviolet irradiation are not particularly limited, and may be appropriately set as necessary.

如圖6所示，藉由將晶片接著用晶片41壓接於被接著體6，而得到附有半導體晶片之被接著體61。附有半導體晶片之被接著體61具備被接著體6、配置於被接著體6上之膜狀接著劑3、及配置於膜狀接著劑3上之半導體晶片5。 As shown in FIG. 6, the wafer is bonded to the adherend 6 by the wafer 41, whereby the adherend 61 to which the semiconductor wafer is attached is obtained. The adherend 61 to which the semiconductor wafer is attached includes the adherend 6 , the film-like adhesive 3 disposed on the adherend 6 , and the semiconductor wafer 5 disposed on the film-like adhesive 3 .

將晶片接著用晶片41壓接於被接著體6之溫度(以下稱為「晶片黏著溫度」)較佳為80℃以上，更佳為90℃以上。又，晶片黏著溫度較佳為150℃以下，更佳為130℃以下。 The temperature at which the wafer is subsequently pressed against the adherend 6 by the wafer 41 (hereinafter referred to as "wafer adhesion temperature") is preferably 80 ° C or higher, more preferably 90 ° C or higher. Further, the wafer adhesion temperature is preferably 150 ° C or lower, more preferably 130 ° C or lower.

藉由將附有半導體晶片之被接著體61於加壓下進行加熱，而使膜狀接著劑3硬化。藉由於加壓下使膜狀接著劑3熱硬化，而可消除於膜狀接著劑3與被接著體6之間存在之孔隙，可確保膜狀接著劑3與被接著體6接觸之面積。 The film-like adhesive 3 is cured by heating the adherend 61 with the semiconductor wafer under pressure. By thermally curing the film-like adhesive 3 under pressure, the pores existing between the film-like adhesive 3 and the adherend 6 can be eliminated, and the area in which the film-like adhesive 3 is in contact with the adherend 6 can be ensured.

作為於加壓下進行加熱之方法，可列舉例如對配置於填充有惰性氣體之腔室內之附有半導體晶片之被接著體61進行加熱之方法等。加壓氣氛之壓力較佳為0.5kg/cm2(4.9×10-2MPa)以上，更佳為1kg/cm2(9.8×10-2MPa)以上，進而較佳為5kg/cm2(4.9×10-1MPa)以上。若為0.5kg/cm2以上，則可容易地消除於膜狀接著劑3與被接著體6之間存在之孔隙。加壓氣氛之壓力較佳為20kg/cm2(1.96MPa)以下，更佳為18kg/cm2(1.77MPa)以下，進而較佳為15kg/cm2(1.47MPa)以下。若為20kg/cm2以下，則可抑制過度加壓導致之膜狀接著劑3之溢出。 The method of heating under pressure may, for example, be a method of heating the adherend 61 with a semiconductor wafer placed in a chamber filled with an inert gas. The pressure in the pressurized atmosphere is preferably 0.5 kg/cm 2 (4.9 × 10 -2 MPa) or more, more preferably 1 kg/cm 2 (9.8 × 10 -2 MPa) or more, and still more preferably 5 kg/cm 2 (4.9). ×10 -1 MPa) or more. When it is 0.5 kg/cm 2 or more, the pores existing between the film-like adhesive 3 and the adherend 6 can be easily eliminated. The pressure of the pressurized atmosphere is preferably 20kg / cm 2 (1.96MPa) or less, more preferably 18kg / cm (1.77MPa) 2 or less, and further preferably 15kg / cm 2 (1.47MPa) or less. When it is 20 kg/cm 2 or less, the overflow of the film-like adhesive 3 due to excessive pressurization can be suppressed.

加熱溫度較佳為80℃以上，更佳為100℃以上，進而較佳為120℃以上，尤佳為170℃以上。若為80℃以上，則可使膜狀接著劑3為適度之硬度，可藉由加壓硬化有效地使孔隙消失。加熱溫度較佳為260℃以下，更佳為220℃以下，進而較佳為200℃以下，尤佳為180℃以下。若為260℃以下，則可防止硬化前之膜狀接著劑3之分解。 The heating temperature is preferably 80 ° C or higher, more preferably 100 ° C or higher, further preferably 120 ° C or higher, and particularly preferably 170 ° C or higher. When it is 80 ° C or more, the film-like adhesive 3 can be made to have a moderate hardness, and the pores can be effectively eliminated by press hardening. The heating temperature is preferably 260 ° C or lower, more preferably 220 ° C or lower, further preferably 200 ° C or lower, and particularly preferably 180 ° C or lower. When it is 260 ° C or less, decomposition of the film-like adhesive 3 before hardening can be prevented.

加熱時間較佳為0.1小時以上，更佳為0.2小時以上，進而較佳為 0.5小時以上。若為0.1小時以上，則可充分地得到加壓之效果。加熱時間較佳為24小時以下，更佳為3小時以下，進而較佳為1小時以下。 The heating time is preferably 0.1 hour or longer, more preferably 0.2 hour or longer, and further preferably More than 0.5 hours. When it is 0.1 hour or more, the effect of pressurization can fully be obtained. The heating time is preferably 24 hours or shorter, more preferably 3 hours or shorter, and still more preferably 1 hour or shorter.

如圖7所示，進行利用接合線7將被接著體6之端子部(內部引線)之前端與半導體晶片5上之電極墊(未圖示)進行電性連接之打線接合步驟。作為接合線7，可使用例如金線、鋁線或銅線等。進行打線接合時之溫度較佳為80℃以上，更佳為120℃以上，該溫度較佳為250℃以下，更佳為175℃以下。又，以其加熱時間為數秒~數分鐘(例如1秒~1分鐘)之條件進行。接線係於加熱達到上述溫度範圍內之狀態下藉由併用超音波帶來之振動能量及施加加壓帶來之壓接能量而進行。 As shown in FIG. 7, a wire bonding step of electrically connecting the front end of the terminal portion (internal lead) of the adherend 6 to the electrode pad (not shown) on the semiconductor wafer 5 by the bonding wire 7 is performed. As the bonding wire 7, for example, a gold wire, an aluminum wire, a copper wire, or the like can be used. The temperature at the time of wire bonding is preferably 80 ° C or higher, more preferably 120 ° C or higher, and the temperature is preferably 250 ° C or lower, more preferably 175 ° C or lower. Further, the heating time is carried out under the conditions of several seconds to several minutes (for example, one second to one minute). The wiring is performed by using the vibration energy of the ultrasonic wave and the pressure of the pressure applied by the pressure in a state where the heating reaches the above temperature range.

繼而，進行利用密封樹脂8將半導體晶片5密封之密封步驟。本步驟係為了保護搭載於被接著體6之半導體晶片5及接合線7而進行。本步驟藉由用模具對密封用樹脂進行成形而進行。作為密封樹脂8，例如使用環氧系樹脂。樹脂密封時之加熱溫度較佳為165℃以上，更佳為170℃以上，加熱溫度較佳為185℃以下，更佳為180℃以下。 Then, a sealing step of sealing the semiconductor wafer 5 with the sealing resin 8 is performed. This step is performed to protect the semiconductor wafer 5 and the bonding wires 7 mounted on the adherend 6 . This step is carried out by molding the sealing resin with a mold. As the sealing resin 8, for example, an epoxy resin is used. The heating temperature at the time of resin sealing is preferably 165 ° C or higher, more preferably 170 ° C or higher, and the heating temperature is preferably 185 ° C or lower, more preferably 180 ° C or lower.

根據需要可進一步對密封物進行加熱(後硬化步驟)。藉此，可使於密封步驟中硬化不足之密封樹脂8完全硬化。加熱溫度可適當設定。 The seal can be further heated as needed (post-hardening step). Thereby, the sealing resin 8 which is insufficiently hardened in the sealing step can be completely cured. The heating temperature can be set as appropriate.

如上所述，藉由包括將具備膜狀接著劑3及配置於膜狀接著劑3上之半導體晶片5之晶片接著用晶片41壓接至被接著體6之步驟的方法，可製造半導體裝置。該方法進而包括如下步驟：對藉由將晶片接著用晶片41壓接於被接著體6之步驟而得到之附有半導體晶片之被接著體61進行加熱，藉此使膜狀接著劑3硬化。 As described above, the semiconductor device can be manufactured by a method including a step of crimping the wafer including the film-like adhesive 3 and the semiconductor wafer 5 disposed on the film-like adhesive 3 to the substrate 6 by the wafer 41. The method further includes the step of heating the adherend 61 with the semiconductor wafer obtained by the step of crimping the wafer to the adherend 6 with the wafer 41, whereby the film-like adhesive 3 is cured.

更詳細而言，實施形態1之方法包括：準備附有膜狀接著劑之切晶帶10之步驟；將半導體晶圓4壓接於膜狀接著劑3之步驟；藉由對配置於膜狀接著劑3上之半導體晶圓4進行切割而形成晶片接著用晶片41之步驟；將晶片接著用晶片41壓接於被接著體6之步驟；對藉由將晶 片接著用晶片41壓接於被接著體6之步驟而得到之附有半導體晶片之被接著體61進行加熱，藉此使膜狀接著劑3硬化之步驟。 More specifically, the method of the first embodiment includes the steps of: preparing a dicing tape 10 with a film-like adhesive; crimping the semiconductor wafer 4 to the film-like adhesive 3; and disposing the film in a film form. The semiconductor wafer 4 on the third agent 3 is diced to form a wafer followed by the wafer 41; the wafer is subsequently bonded to the adherend 6 by the wafer 41; The sheet is then subjected to a step of curing the film-like adhesive 3 by heating the adherend 61 with the semiconductor wafer obtained by the step of pressing the wafer 41 to the adherend 6 to be cured.

[實施例] [Examples]

以下，對於本發明，使用實施例詳細進行說明，但本發明只要不超出其主旨，則不限於以下之實施例。 Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited to the following examples as long as the gist of the invention is not exceeded.

對於實施例中使用之成分進行說明。 The components used in the examples will be described.

熱塑性樹脂：Nagase Chemtex股份有限公司製之Teisan Resin SG-70L(具備羧基及羥基之丙烯酸系共聚物、Mw：90萬、酸值：5mgKOH/g、玻璃轉移溫度：-13℃) Thermoplastic resin: Teisan Resin SG-70L manufactured by Nagase Chemtex Co., Ltd. (acrylic copolymer having carboxyl group and hydroxyl group, Mw: 900,000, acid value: 5 mgKOH/g, glass transition temperature: -13 ° C)

環氧樹脂1：日本化藥股份有限公司製之EOCN-1020-4(環氧當量198g/eq.、於25℃為固體之環氧樹脂) Epoxy Resin 1: EOCN-1020-4, manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent: 198 g/eq., epoxy resin at 25 ° C)

環氧樹脂2：三菱化學股份有限公司製之JER828(具有雙酚型骨架之於25℃為液態之環氧樹脂、環氧當量184g/eq.~194g/eq.) Epoxy Resin 2: JER828 manufactured by Mitsubishi Chemical Corporation (epoxy resin having a bisphenol type skeleton at 25 ° C, epoxy equivalent of 184 g / eq. ~ 194 g / eq.)

環氧樹脂3：DIC股份有限公司製之EPICLON EXA-4816(環氧當量403g/eq.、於25℃為液態之環氧樹脂) Epoxy Resin 3: EPICLON EXA-4816 manufactured by DIC Corporation (epoxy equivalent: 403 g/eq., epoxy resin at 25 ° C)

酚樹脂1：明和化成股份有限公司製之MEH-8000H(羥基當量139g/eq.~143g/eq.之酚樹脂) Phenol Resin 1: MEH-8000H (hydroxyl equivalent of 139 g/eq. to 143 g/eq. of phenol resin) manufactured by Minghe Chemical Co., Ltd.

酚樹脂2：明和化成股份有限公司製之MEH-8005(羥基當量133g/eq.~138g/eq.之酚樹脂) Phenol Resin 2: MEH-8005 (hydroxyl equivalent of 133 g/eq. to 138 g/eq. of phenol resin) manufactured by Minghe Chemical Co., Ltd.

導電性粒子1：三井金屬礦業股份有限公司製之1200YP(薄片狀銅粉、平均粒徑3.5μm、縱橫比：10) Conductive particle 1: 1200YP (flaky copper powder, average particle size 3.5μm, aspect ratio: 10) manufactured by Mitsui Mining Co., Ltd.

導電性粒子2：三井金屬礦業股份有限公司製之1400YP(薄片狀銅粉、平均粒徑7.0μm、縱橫比：25) Conductive particle 2: 1400YP manufactured by Mitsui Mining Co., Ltd. (flaky copper powder, average particle size 7.0 μm, aspect ratio: 25)

導電性粒子3：三井金屬礦業股份有限公司製之SPH02J(銀微粒之凝聚體、凝聚體之平均粒徑1.8μm、無定形) Conductive particle 3: SPH02J manufactured by Mitsui Mining Co., Ltd. (aggregate of silver fine particles, average particle size of aggregates of 1.8 μm, amorphous)

觸媒：北興化學股份有限公司製之TPP-K(四苯基硼酸四苯基鏻) Catalyst: TPP-K (tetraphenylphosphonium tetraphenylborate) manufactured by Beixing Chemical Co., Ltd.

[膜狀接著劑之製作] [Production of film-like adhesive]

根據表1中記載之調配比，將表1中記載之各成分及溶劑(甲基乙基酮)加入混合動力攪拌機(KEYENCE製HM-500)之攪拌釜中，以攪拌模式攪拌混合3分鐘。將所得到之清漆用模嘴塗佈機塗佈於脫模處理膜(三菱樹脂股份有限公司製之MRA50)後，進行乾燥，製作厚度30μm之膜狀接著劑。 The components and the solvent (methyl ethyl ketone) described in Table 1 were placed in a stirred tank of a hybrid stirrer (HM-500 manufactured by Keyence) according to the blending ratios shown in Table 1, and stirred and mixed for 3 minutes in a stirring mode. The obtained varnish was applied to a release-treated film (MRA50, manufactured by Mitsubishi Plastics Co., Ltd.) using a die coater, and then dried to prepare a film-like adhesive having a thickness of 30 μm.

[硬化物之製作] [Production of hardened material]

使用乾燥機將膜狀接著劑於140℃加熱1小時，繼而於200℃加熱2小時，藉此得到硬化物。 The film-like adhesive was heated at 140 ° C for 1 hour using a dryer, followed by heating at 200 ° C for 2 hours, thereby obtaining a cured product.

[評價1] [Evaluation 1]

對於所得到之膜狀接著劑、硬化物進行以下之評價。將結果示於表1。 The following film-like adhesive and cured product were evaluated as follows. The results are shown in Table 1.

(熱導率) (Thermal conductivity)

藉由使用Ai-phase股份有限公司製之Ai-Phase Mobile之溫度波熱分析法(TWA法)，測定熱擴散係數α(m2/s)。使用SII Nanotechnology股份有限公司製之DSC6220，於升溫速度10℃/分鐘、溫度20℃~300℃之條件下進行DSC測定，用JIS手冊(比熱容測定方法K-7123 1987)中記載之方法求出比熱容Cp(J/g‧℃)。測定比重。然後，藉由下式求出熱導率。 The thermal diffusivity α (m 2 /s) was measured by a temperature wave thermal analysis method (TWA method) using Ai-Phase Mobile manufactured by Ai-phase Co., Ltd. Using DSC6220 manufactured by SII Nanotechnology Co., Ltd., the DSC measurement was carried out under the conditions of a temperature increase rate of 10 ° C / min and a temperature of 20 ° C to 300 ° C, and the specific heat capacity was determined by the method described in JIS Manual (specific heat capacity measurement method K-7123 1987). Cp (J/g‧°C). Determine the specific gravity. Then, the thermal conductivity was obtained by the following formula.

[數1] [Number 1]

λ=α×ρ×Cρ λ=α×ρ×Cρ

λ：熱導率(W/m‧K) λ: thermal conductivity (W/m‧K)

α：熱擴散係數α(m2/s) α: thermal diffusivity α (m 2 /s)

ρ：密度(kg/m3) ρ: density (kg/m 3 )

Cρ：比熱容(kJ/(kg‧K)) Cρ: specific heat capacity (kJ/(kg‧K))

(電阻率) (resistivity)

如圖8所示，準備具有基板101及配置於基板101上之佈線寬度2mm、佈線厚度10μm之銅佈線102a、102b、102c、102d的評價基板100。銅佈線102a與銅佈線102b之間隔、銅佈線102b與銅佈線102c之間隔、銅佈線102c與銅佈線102d之間隔為15mm。自膜狀接著劑切取10mm×50mm×30μm之試驗膜200。如圖9所示，於70℃、0.5MPa、10mm/s之條件下將試驗膜200壓接於銅佈線102a、102b、102c、102d，製作試驗基板300。將試驗基板300於氮氣氣氛中於140℃加熱1小時，繼而於200℃加熱2小時，藉此使試驗膜200硬化。使用毫歐計測定銅佈線102a與銅佈線102b間之電阻值、銅佈線102a與銅佈線102c間之電阻值、銅佈線102a與銅佈線102d間之電阻值。根據各電阻值算出銅佈線102a與銅佈線102b間之體電阻值、銅佈線102b與銅佈線102c間之體電阻值、銅佈線102c與銅佈線102d間之體電阻值。進而，算出三個體電阻值之平均值。然後，藉由下式算出電阻率。 As shown in FIG. 8, the evaluation substrate 100 having the substrate 101 and the copper wirings 102a, 102b, 102c, and 102d having a wiring width of 2 mm and a wiring thickness of 10 μm disposed on the substrate 101 was prepared. The distance between the copper wiring 102a and the copper wiring 102b, the distance between the copper wiring 102b and the copper wiring 102c, and the interval between the copper wiring 102c and the copper wiring 102d are 15 mm. A test film 200 of 10 mm × 50 mm × 30 μm was cut out from the film-like adhesive. As shown in FIG. 9, the test film 200 was pressure-bonded to the copper wirings 102a, 102b, 102c, and 102d under conditions of 70 ° C, 0.5 MPa, and 10 mm/s to prepare a test substrate 300. The test substrate 300 was heated at 140 ° C for 1 hour in a nitrogen atmosphere, followed by heating at 200 ° C for 2 hours, whereby the test film 200 was cured. The resistance value between the copper wiring 102a and the copper wiring 102b, the resistance value between the copper wiring 102a and the copper wiring 102c, and the resistance value between the copper wiring 102a and the copper wiring 102d were measured using a milliohm meter. The volume resistance value between the copper wiring 102a and the copper wiring 102b, the bulk resistance value between the copper wiring 102b and the copper wiring 102c, and the bulk resistance value between the copper wiring 102c and the copper wiring 102d are calculated from the respective resistance values. Further, the average value of the three bulk resistance values was calculated. Then, the specific resistance was calculated by the following formula.

[數2] [Number 2]

ρ=R×A/L ρ=R×A/L

ρ：電阻率 ρ: resistivity

R：電阻 R: resistance

A：截面面積 A: sectional area

L：導體長度 L: conductor length

[評價2] [Evaluation 2]

對導電性粒子1~3進行以下之評價。 The following evaluations were performed on the conductive particles 1 to 3.

(燒結) (sintering)

將配置於玻璃板上之導電性粒子1~3於140℃加熱1小時，繼而於200℃加熱2小時。於加熱前後，利用掃描型電子顯微鏡(SEM)觀察導電性粒子1~3。對於導電性粒子3，於加熱前未確認到燒結(熔合現象)，但於加熱後確認到燒結。另一方面，對於導電性粒子1~2，於 加熱前後未確認到燒結。 The conductive particles 1 to 3 placed on the glass plate were heated at 140 ° C for 1 hour, and then heated at 200 ° C for 2 hours. The conductive particles 1 to 3 were observed by a scanning electron microscope (SEM) before and after heating. In the conductive particles 3, sintering (fusion phenomenon) was not confirmed before heating, but sintering was confirmed after heating. On the other hand, for the conductive particles 1 to 2, No sintering was confirmed before and after heating.

3‧‧‧膜狀接著劑 3‧‧‧membranous adhesive

Claims (10)

一種導電性膜狀接著劑，其藉由加熱進行硬化得到之硬化物之第1熱導率相對於上述加熱前之第2熱導率之比之值(上述第1熱導率/上述第2熱導率)為2.0以上。 A conductive film-like adhesive which has a ratio of a first thermal conductivity of a cured product obtained by curing by heating to a second thermal conductivity before heating (the first thermal conductivity / the second The thermal conductivity) is 2.0 or more. 如請求項1之導電性膜狀接著劑，其中上述第1熱導率為1.7W/m‧K以上。 The conductive film-like adhesive according to claim 1, wherein the first thermal conductivity is 1.7 W/m‧K or more. 如請求項1之導電性膜狀接著劑，其含有導電性粒子，且上述導電性粒子含有薄片狀金屬粒子及於200℃至少一部分會燒結之燒結性金屬粒子。 The conductive film-like adhesive according to claim 1, which contains conductive particles, and the conductive particles contain flaky metal particles and sinter metal particles which are sintered at least at 200 ° C. 如請求項3之導電性膜狀接著劑，其中上述導電性粒子100重量%中之上述燒結性金屬粒子之含量為5重量%~50重量%。 The conductive film-like adhesive according to claim 3, wherein the content of the sinter metal particles in 100% by weight of the conductive particles is 5% by weight to 50% by weight. 如請求項1之導電性膜狀接著劑，其中含有樹脂成分，且上述樹脂成分含有熱塑性樹脂、熱硬化性樹脂。 The conductive film-like adhesive of claim 1, which contains a resin component, and the resin component contains a thermoplastic resin or a thermosetting resin. 如請求項5之導電性膜狀接著劑，其中進而含有硬化劑。 The conductive film-like adhesive of claim 5, which further contains a curing agent. 如請求項1之導電性膜狀接著劑，其係晶片接著用。 The conductive film-like adhesive of claim 1 is used in the following wafer. 一種附有膜狀接著劑之切晶帶，其具備：切晶帶、及配置於上述切晶帶上之如請求項1之導電性膜狀接著劑。 A dicing tape provided with a film-like adhesive comprising: a dicing tape; and a conductive film-like adhesive according to claim 1 disposed on the dicing tape. 如請求項8之附有膜狀接著劑之切晶帶，其中上述切晶帶具備基材及配置於上述基材上之黏著劑層。 A zoning tape having a film-like adhesive agent as claimed in claim 8, wherein the dicing tape comprises a substrate and an adhesive layer disposed on the substrate. 一種半導體裝置之製造方法，其包括如下步驟：將具備如請求項1至7中任一項之導電性膜狀接著劑、及配置於上述導電性膜狀接著劑上之半導體晶片的晶片接著用晶片壓接於被接著體。 A method of manufacturing a semiconductor device, comprising the steps of: using a conductive film-like adhesive according to any one of claims 1 to 7 and a semiconductor wafer disposed on the conductive film-like adhesive The wafer is crimped to the adherend.
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