TW202013534A - Dicing die bond film - Google Patents

Dicing die bond film Download PDF

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TW202013534A
TW202013534A TW108115440A TW108115440A TW202013534A TW 202013534 A TW202013534 A TW 202013534A TW 108115440 A TW108115440 A TW 108115440A TW 108115440 A TW108115440 A TW 108115440A TW 202013534 A TW202013534 A TW 202013534A
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adhesive layer
adhesive
die
bonding film
cut
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TW108115440A
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Chinese (zh)
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木村雄大
高本尚英
大西謙司
宍戸雄一郎
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日商日東電工股份有限公司
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/77Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
    • H01L21/78Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
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Abstract

To provide a dicing die bond film provided with an adhesive layer suitable for realizing good adhesion to a frame member such as a ring frame while securing the cleaving property in an expanding process. A dicing die bond film X according to the present invention includes a dicing tape 10 and an adhesive layer 20. The dicing tape 10 has a laminated structure including a base material 11 and an adhesive layer 12. The adhesive layer 20 is in close contact with the adhesive layer 12 so as to be peelable. The adhesive layer 20 has a tensile storage modulus of 5 to 120 MPa at 25 DEG C measured under a predetermined condition for an adhesive layer sample piece having a width of 10 mm and a thickness of 160 [mu]m. In addition, the adhesive layer 20 has a tensile storage modulus of 3000 to 6000 MPa at -15 DEG C measured under a predetermined condition for an adhesive layer sample piece having a width of 5 mm and a thickness of 80 [mu]m.

Description

切晶黏晶膜Crystal cutting film

本發明係關於一種可於半導體裝置之製造過程中使用之切晶黏晶膜。The invention relates to a die-cut crystal bonding film which can be used in the manufacturing process of semiconductor devices.

於半導體裝置之製造過程中,於獲得帶黏晶用之晶片相當尺寸之接著膜之半導體晶片、即,附有黏晶膜之半導體晶片之方面,存在使用切晶黏晶膜之情形。切晶黏晶膜具有與作為加工對象之半導體晶圓相對應之尺寸,例如具有:切晶帶,其包含基材及黏著劑層;及黏晶膜(接著劑層),其可剝離地密接於該黏著劑層側。In the manufacturing process of a semiconductor device, in order to obtain a semiconductor wafer with a bonding film of a size equivalent to that of a die-bonding wafer, that is, a semiconductor wafer with a die-bonding film, there is a case where a die-cut die-bonding film is used. The die-bonding die-bonding film has a size corresponding to the semiconductor wafer to be processed, for example, it includes: a die-cutting tape, which includes a substrate and an adhesive layer; and a die-bonding film (adhesive layer), which can be peelably adhered On the side of the adhesive layer.

作為使用切晶黏晶膜而獲得附有黏晶膜之半導體晶片之方法之一,已知有經過用以使切晶黏晶膜中之切晶帶延伸而割斷黏晶膜之步驟之方法。於該方法中,首先,於切晶黏晶膜之黏晶膜上貼合半導體晶圓。該半導體晶圓例如係以其後可與黏晶膜一併被割斷而單片化為複數個半導體晶片之方式進行加工而成者。其次,為了以分別與半導體晶片密接之複數個黏晶膜小片由切晶帶上之黏晶膜所產生之方式割斷該黏晶膜,使用延伸裝置而使切晶黏晶膜之切晶帶延伸。於該延伸步驟中,於黏晶膜中之相當於割斷部位之部位於黏晶膜上之半導體晶圓上亦發生割斷,於切晶黏晶膜或切晶帶上半導體晶圓被單片化為複數個半導體晶片。其次,為了對切晶帶上之割斷後之複數個附有黏晶膜之半導體晶片擴大相隔距離,而再次進行延伸步驟。其次,例如於經過洗淨步驟後,各半導體晶片與和其密接之晶片相當尺寸之黏晶膜一併自切晶帶之下側被拾取機構之銷頂起後,自切晶帶上被拾取。以上述方式獲得帶黏晶膜之半導體晶片。該附有黏晶膜之半導體晶片經由該黏晶膜,藉由黏晶而固著於安裝基板等被接著體。例如關於與如上所述般使用之切晶黏晶膜相關之技術,例如係記載於下述專利文獻1~3中。 [先前技術文獻] [專利文獻]As one of the methods for obtaining a semiconductor wafer to which a die-bonding film is attached using a die-bonding film, there is known a method of cutting a die-bonding film by extending a dicing tape in the die-bonding film. In this method, first, a semiconductor wafer is bonded on the die-bonding film of the dicing die-bonding film. The semiconductor wafer is processed, for example, in such a manner that it can be cut together with the crystal bonding film and singulated into a plurality of semiconductor chips. Secondly, in order to cut the die-bonding film in such a manner that a plurality of die-bonding film pieces which are in close contact with the semiconductor wafer are generated by the die-bonding film on the die-cutting tape, an extension device is used to extend the die-cutting tape of the die-cutting die-bonding film . In this extension step, the semiconductor wafer on which the portion corresponding to the cut-off portion of the bonding film is located on the bonding film also cuts, and the semiconductor wafer is singulated on the bonding wafer or the cutting tape It is a plurality of semiconductor wafers. Secondly, in order to increase the separation distance of the plurality of semiconductor wafers with a crystal bonding film after being cut on the dicing tape, the stretching step is performed again. Secondly, for example, after the cleaning step, each semiconductor wafer and the die-bonding film of the same size as the wafer that is in close contact with it are lifted from the lower side of the dicing tape by the pins of the pick-up mechanism, and then picked up from the dicing tape . In this way, a semiconductor wafer with a viscous crystal film is obtained. The semiconductor wafer with a die-bonding film is fixed to a substrate such as a mounting substrate by die-bonding through the die-bonding film. For example, the technology related to the die-cut crystal bonding film used as described above is described in Patent Documents 1 to 3 below, for example. [Prior Technical Literature] [Patent Literature]

[專利文獻1]日本專利特開2007-2173號公報 [專利文獻2]日本專利特開2010-177401號公報 [專利文獻3]日本專利特開2012-23161號公報[Patent Document 1] Japanese Patent Laid-Open No. 2007-2173 [Patent Document 2] Japanese Patent Laid-Open No. 2010-177401 [Patent Document 3] Japanese Patent Laid-Open No. 2012-23161

[發明所欲解決之問題][Problems to be solved by the invention]

圖15係對先前型之切晶黏晶膜Y利用其剖面模式圖表示者。切晶黏晶膜Y包含切晶帶60及黏晶膜70。切晶帶60呈現基材61與發揮黏著力之黏著劑層62之積層構造。黏晶膜70利用黏著劑層62之黏著力而與黏著劑層62密接。此種切晶黏晶膜Y具有與作為半導體裝置之製造過程中之加工對象或工件之半導體晶圓相對應之尺寸之圓盤形狀,可用於上述延伸步驟。例如,如圖16所示,於半導體晶圓81貼合於黏晶膜70,且環狀框82貼附於黏著劑層62之狀態下,實施上述延伸步驟。半導體晶圓81例如係以可單片化為複數個半導體晶片之方式加工而成者。FIG. 15 shows the cross-sectional schematic diagram of the previous type of die-cut crystal bonding film Y. The die-cut die-bonding film Y includes a die-cutting tape 60 and a die-bonding film 70. The dicing tape 60 has a laminated structure of a base material 61 and an adhesive layer 62 exerting an adhesive force. The adhesive film 70 utilizes the adhesive force of the adhesive layer 62 to be in close contact with the adhesive layer 62. Such a die-cut die-bonding film Y has a disc shape of a size corresponding to a semiconductor wafer that is a processing object or a workpiece in the manufacturing process of a semiconductor device, and can be used for the above-mentioned extending step. For example, as shown in FIG. 16, the above-mentioned extending step is performed in a state where the semiconductor wafer 81 is bonded to the die-bonding film 70 and the ring frame 82 is attached to the adhesive layer 62. The semiconductor wafer 81 is processed by, for example, singulation into a plurality of semiconductor chips.

環狀框82係於貼附於切晶黏晶膜Y之狀態下,延伸裝置所具備之搬送臂等搬送機構於工件搬送時機械性地抵接之框構件。先前型之切晶黏晶膜Y係以此種環狀框82可利用切晶帶60之黏著劑層62之黏著力而固定於該膜之方式進行設計。即,先前型之切晶黏晶膜Y係具有於切晶帶60之黏著劑層62中於黏晶膜70之周圍確保環狀框貼合用區域之設計者。於此種設計中,黏著劑層62之外周端62e與黏晶膜70之外周端70e之間之膜面內方向之距離為10~30 mm左右。The ring frame 82 is a frame member that mechanically abuts a conveying mechanism such as a conveying arm provided in the stretching device when the workpiece is conveyed in a state of being attached to the die-bonding film Y. The previous die-cut die-bonding film Y is designed in such a manner that the ring frame 82 can be fixed to the film by using the adhesive force of the adhesive layer 62 of the die-cut tape 60. That is, the prior-type die-cut die-bonding film Y is a designer having an area around the die-bonding film 70 in the adhesive layer 62 of the die-cut tape 60 to secure the area for bonding the ring frame. In this design, the distance in the film plane direction between the outer peripheral end 62e of the adhesive layer 62 and the outer peripheral end 70e of the adhesive film 70 is about 10 to 30 mm.

本發明係基於如上所述之情況而構思出者,其目的在於提供一種切晶黏晶膜,該切晶黏晶膜具備作為適合於確保延伸步驟中之割斷性,並且實現對於環狀框等框構件之良好之貼合性之黏晶膜之黏著接著劑層。 [解決問題之技術手段]The present invention was conceived based on the circumstances described above, and its object is to provide a die-cut die-bonding film which is suitable for ensuring the cut-off property in the extension step and realize Adhesive layer of the adhesive film of the frame member with good adhesion. [Technical means to solve the problem]

由本發明所提供之切晶黏晶膜具備切晶帶及作為黏晶膜之黏著接著劑層。切晶帶具有包含基材與黏著劑層之積層構造。黏著接著劑層係可剝離地密接於切晶帶中之黏著劑層。黏著接著劑層對寬度10 mm及厚度160 μm之黏著接著劑層試樣片於初始夾頭間距離22.5 mm、頻率1 Hz、動態應變0.005%、及升溫速度10℃/min之條件下測定之25℃下之拉伸儲存模數(第1拉伸儲存模數)為5~120 MPa。並且,黏著接著劑層對寬度5 mm及厚度80 μm之黏著接著劑層試樣片於初始夾頭間距離10 mm、頻率900 Hz、動態應變0.005%、及升溫速度5℃/min之條件下測定之-15℃下之拉伸儲存模數(第2拉伸儲存模數)為3000~6000 MPa。此種構成之切晶黏晶膜可用於在半導體裝置之製造過程中獲得附有黏晶膜之半導體晶片。The die-cut adhesive film provided by the present invention includes a die-cut tape and an adhesive adhesive layer as the adhesive film. The dicing tape has a laminated structure including a base material and an adhesive layer. The adhesive layer is a layer of adhesive that can be peelably adhered to the dicing tape. The adhesive adhesive layer was measured under the conditions of an initial chuck distance of 22.5 mm, a frequency of 1 Hz, a dynamic strain of 0.005%, and a heating rate of 10 °C/min. The tensile storage modulus (first tensile storage modulus) at 25°C is 5 to 120 MPa. In addition, the thickness of the adhesive layer on the sample sheet of the adhesive layer with a width of 5 mm and a thickness of 80 μm is under the conditions of an initial chuck distance of 10 mm, a frequency of 900 Hz, a dynamic strain of 0.005%, and a heating rate of 5°C/min. The measured tensile storage modulus (second tensile storage modulus) at -15°C is 3000 to 6000 MPa. The die-cut die-bonding film with such a structure can be used to obtain a semiconductor wafer with a die-bonding film attached during the manufacturing process of a semiconductor device.

於半導體裝置之製造過程中,於如上所述般獲得附有黏晶膜之半導體晶片之方面,存在實施使用切晶黏晶膜而進行之延伸步驟、即,用於割斷之延伸步驟之情形。於該延伸步驟中,需要半導體晶圓等工件與環狀框等框構件均保持於切晶黏晶膜,並且黏晶膜可藉由切晶帶之延伸而被割斷。In the manufacturing process of a semiconductor device, in order to obtain a semiconductor wafer with a die-bonding film attached as described above, there are cases where an extension step performed using a die-bonding film, that is, an extension step for dicing is performed. In this extension step, it is required that both the workpiece such as a semiconductor wafer and the frame member such as the ring frame are held in the die-bonding die-bonding film, and the die-bonding film can be cut by the extension of the die-cutting tape.

關於作為本切晶黏晶膜之黏晶膜之黏著接著劑層,如上所述,於25℃下之上述第1拉伸儲存模數為5~120 MPa。此種構成於在切晶黏晶膜或其於黏著接著劑層中確保對於環狀框等框構件之常溫下之貼合力之方面較適宜。具體而言,該構成於在常溫下將框構件適當地貼附於切晶黏晶膜或其黏著接著劑層之方面較適宜。又,該構成於在延伸步驟之前後處於常溫之黏著接著劑層中實現良好之黏著力之方面較適宜。對切晶黏晶膜要求於自貼附於其之框構件剝離時於該框構件上不會產生糊劑殘留(剝離時殘渣之防止),結果就於本切晶黏晶膜中之黏著接著劑層中防止於常溫下之剝離時殘渣之觀點而言,於25℃下之第1拉伸儲存模數較佳為6 MPa以上,更佳為7 MPa以上。就於黏著接著劑層中實現對於框構件之常溫下之較高之貼合力之觀點而言,於25℃下之第1拉伸儲存模數較佳為110 MPa以下,更佳為100 MPa以下。Regarding the adhesive bonding agent layer of the die-bonding film as the present die-cutting die-bonding film, as described above, the first tensile storage modulus at 25°C is 5 to 120 MPa. Such a structure is more suitable for ensuring the bonding force to the frame member such as a ring frame at room temperature in the die-cut adhesive film or in the adhesive adhesive layer. Specifically, this configuration is suitable in that the frame member is appropriately attached to the die-cut die-bonding film or its adhesive adhesive layer at normal temperature. In addition, this configuration is more suitable for achieving good adhesion in the adhesive adhesive layer at normal temperature before and after the stretching step. The die-cut die-bonding film requires no paste residue on the frame member when peeling from the frame member attached to it (prevention of residue during peeling), and the result is adhesion to the die-cut die-bonding film From the viewpoint of preventing residues during peeling at normal temperature in the agent layer, the first tensile storage modulus at 25°C is preferably 6 MPa or more, and more preferably 7 MPa or more. From the viewpoint of achieving a higher bonding force to the frame member at normal temperature in the adhesive layer, the first tensile storage modulus at 25°C is preferably 110 MPa or less, more preferably 100 MPa or less .

並且,本切晶黏晶膜之黏著接著劑層如上所述,於-15℃下之第2拉伸儲存模數為3000~6000 MPa。此種構成適合於在-15℃及其附近之低溫下實施之延伸步驟中割斷黏著接著劑層,並且於在黏著接著劑層中確保對於框構件之低溫下之貼合力之方面較適宜。就於黏著接著劑層中實現低溫下之良好之割斷性之觀點而言,於-15℃下之第2拉伸儲存模數較佳為3200 MPa以上,更佳為3500 MPa以上。就於黏著接著劑層中實現低溫下之較高之貼合力之觀點而言,於-15℃下之第2拉伸儲存模數較佳為5800 MPa以下,更佳為5500 MPa以下。有延伸步驟實施溫度下之對框構件貼合力越高,該延伸步驟中之黏著接著劑層或切晶黏晶膜自框構件之剝離越得到抑制之傾向。In addition, as described above, the adhesive bonding agent layer of the die-cut adhesive film is as described above, and the second tensile storage modulus at -15°C is 3000 to 6000 MPa. This configuration is suitable for cutting off the adhesive layer in the extension step carried out at a low temperature of -15°C and its vicinity, and is more suitable in terms of securing the bonding force to the frame member at a low temperature in the adhesive layer. From the viewpoint of achieving good cleavage at low temperatures in the adhesive layer, the second tensile storage modulus at -15°C is preferably 3200 MPa or more, and more preferably 3500 MPa or more. From the viewpoint of achieving higher adhesion at low temperature in the adhesive layer, the second tensile storage modulus at -15°C is preferably 5800 MPa or less, and more preferably 5500 MPa or less. There is a tendency that the higher the bonding force to the frame member at the temperature of the extension step is, the more the peeling of the adhesive layer or the die-cut adhesive film from the frame member in the extension step is suppressed.

如上所述,本切晶黏晶膜適合於在其黏著接著劑層中,確保延伸步驟中之割斷性,並且實現對於環狀框等框構件之良好之貼合性。As described above, the die-cut die-bonding film is suitable for its adhesive bond layer to ensure the cutting property in the extending step, and to achieve good adhesion to frame members such as ring frames.

此種本切晶黏晶膜能夠以於其黏著接著劑層中除工件貼合用區域以外,且包含框架貼合用區域之方式,對切晶帶或其黏著劑層與其上之黏著接著劑層於膜面內方向,以實質上相同之尺寸進行設計。例如可採用於切晶黏晶膜之面內方向,黏著接著劑層之外周端位於距切晶帶之基材或黏著劑層之各外周端1000 μm以內之距離之設計。此種本切晶黏晶膜適合於以一個衝壓加工等加工一次性地實施用以形成具有基材與黏著劑層之積層構造之一個切晶帶之加工、及用以形成一個黏著接著劑層或黏晶膜之加工。Such a die-cut die-bonding film can be applied to the die-cut tape or its adhesive layer and the adhesive agent on the die-bonding adhesive layer in addition to the work bonding area and including the frame bonding area The layers are designed with substantially the same size in the in-plane direction of the film. For example, it can be designed in the in-plane direction of the die-cut adhesive film, and the outer peripheral end of the adhesive layer is located within a distance of 1000 μm from each peripheral end of the substrate of the die-cut tape or the adhesive layer. This type of die-cut crystal bonding film is suitable for performing a process for forming a dicing tape having a laminated structure of a substrate and an adhesive layer at one time by a stamping process and the like, and for forming an adhesive adhesive layer Or processing of crystal film.

於上述先前型之切晶黏晶膜Y之製造過程中,用以形成特定之尺寸及形狀之切晶帶60之加工步驟(第1加工步驟)、與用以形成特定之尺寸及形狀之黏晶膜70之加工步驟(第2加工步驟)作為另一步驟而必需。於第1加工步驟中,例如,對具有特定之隔片、形成為基材61之基材層、及位於該等之間而形成為黏著劑層62之黏著劑層之積層構造之積層片材體,實施將加工刀自基材層之側插入至隔片之加工。藉此,具有隔片上之黏著劑層62與基材61之積層構造之切晶帶60形成於隔片上。於第2加工步驟中,例如,對具有特定之隔片與形成為黏晶膜70之黏晶膜之積層構造之積層片材體,實施將加工刀自黏晶膜之側插入至隔片之加工。藉此,於隔片上形成黏晶膜70。如此於另一步驟中形成之切晶帶60與黏晶膜70其後進行對位而貼合。圖17中表示帶覆蓋黏晶膜70表面及黏著劑層62表面之隔片83之先前型之切晶黏晶膜Y。In the manufacturing process of the above-mentioned prior-type crystalline die-bonding film Y, a processing step (first processing step) for forming a dicing tape 60 of a specific size and shape, and a bonding step for forming a specific size and shape The processing step (second processing step) of the crystal film 70 is necessary as another step. In the first processing step, for example, for a laminated sheet having a specific separator, a base material layer formed as a base material 61, and an adhesive layer formed therebetween as an adhesive layer 62 Body, inserting the processing knife into the separator from the side of the base material layer. Thereby, the dicing tape 60 having the laminated structure of the adhesive layer 62 and the base material 61 on the spacer is formed on the spacer. In the second processing step, for example, for a laminated sheet body having a laminated structure of a specific spacer and a viscous film formed as a viscous film 70, a process of inserting a processing knife from the side of the viscous film to the spacer is performed . Thereby, the crystal bonding film 70 is formed on the spacer. The dicing tape 60 and the die-bonding film 70 thus formed in another step are then aligned and bonded. FIG. 17 shows a previous type of die-cut die-bonding film Y with a spacer 83 covering the surface of the die-bonding film 70 and the surface of the adhesive layer 62.

相對於此,切晶帶或其黏著劑層與其上之黏著接著劑層於膜面內方向具有實質上相同之設計尺寸之情形時之本發明之切晶黏晶膜適合於以一次衝壓加工等加工來一次性地實施如下加工,即用以形成具有基材與黏著劑層之積層構造之一個切晶帶之加工、及用以形成一個黏著接著劑層之加工。此種本切晶黏晶膜適合於在黏著接著劑層中確保延伸步驟中之割斷性,且實現對於框構件之良好之黏著力,並且適合於在製造步驟數削減或製造成本抑制之方面等有效率地進行製造。In contrast, when the die-cut tape or its adhesive layer and the adhesive layer thereon have substantially the same design dimensions in the film plane direction, the die-cut adhesive film of the present invention is suitable for one-time stamping processing, etc. In the processing, the following processing is performed at once, that is, processing for forming a dicing tape having a laminated structure of a base material and an adhesive layer, and processing for forming an adhesive adhesive layer. Such an original die-cut adhesive film is suitable for ensuring the cutting property in the extension step in the adhesive adhesive layer, and achieving good adhesion to the frame member, and is suitable for reducing the number of manufacturing steps or suppressing the manufacturing cost, etc. Manufacturing efficiently.

本切晶黏晶膜對於黏著接著劑層之SUS平面之-15℃下之剪切黏著力較佳為66 N/cm2 以上,更佳為68 N/cm2 以上,更佳為70 N/cm2 以上。剪切黏著力係設為藉由關於實施例而於下文中所說明之剪切黏著力測定方法所測定之值。與剪切黏著力相關之該構成於確保利用-15℃及其附近之低溫下之本切晶黏晶膜之框構件之保持之方面較適宜。The shear adhesion of the die-cut adhesive film to the SUS plane of the adhesive layer at -15°C is preferably 66 N/cm 2 or more, more preferably 68 N/cm 2 or more, and even more preferably 70 N/ cm 2 or more. The shear adhesion is set to the value measured by the shear adhesion measurement method described below with respect to the examples. The structure related to the shear adhesive force is more suitable for ensuring the maintenance of the frame member of the original crystal-cut adhesive film at a low temperature of -15°C and its vicinity.

本切晶黏晶膜之黏著接著劑層較佳為包含重量平均分子量800000~2000000且玻璃轉移溫度-10~3℃之聚合物成分。此種構成於謀求黏著接著劑層於低溫下之割斷性、黏著接著劑層對於框構件之貼合力、及黏著接著劑層之剝離時殘渣之防止之平衡性之方面較適宜。就黏著接著劑層之低溫下之割斷性之確保之觀點或剝離時殘渣之防止之觀點而言,該聚合物之重量平均分子量更佳為900000以上,更佳為1000000以上。就確保黏著接著劑層之對框構件貼合力之觀點而言,該聚合物之重量平均分子量更佳為1800000以下,更佳為1500000以下。就確保黏著接著劑層之低溫下之割斷性之觀點而言,該聚合物之玻璃轉移溫度更佳為-8℃以上,更佳為-6.5℃以上。就確保黏著接著劑層之低溫下之對框構件黏著力之觀點而言,該聚合物之玻璃轉移溫度更佳為0℃以下,更佳為-1.5℃以下。The adhesive layer of the die-cut adhesive film preferably contains a polymer component having a weight average molecular weight of 800,000 to 2,000,000 and a glass transition temperature of -10 to 3°C. Such a configuration is more suitable for achieving balance between the cutoff property of the adhesive agent layer at a low temperature, the adhesion force of the adhesive agent layer to the frame member, and the prevention of residues during peeling of the adhesive agent layer. From the viewpoint of ensuring the cut-off property at a low temperature of the adhesive layer or preventing the residue during peeling, the weight average molecular weight of the polymer is more preferably 900,000 or more, and still more preferably 1,000,000 or more. From the viewpoint of ensuring the adhesion of the adhesive layer to the frame member, the weight-average molecular weight of the polymer is preferably 1.8 million or less, and more preferably 1.5 million or less. From the viewpoint of ensuring the cut-off property at a low temperature of the adhesive layer, the glass transition temperature of the polymer is more preferably -8°C or higher, more preferably -6.5°C or higher. From the standpoint of ensuring the adhesion to the frame member at a low temperature of the adhesive layer, the glass transition temperature of the polymer is more preferably 0°C or lower, more preferably -1.5°C or lower.

黏著接著劑層中之聚合物成分較佳為包含源自丙烯腈之構成單元。此種構成因黏著接著劑層中聚合物成分之該單元內之腈基為高極性,故而於在黏著接著劑層中,實現對於SUS製環狀框等金屬製框構件之較高之密接性之方面較佳。The polymer component in the adhesive layer preferably contains a structural unit derived from acrylonitrile. In this structure, the nitrile group in the unit of the polymer component in the adhesive layer is highly polarized, so in the adhesive layer, high adhesion to metal frame members such as ring frames made of SUS is achieved It’s better.

本切晶黏晶膜之黏著接著劑層較佳為以10~40質量%之比率含有二氧化矽填料。於黏著接著劑層中之二氧化矽填料含量為10質量%以上之構成於在黏著接著劑層中確保延伸步驟中之割斷性之方面較佳,又,於在黏著接著劑層中確保凝聚力而謀求上述剝離時殘渣之防止之方面較佳。於在黏著接著劑層中確保對於框構件之低溫下之貼合力之方面,黏著接著劑層之二氧化矽填料含量較佳為40質量%以下,更佳為30質量%以下,更佳為25質量%以下。The adhesive bonding agent layer of the present die-cut adhesive film preferably contains a silica filler at a ratio of 10 to 40% by mass. The content of the silica filler in the adhesive adhesive layer is 10% by mass or more. It is preferable in terms of ensuring the cut-off property in the extension step in the adhesive adhesive layer, and in order to ensure the cohesive force in the adhesive adhesive layer. It is preferable to seek the prevention of the residue at the time of peeling. In terms of ensuring the adhesion to the frame member at low temperature in the adhesive layer, the content of the silica filler in the adhesive layer is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 25 Mass% or less.

本切晶黏晶膜之切晶帶之黏著劑層較佳為放射線硬化型黏著劑層。於切晶帶黏著劑層為放射線硬化型黏著劑層之情形時,於本切晶黏晶膜中,於23℃及剝離速度300 mm/min之條件下之T型剝離試驗中之放射線硬化前之黏著劑層與黏著接著劑層之間之剝離力較佳為0.5 N/20 mm以上。與剝離黏著力相關之此種構成於在黏著接著劑層中確保對框構件貼合力之方面較佳。The adhesive layer of the dicing tape of the dicing adhesive film is preferably a radiation hardening type adhesive layer. When the adhesive layer of the dicing tape is a radiation hardening type adhesive layer, before the radiation hardening in the T-type peeling test under the conditions of 23° C. and a peeling speed of 300 mm/min in this dicing film The peeling force between the adhesive layer and the adhesive layer is preferably 0.5 N/20 mm or more. Such a structure related to peeling adhesion is preferable in terms of ensuring the adhesion force to the frame member in the adhesive adhesive layer.

本切晶黏晶膜中之黏著接著劑層之厚度較佳為7~30 μm。黏著接著劑層之厚度為7 μm以上之構成於貼附有框構件之黏著接著劑層追隨該框構件表面之微細凹凸而發揮出良好之框構件貼合性之方面較佳。黏著接著劑層之厚度為30 μm以下之構成於在黏著接著劑層中確保延伸步驟中之割斷性之方面較佳。The thickness of the adhesive layer in the die-cut adhesive film is preferably 7-30 μm. It is preferable that the adhesive layer with a thickness of 7 μm or more is formed in such a manner that the adhesive layer to which the frame member is attached follows the fine irregularities on the surface of the frame member to exhibit good frame member adhesion. It is preferable that the thickness of the adhesive layer is 30 μm or less in terms of ensuring the cutting property in the extending step in the adhesive layer.

圖1為本發明之一實施形態之切晶黏晶膜X之剖面模式圖。切晶黏晶膜X具有包含切晶帶10與黏著接著劑層20之積層構造。切晶帶10具有包含基材11與黏著劑層12之積層構造。黏著劑層12於黏著接著劑層20側具有黏著面12a。黏著接著劑層20包含工件貼合用區域及框架貼合用區域,且可剝離地密接於切晶帶10之黏著劑層12或其黏著面12a密接。切晶黏晶膜X於半導體裝置之製造中可用於獲得附有黏晶膜之半導體晶片之過程中之例如如下所述之延伸步驟中。又,切晶黏晶膜X具有與半導體裝置之製造過程中之加工對象之半導體晶圓相對應之尺寸之圓盤形狀,其直徑例如處於345~380 mm之範圍內(12英吋晶圓對應型)、245~280 mm之範圍內(8英吋晶圓對應型)、195~230 mm之範圍內(6英吋晶圓對應型)、或495~530 mm之範圍內(18英吋晶圓對應型)。FIG. 1 is a schematic cross-sectional view of a die-cut crystal bonding film X according to an embodiment of the present invention. The die cut adhesive film X has a laminated structure including the die cut tape 10 and the adhesive layer 20. The dicing tape 10 has a laminated structure including a base material 11 and an adhesive layer 12. The adhesive layer 12 has an adhesive surface 12a on the adhesive layer 20 side. The adhesive layer 20 includes a work bonding area and a frame bonding area, and is peelably adhered to the adhesive layer 12 of the dicing tape 10 or its adhesive surface 12a. The die-bonding die-bonding film X can be used in the process of obtaining a semiconductor wafer with a die-bonding film attached in the manufacturing process of a semiconductor device, for example, in the extending step described below. Moreover, the die-bonding film X has a disc shape with a size corresponding to the semiconductor wafer to be processed in the manufacturing process of the semiconductor device, and its diameter is, for example, in the range of 345 to 380 mm (corresponding to a 12-inch wafer) Type), within the range of 245 to 280 mm (8-inch wafer corresponding type), within the range of 195 to 230 mm (6 inch wafer corresponding type), or within the range of 495 to 530 mm (18 inch crystal Circle corresponding type).

切晶帶10之基材11係於切晶帶10或切晶黏晶膜X中作為支持體而發揮功能之要素。基材11例如為塑膠基材,作為該塑膠基材,可適宜地使用塑膠膜。作為該塑膠基材之構成材料,例如可列舉:聚氯乙烯、聚偏二氯乙烯、聚烯烴、聚酯、聚胺基甲酸酯、聚碳酸酯、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、氟樹脂、纖維素系樹脂、及聚矽氧樹脂。作為聚烯烴,例如可列舉:低密度聚乙烯、直鏈狀低密度聚乙烯、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、乙烯-乙酸乙烯酯共聚物(EVA)、離子聚合物樹脂、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯共聚物、乙烯-丁烯共聚物、及乙烯-己烯共聚物。作為聚酯,例如可列舉:聚對苯二甲酸乙二酯(PET)、聚萘二甲酸乙二酯、及聚對苯二甲酸丁二酯(PBT)。基材11可包含一種材料,亦可包含兩種以上之材料。基材11可具有單層構造,亦可具有多層構造。又,基材11於包含塑膠膜之情形時,可為無延伸膜,可為單軸延伸膜,亦可為雙軸延伸膜。於基材11上之黏著劑層12如下所述般具有紫外線硬化性之情形時,基材11較佳為具有紫外線透過性。The base material 11 of the dicing tape 10 is an element that functions as a support in the dicing tape 10 or the dicing die-bonding film X. The substrate 11 is, for example, a plastic substrate, and as the plastic substrate, a plastic film can be suitably used. Examples of the constituent material of the plastic substrate include polyvinyl chloride, polyvinylidene chloride, polyolefin, polyester, polyurethane, polycarbonate, polyetheretherketone, and polyimide, Polyetherimide, polyamide, fully aromatic polyamide, polyphenylene sulfide, aromatic polyamide, fluororesin, cellulose resin, and polysiloxane resin. Examples of polyolefins include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, ultra-low-density polyethylene, random copolymer polypropylene, block copolymer polypropylene, and homopolymers. Polypropylene, polybutene, polymethylpentene, ethylene-vinyl acetate copolymer (EVA), ionic polymer resin, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, Ethylene-butene copolymer and ethylene-hexene copolymer. Examples of the polyester include polyethylene terephthalate (PET), polyethylene naphthalate, and polybutylene terephthalate (PBT). The substrate 11 may include one kind of material, or two or more kinds of materials. The base material 11 may have a single-layer structure or a multi-layer structure. In addition, when the base material 11 includes a plastic film, it may be a non-stretched film, a uniaxially stretched film, or a biaxially stretched film. When the adhesive layer 12 on the base material 11 has ultraviolet curability as described below, the base material 11 preferably has ultraviolet transmittance.

於切晶黏晶膜X之使用過程中,例如於藉由部分加熱使切晶帶10或基材11收縮之情形時,基材11較佳為具有熱收縮性。就於基材11中確保良好之熱收縮性之觀點而言,基材11較佳為包含乙烯-乙酸乙烯酯共聚物作為主成分。所謂基材11之主成分係設為於基材構成成分中占最大質量比率之成分。又,於基材11包含塑膠膜之情形時,就關於切晶帶10或基材11實現各向同性之熱收縮性而言,基材11較佳為雙軸延伸膜。關於切晶帶10或基材11,於加熱溫度100℃及加熱處理時間60秒之條件下進行之加熱處理試驗中之熱收縮率例如為2~30%。In the process of using the die-cut die-bonding film X, for example, when the die-cut tape 10 or the substrate 11 is shrunk by partial heating, the substrate 11 preferably has heat shrinkability. From the viewpoint of ensuring good heat shrinkability in the base material 11, the base material 11 preferably contains an ethylene-vinyl acetate copolymer as a main component. The main component of the base material 11 is the component that accounts for the largest mass ratio among the base component components. In addition, when the base material 11 includes a plastic film, the base material 11 is preferably a biaxially stretched film in terms of achieving isotropic thermal shrinkage of the dicing tape 10 or the base material 11. Regarding the dicing tape 10 or the base material 11, the heat shrinkage rate in the heat treatment test performed under the conditions of a heating temperature of 100°C and a heat treatment time of 60 seconds is, for example, 2 to 30%.

基材11中之黏著劑層12側之表面亦可實施用以提高與黏著劑層12之密接性之物理處理、化學處理、或底塗處理。作為物理處理,例如可列舉:電暈處理、電漿處理、噴砂加工處理、臭氧暴露處理、火焰暴露處理、高壓電擊暴露處理、及離子化放射線處理。作為化學處理,例如可列舉鉻酸處理。用以提高密接性之該處理較佳為對基材11中之黏著劑層12側之整個表面實施。The surface of the substrate 11 on the side of the adhesive layer 12 may also be subjected to physical treatment, chemical treatment, or primer treatment to improve the adhesion with the adhesive layer 12. Examples of the physical treatment include corona treatment, plasma treatment, sandblasting treatment, ozone exposure treatment, flame exposure treatment, high-voltage electric shock exposure treatment, and ionizing radiation treatment. Examples of the chemical treatment include chromic acid treatment. The treatment for improving the adhesion is preferably performed on the entire surface of the substrate 11 on the adhesive layer 12 side.

關於基材11之厚度,就確保用以切晶帶10或切晶黏晶膜X中之作為支持體之基材11發揮功能之強度之觀點而言,較佳為40 μm以上,更佳為50 μm以上,更佳為55 μm以上,更佳為60 μm以上。又,就於切晶帶10或切晶黏晶膜X中實現適度之可撓性之觀點而言,基材11之厚度較佳為200 μm以下,更佳為180 μm以下,更佳為150 μm以下。The thickness of the base material 11 is preferably 40 μm or more in view of ensuring the strength of the base material 11 serving as a support in the dicing tape 10 or the crystalline die bonding film X to function. 50 μm or more, more preferably 55 μm or more, and more preferably 60 μm or more. Also, from the viewpoint of achieving moderate flexibility in the dicing tape 10 or the dicing die-bonding film X, the thickness of the substrate 11 is preferably 200 μm or less, more preferably 180 μm or less, and still more preferably 150 Below μm.

切晶帶10之黏著劑層12含有黏著劑。黏著劑可為能夠藉由放射線照射或加熱等來自外部之作用而有意地減少黏著力之黏著劑(黏著力減少型黏著劑),亦可為黏著力幾乎或完全不會因來自外部之作用而減少之黏著劑(黏著力非減少型黏著劑)。關於使用黏著力減少型黏著劑作為黏著劑層12中之黏著劑還是使用黏著力非減少型黏著劑作為黏著劑層12中之黏著劑,可視使用切晶黏晶膜X而單片化之半導體晶片之單片化方法或條件等切晶黏晶膜X之使用態樣,而適當地加以選擇。The adhesive layer 12 of the dicing tape 10 contains an adhesive. The adhesive may be an adhesive that can intentionally reduce the adhesive force by an external effect such as radiation irradiation or heating (adhesive-reducing adhesive), or it may be an adhesive force that is hardly or completely not affected by an external effect Reduced adhesive (non-reduced adhesive). Regarding whether to use an adhesive-reducing adhesive as the adhesive in the adhesive layer 12 or whether to use a non-adhesive-type adhesive as the adhesive in the adhesive layer 12, the singulated semiconductor can be regarded as using the diced die-bonding film X The use of the die-bonding die-bonding film X such as the singulation method or conditions of the wafer is appropriately selected.

於使用黏著力減少型黏著劑作為黏著劑層12中之黏著劑之情形時,於切晶黏晶膜X之使用過程中,可分開使用黏著劑層12顯示出相對較高之黏著力之狀態、與顯示出相對較低之黏著力之狀態。例如,於將切晶黏晶膜X用於下述延伸步驟中時,為了抑制、防止黏著接著劑層20自黏著劑層12隆起或剝離,而利用黏著劑層12之高黏著力狀態,另一方面,其後,於用以自切晶黏晶膜X之切晶帶10拾取附有黏著接著劑層之半導體晶片之下述拾取步驟中,為了自黏著劑層12容易地拾取附有黏著接著劑層之半導體晶片,可利用黏著劑層12之低黏著力狀態。In the case of using an adhesive-reducing adhesive as the adhesive in the adhesive layer 12, during the use of the slicing adhesive film X, the adhesive layer 12 can be used separately to show a relatively high adhesive state , And show a relatively low adhesion state. For example, when the die-cut adhesive film X is used in the following extension step, in order to suppress and prevent the adhesive layer 20 from bulging or peeling off from the adhesive layer 12, the high adhesive state of the adhesive layer 12 is used, and On the one hand, thereafter, in the following pickup step for picking up the semiconductor wafer with the adhesive layer from the dicing tape 10 of the dicing die-bonding film X, in order to easily pick up the adhesion with the adhesive layer 12 The semiconductor wafer with the adhesive layer can utilize the low adhesive state of the adhesive layer 12.

作為此種黏著力減少型黏著劑,例如可列舉具有放射線硬化性之黏著劑(放射線硬化性黏著劑)或加熱發泡型黏著劑等。於本實施形態之黏著劑層12中,可使用一種黏著力減少型黏著劑,亦可使用兩種以上之黏著力減少型黏著劑。又,黏著劑層12之整體可由黏著力減少型黏著劑所形成,亦可黏著劑層12之一部分由黏著力減少型黏著劑所形成。例如,於黏著劑層12具有單層構造之情形時,可黏著劑層12之整體由黏著力減少型黏著劑所形成,亦可黏著劑層12中之特定部位由黏著力減少型黏著劑所形成,而其他部位由黏著力非減少型黏著劑所形成。又,於黏著劑層12具有積層構造之情形時,可構成積層構造之所有層由黏著力減少型黏著劑所形成,亦可積層構造中之一部分層由黏著力減少型黏著劑所形成。Examples of such adhesive force-reducing adhesives include radiation-curing adhesives (radiation-curing adhesives) and heat-foaming adhesives. In the adhesive layer 12 of the present embodiment, one kind of adhesive-reducing adhesive may be used, or two or more kinds of adhesive-reducing adhesives may be used. In addition, the whole of the adhesive layer 12 may be formed of an adhesive with reduced adhesion, or a part of the adhesive layer 12 may be formed of an adhesive with reduced adhesion. For example, in the case where the adhesive layer 12 has a single-layer structure, the entire adhesive layer 12 may be formed by an adhesive reduction type adhesive, or a specific portion of the adhesive layer 12 may be formed by an adhesive reduction type adhesive. Formation, while the other parts are formed by non-adhesive adhesives. In addition, when the adhesive layer 12 has a laminated structure, all the layers that can constitute the laminated structure are formed by the adhesive reduction type adhesive, or a part of the layers in the laminated structure may be formed by the adhesive reduction type adhesive.

作為黏著劑層12中之放射線硬化性黏著劑,例如可使用藉由電子束、紫外線、α射線、β射線、γ射線、或X射線之照射而硬化之類型之黏著劑,可尤其適宜地使用藉由紫外線照射而硬化之類型之黏著劑(紫外線硬化性黏著劑)。As the radiation-curable adhesive in the adhesive layer 12, for example, an adhesive that is hardened by irradiation with electron beams, ultraviolet rays, α rays, β rays, γ rays, or X rays can be used, and it can be particularly suitably used Adhesive of the type hardened by ultraviolet irradiation (ultraviolet-curable adhesive).

作為黏著劑層12中之放射線硬化性黏著劑,例如可列舉如下添加型之放射線硬化性黏著劑,其含有作為丙烯酸系黏著劑之丙烯酸系聚合物等基礎聚合物、與具有放射線聚合性之碳-碳雙鍵等官能基之放射線聚合性之單體成分或低聚物成分。Examples of the radiation-curable adhesive in the adhesive layer 12 include the following addition-type radiation-curable adhesives, which contain a base polymer such as an acrylic polymer as an acrylic adhesive and a carbon having radiation polymerization -Radiation polymerizable monomer components or oligomer components of functional groups such as carbon double bonds.

上述丙烯酸系聚合物較佳為包含源自丙烯酸酯及/或甲基丙烯酸酯之單體單元作為以質量比率計最多之單體單元。以下以「(甲基)丙烯酸」表示「丙烯酸」及/或「甲基丙烯酸」,以「(甲基)丙烯酸酯」表示「丙烯酸酯」及/或「甲基丙烯酸酯」。The acrylic polymer preferably contains monomer units derived from acrylate and/or methacrylate as the most monomer units in terms of mass ratio. In the following, "(meth)acrylic acid" means "acrylic acid" and/or "methacrylic acid", and "(meth)acrylate" means "acrylate" and/or "methacrylate".

作為用以構成丙烯酸系聚合物之單體單元之(甲基)丙烯酸酯,例如可列舉:(甲基)丙烯酸烷基酯、(甲基)丙烯酸環烷基酯、(甲基)丙烯酸芳酯等含烴基之(甲基)丙烯酸酯。作為(甲基)丙烯酸烷基酯,例如可列舉:(甲基)丙烯酸之甲酯、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、及二十烷基酯。作為(甲基)丙烯酸環烷基酯,例如可列舉(甲基)丙烯酸之環戊酯及環己酯。作為(甲基)丙烯酸芳酯,例如可列舉(甲基)丙烯酸苯酯及(甲基)丙烯酸苄酯。作為用以構成丙烯酸系聚合物之單體單元之單體成分,可使用一種(甲基)丙烯酸酯,亦可使用兩種以上(甲基)丙烯酸酯。作為用以構成丙烯酸系聚合物之單體單元之(甲基)丙烯酸酯,較佳為烷基之碳數為10以上之(甲基)丙烯酸烷基酯,更佳為丙烯酸十二烷基酯。又,於在黏著劑層12中適當地表現出由(甲基)丙烯酸酯所引起之黏著性等基本特性之方面,用以形成丙烯酸系聚合物之全部單體成分中之(甲基)丙烯酸酯之比率較佳為40質量%以上,更佳為60質量%以上。Examples of (meth)acrylic acid esters used to form monomer units of acrylic polymers include alkyl (meth)acrylates, cycloalkyl (meth)acrylates, and aryl (meth)acrylates. (Hydroxy)-containing (meth) acrylate. Examples of alkyl (meth)acrylates include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, and third butyl (meth)acrylate. Amyl, isoamyl, hexyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, decyl, isodecyl, undecyl, dodecyl, deca Trialkyl ester, myristyl ester, hexadecyl ester, octadecyl ester, and eicosyl ester. Examples of cycloalkyl (meth)acrylates include cyclopentyl (meth)acrylate and cyclohexyl ester. Examples of aryl (meth)acrylates include phenyl (meth)acrylate and benzyl (meth)acrylate. As the monomer component for constituting the monomer unit of the acrylic polymer, one (meth)acrylate may be used, or two or more (meth)acrylates may be used. As the (meth)acrylate used to constitute the monomer unit of the acrylic polymer, it is preferably an alkyl (meth)acrylate having an alkyl group of 10 or more carbon atoms, more preferably dodecyl acrylate . In addition, in order to properly display the basic characteristics such as adhesion caused by (meth)acrylate in the adhesive layer 12, (meth)acrylic acid is used to form all the monomer components of the acrylic polymer The ratio of the ester is preferably 40% by mass or more, and more preferably 60% by mass or more.

丙烯酸系聚合物為了對其凝聚力或耐熱性等進行改質,可含有源自可與(甲基)丙烯酸酯進行共聚之其他單體之單體單元。作為此種其他單體,例如可列舉:含羧基之單體、酸酐單體、含羥基之單體、含縮水甘油基之單體、含磺酸基之單體、含磷酸基之單體、丙烯醯胺、及丙烯腈等含官能基之單體。作為含羧基之單體,例如可列舉:丙烯酸、甲基丙烯酸、(甲基)丙烯酸2-羧基乙酯、(甲基)丙烯酸5-羧基戊酯、伊康酸、順丁烯二酸、反丁烯二酸、及丁烯酸。作為酸酐單體,例如可列舉順丁烯二酸酐及伊康酸酐。作為含羥基之單體,例如可列舉:(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-羥基十二烷基酯、及(甲基)丙烯酸(4-羥基甲基環己基)甲酯。作為含縮水甘油基之單體,例如可列舉(甲基)丙烯酸縮水甘油酯及(甲基)丙烯酸甲基縮水甘油酯。作為含磺酸基之單體,例如可列舉: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、及(甲基)丙烯酸磺丙酯。作為含磷酸基之單體,例如可列舉磷酸2-羥基乙基丙烯醯酯。作為用於丙烯酸系聚合物之該其他共聚性單體,可使用一種單體,亦可使用兩種以上之單體。The acrylic polymer may contain monomer units derived from other monomers copolymerizable with (meth)acrylate in order to modify its cohesive strength, heat resistance, and the like. Examples of such other monomers include carboxyl group-containing monomers, acid anhydride monomers, hydroxyl group-containing monomers, glycidyl group-containing monomers, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, Functional monomers such as acrylamide and acrylonitrile. Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, 2-carboxyethyl (meth)acrylate, 5-carboxypentyl (meth)acrylate, itaconic acid, maleic acid, trans Crotonic acid and crotonic acid. Examples of the acid anhydride monomer include maleic anhydride and itaconic anhydride. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and (meth)acrylic acid 6. -Hydroxyhexyl ester, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxydodecyl (meth)acrylate, and (4- (meth)acrylic acid) Hydroxymethylcyclohexyl) methyl ester. Examples of the glycidyl group-containing monomer include glycidyl (meth)acrylate and methylglycidyl (meth)acrylate. Examples of sulfonic acid group-containing monomers include styrene sulfonic acid, allyl sulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, and (meth)acrylamide propane Sulfonic acid, and sulfopropyl (meth)acrylate. Examples of phosphoric acid group-containing monomers include 2-hydroxyethyl acryl phosphate. As the other copolymerizable monomer used in the acrylic polymer, one kind of monomer may be used, or two or more kinds of monomers may be used.

丙烯酸系聚合物為了於其聚合物骨架中形成交聯結構,可含有源自可與(甲基)丙烯酸酯等單體成分共聚之多官能性單體之單體單元。作為此種多官能性單體,例如可列舉: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、聚(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸聚酯、及(甲基)丙烯酸胺基甲酸酯。作為用於丙烯酸系聚合物之單體成分,可使用一種多官能性單體,亦可使用兩種以上之多官能性單體。關於用以形成丙烯酸系聚合物之全部單體成分中之多官能性單體之比率,於在黏著劑層12中適當地表現出由(甲基)丙烯酸酯所引起之黏著性等基本特性之方面,較佳為40質量%以下,較佳為30質量%以下。In order to form a cross-linked structure in its polymer backbone, the acrylic polymer may contain monomer units derived from a multifunctional monomer copolymerizable with monomer components such as (meth)acrylate. Examples of such multifunctional monomers include hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (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, poly(glycidyl) (meth)acrylate, (meth)acrylic polyester, and (meth)acrylic acid urethane. As the monomer component for the acrylic polymer, one type of multifunctional monomer may be used, or two or more types of multifunctional monomers may be used. Regarding the ratio of polyfunctional monomers in all monomer components used to form the acrylic polymer, the adhesive layer 12 appropriately exhibits basic characteristics such as adhesion caused by (meth)acrylate In respect of this, it is preferably 40% by mass or less, and preferably 30% by mass or less.

丙烯酸系聚合物可使用以形成其之原料單體進行聚合而獲得。作為聚合方法,例如可列舉:溶液聚合、乳化聚合、塊狀聚合、及懸浮聚合。就使用切晶帶10或切晶黏晶膜X之半導體裝置製造方法中之高度之清潔性之觀點而言,較佳為切晶帶10或切晶黏晶膜X中之黏著劑層12中之低分子量物質較少,丙烯酸系聚合物之重量平均分子量較佳為100000以上,更佳為200000~3000000。The acrylic polymer can be obtained by polymerizing raw material monomers used to form it. Examples of the polymerization method include solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization. From the viewpoint of the high degree of cleanliness in the method of manufacturing a semiconductor device using the dicing tape 10 or the dicing adhesive film X, it is preferably in the adhesive layer 12 in the dicing tape 10 or the crystalline die bonding film X There are few low molecular weight substances, and the weight average molecular weight of the acrylic polymer is preferably 100,000 or more, more preferably 200,000 to 3,000,000.

黏著劑層12或用以構成其之黏著劑為了提高丙烯酸系聚合物等基礎聚合物之重量平均分子量,例如可含有外部交聯劑。作為用以與丙烯酸系聚合物等基礎聚合物進行反應而形成交聯結構之外部交聯劑,可列舉:聚異氰酸酯化合物、環氧化合物、多元醇化合物(多酚系化合物等)、氮丙啶化合物、及三聚氰胺系交聯劑。黏著劑層12或用以構成其之黏著劑中之外部交聯劑之含量相對於基礎聚合物100質量份,較佳為6質量份以下,更佳為0.1~5質量份。In order to increase the weight average molecular weight of a base polymer such as an acrylic polymer, the adhesive layer 12 or the adhesive used to constitute it may contain an external crosslinking agent, for example. Examples of the external crosslinking agent that reacts with a base polymer such as an acrylic polymer to form a crosslinked structure include polyisocyanate compounds, epoxy compounds, polyol compounds (polyphenolic compounds, etc.), aziridine Compounds, and melamine-based crosslinking agents. The content of the external crosslinking agent in the adhesive layer 12 or the adhesive used to constitute it is preferably 6 parts by mass or less relative to 100 parts by mass of the base polymer, and more preferably 0.1 to 5 parts by mass.

作為用以構成放射線硬化性黏著劑之上述放射線聚合性單體成分,例如可列舉:(甲基)丙烯酸胺基甲酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、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、及1,4-丁二醇二(甲基)丙烯酸酯。作為用以構成放射線硬化性黏著劑之上述放射線聚合性低聚物成分,例如可列舉: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,較適宜為分子量100~30000左右者。放射線硬化性黏著劑中之放射線聚合性之單體成分或低聚物成分之總含量係於可藉由放射線照射而適當地降低所形成之黏著劑層12之黏著力之範圍內決定,相對於丙烯酸系聚合物等基礎聚合物100質量份,例如為5~500質量份,較佳為40~150質量份。又,作為添加型之放射線硬化性黏著劑,例如可使用於日本專利特開昭60-196956號公報中所揭示者。Examples of the above-mentioned radiation-polymerizable monomer component constituting the radiation-curable adhesive include, for example, (meth)acrylate carbamate, trimethylolpropane tri(meth)acrylate, and pentaerythritol tri(meth) Base) acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and 1,4-butanediol di(meth)acrylate ester. Examples of the radiation-polymerizable oligomer component constituting the radiation-curable adhesive include various types such as urethane-based, polyether-based, polyester-based, polycarbonate-based, and polybutadiene-based. The oligomer is preferably about 100 to 30,000 in molecular weight. The total content of the radiation-polymerizable monomer component or oligomer component in the radiation-curing adhesive is determined within a range in which the adhesive force of the formed adhesive layer 12 can be appropriately reduced by radiation irradiation, relative to 100 parts by mass of the base polymer such as acrylic polymer is, for example, 5 to 500 parts by mass, preferably 40 to 150 parts by mass. In addition, as an additive type radiation-curable adhesive, for example, it can be used as disclosed in Japanese Patent Laid-Open No. 60-196956.

作為黏著劑層12中之放射線硬化性黏著劑,例如亦可列舉內在型之放射線硬化性黏著劑,其含有於聚合物側鏈、或聚合物主鏈中、聚合物主鏈末端具有放射線聚合性之碳-碳雙鍵等官能基之基礎聚合物。此種內在型之放射線硬化性黏著劑於抑制由所形成之黏著劑層12內之低分子量成分之移動引起之黏著特性之非期望之經時性變化之方面較適宜。As the radiation-curing adhesive in the adhesive layer 12, for example, an intrinsic type radiation-curing adhesive can also be mentioned, which is contained in the polymer side chain, or the polymer main chain, and the polymer main chain terminal has radiation polymerizability The basic polymer of carbon-carbon double bond and other functional groups. Such an internal type radiation-curing adhesive is suitable for suppressing undesirable temporal changes in adhesive properties caused by the movement of low-molecular-weight components in the formed adhesive layer 12.

作為內在型之放射線硬化性黏著劑中所含之基礎聚合物,較佳為將丙烯酸系聚合物作為基本骨架者。作為此種構成基本骨架之丙烯酸系聚合物,可採用上述者作為添加型之放射線硬化性黏著劑中之丙烯酸系聚合物。作為向丙烯酸系聚合物中之放射線聚合性之碳-碳雙鍵之導入方法,例如可列舉如下方法:於使包含具有特定之官能基(第1官能基)之單體之原料單體進行共聚而獲得丙烯酸系聚合物後,於維持碳-碳雙鍵之放射線聚合性之狀態下,使具有可於與第1官能基之間產生反應而鍵結之特定之官能基(第2官能基)與放射線聚合性碳-碳雙鍵之化合物對丙烯酸系聚合物進行縮合反應或加成反應。As the base polymer contained in the internal radiation-curing adhesive, an acrylic polymer is preferably used as a basic skeleton. As the acrylic polymer constituting such a basic skeleton, the above-mentioned acrylic polymer in the additive type radiation-curing adhesive can be used. As a method of introducing a radiation-polymerizable carbon-carbon double bond into an acrylic polymer, for example, the following method may be mentioned: copolymerizing a raw material monomer containing a monomer having a specific functional group (first functional group) After the acrylic polymer is obtained, a specific functional group (second functional group) capable of bonding with the first functional group by reacting with the first functional group is maintained while maintaining the radiation polymerizability of the carbon-carbon double bond Compounds with radiation-polymerizable carbon-carbon double bonds undergo condensation reactions or addition reactions with acrylic polymers.

作為第1官能基與第2官能基之組合,例如可列舉:羧基與環氧基、環氧基與羧基、羧基與氮丙啶基、氮丙啶基與羧基、羥基與異氰酸酯基、異氰酸酯基與羥基。該等組合之中,就反應追蹤之容易性之觀點而言,較適宜為羥基與異氰酸酯基之組合、或異氰酸酯基與羥基之組合。又,由於製作具有反應性較高之異氰酸酯基之聚合物之技術難易度較高,故而就丙烯酸系聚合物之製作或獲取之容易性之方面而言,更適宜為丙烯酸系聚合物側之上述第1官能基為羥基且上述第2官能基為異氰酸酯基之情形。於該情形時,作為兼有放射線聚合性碳-碳雙鍵與作為第2官能基之異氰酸酯基之異氰酸酯化合物、即,含放射線聚合性之不飽和官能基之異氰酸酯化合物,例如可列舉:異氰酸甲基丙烯醯酯、異氰酸-2-甲基丙烯醯氧乙酯(MOI)、及α,α-二甲基苄基異氰酸間異丙烯酯。Examples of the combination of the first functional group and the second functional group include carboxyl group and epoxy group, epoxy group and carboxyl group, carboxyl group and aziridine group, aziridine group and carboxyl group, hydroxyl group and isocyanate group, and isocyanate group With hydroxyl. Among these combinations, from the viewpoint of ease of reaction tracking, a combination of a hydroxyl group and an isocyanate group, or a combination of an isocyanate group and a hydroxyl group is more suitable. In addition, since the technical difficulty of producing a polymer having an isocyanate group with higher reactivity is higher, it is more suitable for the acrylic polymer side as described above in terms of the ease of production or acquisition of the acrylic polymer When the first functional group is a hydroxyl group and the second functional group is an isocyanate group. In this case, examples of the isocyanate compound having a radiation-polymerizable carbon-carbon double bond and an isocyanate group as the second functional group, that is, an isocyanate compound containing a radiation-polymerizable unsaturated functional group include, for example, isocyanate Methacrylic acid methacrylate, 2-methacrylic acid ethyl isocyanate (MOI), and α,α-dimethylbenzyl isopropenyl isocyanate.

黏著劑層12中之放射線硬化性黏著劑較佳為含有光聚合起始劑。作為光聚合起始劑,例如可列舉:α-酮醇系化合物、苯乙酮系化合物、安息香醚系化合物、縮酮系化合物、芳香族磺醯氯系化合物、光活性肟系化合物、二苯甲酮系化合物、9-氧硫𠮿

Figure 108115440-xxxx-3
系化合物、樟腦醌、鹵化酮、醯基氧化膦、及醯基磷酸酯。作為α-酮醇系化合物,例如可列舉: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、及1-羥基環己基苯基酮。作為苯乙酮系化合物,例如可列舉:甲氧基苯乙酮、2,2-二甲氧基-1,2-二苯乙烷-1-酮、2,2-二乙氧基苯乙酮、及2-甲基-1-[4-(甲硫基)-苯基]-2-嗎啉基丙烷-1。作為安息香醚系化合物,例如可列舉:安息香乙醚、安息香異丙醚、及茴香偶姻甲醚。作為縮酮系化合物,例如可列舉苯偶醯二甲基縮酮。作為芳香族磺醯氯系化合物,例如可列舉2-萘磺醯氯。作為光活性肟系化合物,例如可列舉1-苯基-1,2-丙二酮-2-(O-乙氧基羰基)肟。作為二苯甲酮系化合物,例如可列舉:二苯甲酮、苯甲醯苯甲酸、及3,3'-二甲基-4-甲氧基二苯甲酮。作為9-氧硫𠮿
Figure 108115440-xxxx-3
系化合物,例如可列舉:9-氧硫𠮿
Figure 108115440-xxxx-3
、2-氯-9-氧硫𠮿
Figure 108115440-xxxx-3
、2-甲基-9-氧硫𠮿
Figure 108115440-xxxx-3
、2,4-二甲基-9-氧硫𠮿
Figure 108115440-xxxx-3
、異丙基-9-氧硫𠮿
Figure 108115440-xxxx-3
、2,4-二氯-9-氧硫𠮿
Figure 108115440-xxxx-3
、2,4-二乙基-9-氧硫𠮿
Figure 108115440-xxxx-3
、及2,4-二異丙基-9-氧硫𠮿
Figure 108115440-xxxx-3
。黏著劑層12中之放射線硬化性黏著劑中之光聚合起始劑之含量相對於丙烯酸系聚合物等基礎聚合物100質量份,例如為0.05~20質量份。The radiation hardening adhesive in the adhesive layer 12 preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include: α-ketol-based compounds, acetophenone-based compounds, benzoin ether-based compounds, ketal-based compounds, aromatic sulfonyl chloride-based compounds, photoactive oxime-based compounds, and diphenyl Ketone-based compounds, 9-oxygen sulfur 𠮿
Figure 108115440-xxxx-3
Compounds, camphorquinones, halogenated ketones, acyl phosphine oxides, and acyl phosphates. Examples of the α-keto alcohol-based compound include 4-(2-hydroxyethoxy)phenyl (2-hydroxy-2-propyl) ketone, α-hydroxy-α,α'-dimethyl styrene Ketone, 2-methyl-2-hydroxyphenylacetone, and 1-hydroxycyclohexylphenyl ketone. Examples of the acetophenone-based compound include methoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and 2,2-diethoxyphenethyl Ketone, and 2-methyl-1-[4-(methylthio)-phenyl]-2-morpholinylpropane-1. Examples of the benzoin ether-based compound include benzoin ether, benzoin isopropyl ether, and anisin methyl ether. Examples of the ketal-based compound include benzoyl dimethyl ketal. Examples of the aromatic sulfonyl chloride-based compound include 2-naphthalene sulfonyl chloride. Examples of the photoactive oxime-based compound include 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime. Examples of the benzophenone-based compound include benzophenone, benzoyl benzoic acid, and 3,3′-dimethyl-4-methoxybenzophenone. As 9-oxygen sulfur 𠮿
Figure 108115440-xxxx-3
Compounds, for example, 9-oxosulfur 𠮿
Figure 108115440-xxxx-3
、2-chloro-9-oxygen and sulfur 𠮿
Figure 108115440-xxxx-3
、2-Methyl-9-oxysulfur 𠮿
Figure 108115440-xxxx-3
、2,4-Dimethyl-9-oxysulfur𠮿
Figure 108115440-xxxx-3
、Isopropyl-9-oxysulfur 𠮿
Figure 108115440-xxxx-3
、2,4-Dichloro-9-oxysulfur 𠮿
Figure 108115440-xxxx-3
、2,4-Diethyl-9-oxysulfur𠮿
Figure 108115440-xxxx-3
, And 2,4-diisopropyl-9-oxysulfur 𠮿
Figure 108115440-xxxx-3
. The content of the photopolymerization initiator in the radiation-curable adhesive in the adhesive layer 12 is, for example, 0.05 to 20 parts by mass relative to 100 parts by mass of the base polymer such as acrylic polymer.

黏著劑層12中之上述加熱發泡型黏著劑係含有藉由加熱進行發泡或膨脹之成分之黏著劑。作為藉由加熱進行發泡或膨脹之成分,例如可列舉發泡劑及熱膨脹性微球。The above-mentioned heat-foaming adhesive in the adhesive layer 12 is an adhesive containing a component that foams or expands by heating. Examples of components that foam or expand by heating include foaming agents and thermally expandable microspheres.

作為加熱發泡型黏著劑用之發泡劑,可列舉各種無機系發泡劑及有機系發泡劑。作為無機系發泡劑,例如可列舉:碳酸銨、碳酸氫銨、碳酸氫鈉、亞硝酸銨、氫化硼鈉、及疊氮類。作為有機系發泡劑,例如可列舉:三氯單氟甲烷或二氯單氟甲烷等鹽氟化烷烴;偶氮二異丁腈或偶氮二甲醯胺、偶氮二羧酸鋇等偶氮系化合物;對甲苯磺醯肼或二苯基碸-3,3'-二磺醯基醯肼、4,4'-氧基雙(苯磺醯肼)、烯丙基雙(磺醯基醯肼)等肼系化合物;ρ-1,2-二苯乙烯磺醯胺基脲或4,4'-氧基雙(苯磺醯胺基脲)等胺基脲系化合物;5-嗎啉基-1,2,3,4-噻三唑等三唑系化合物;以及N,N'-二亞硝基五亞甲基四胺或N,N'-二甲基-N,N'-二亞硝基對苯二甲醯胺等N-亞硝基系化合物。Examples of the foaming agent for the heat-foaming adhesive include various inorganic foaming agents and organic foaming agents. Examples of the inorganic foaming agent include ammonium carbonate, ammonium bicarbonate, sodium bicarbonate, ammonium nitrite, sodium boron hydride, and azides. Examples of the organic foaming agent include salt fluorinated alkanes such as trichloromonofluoromethane and dichloromonofluoromethane; azobisisobutyronitrile, azodimethylformamide, and barium azodicarboxylate. Nitrogen compounds; p-toluenesulfonyl hydrazide or diphenylsulfon-3,3'-disulfonyl hydrazide, 4,4'-oxybis(benzenesulfonyl hydrazide), allyl bis(sulfonyl hydrazide) (Hydrazide) and other hydrazine compounds; ρ-1,2-stilbene sulfonylamidourea or 4,4'-oxybis(benzenesulfonylamidourea) and other aminourea compounds; 5-morpholine -1,2,3,4-thitriazole and other triazole compounds; and N,N'-dinitrosopentamethylenetetramine or N,N'-dimethyl-N,N'- N-nitroso compounds such as dinitroso-p-xylylenediamine.

作為加熱發泡型黏著劑用之熱膨脹性微球,例如可列舉將藉由加熱容易地氣化而膨脹之物質封入至殼內之構成之微球。作為藉由加熱容易地氣化而膨脹之物質,例如可列舉:異丁烷、丙烷、及戊烷。藉由利用凝聚法或界面聚合法等將因加熱容易地氣化而膨脹之物質封入至殼形成物質內,可製作熱膨脹性微球。作為殼形成物質,可使用顯示出熱熔融性之物質、或可藉由封入物質之熱膨脹之作用而破裂之物質。作為此種物質,例如可列舉:偏二氯乙烯-丙烯腈共聚物、聚乙烯醇、聚乙烯丁醛、聚甲基丙烯酸甲酯、聚丙烯腈、聚偏二氯乙烯、及聚碸。Examples of the heat-expandable microspheres for heating and foaming adhesives include microspheres composed of a substance that is easily vaporized by heating and expanded into a shell. Examples of the substance that easily evaporates by heating and expands include isobutane, propane, and pentane. Thermally expandable microspheres can be produced by encapsulating substances that are easily vaporized by heating and encapsulated in shell-forming substances by agglomeration method, interfacial polymerization method, or the like. As the shell-forming substance, a substance exhibiting thermal melting property or a substance that can be broken by the thermal expansion of the enclosed substance can be used. Examples of such a substance include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, and polyphenol.

作為黏著劑層12中之上述黏著力非減少型黏著劑,例如可列舉感壓性黏著劑。作為該感壓性黏著劑,例如可使用將丙烯酸系聚合物作為基礎聚合物之丙烯酸系黏著劑或橡膠系黏著劑。於黏著劑層12含有丙烯酸系黏著劑作為感壓性黏著劑之情形時,作為該丙烯酸系黏著劑之基礎聚合物之丙烯酸系聚合物較佳為包含源自(甲基)丙烯酸酯之單體單元作為以質量比率計最多之單體單元。作為此種丙烯酸系聚合物,例如,關於放射線硬化性黏著劑,可列舉上述丙烯酸系聚合物。Examples of the adhesive non-reducing adhesive in the adhesive layer 12 include pressure-sensitive adhesives. As the pressure-sensitive adhesive, for example, an acrylic adhesive or a rubber adhesive using an acrylic polymer as a base polymer can be used. When the adhesive layer 12 contains an acrylic adhesive as a pressure-sensitive adhesive, the acrylic polymer as the base polymer of the acrylic adhesive preferably contains a monomer derived from (meth)acrylate The unit serves as the largest monomer unit in terms of mass ratio. As such an acrylic polymer, for example, the radiation-curable adhesive includes the above-mentioned acrylic polymer.

作為黏著劑層12中之感壓性黏著劑,關於黏著力減少型黏著劑,可利用藉由放射線照射使上述放射線硬化性黏著劑硬化之形態之黏著劑。此種已硬化之放射線硬化類型之黏著劑即便因放射線照射黏著力減少,亦可藉由聚合物成分之含量,顯示出由該聚合物成分引起之黏著性,可於特定之使用態樣中發揮出可用於黏著保持被接著體之黏著力。As the pressure-sensitive adhesive in the adhesive layer 12, as the adhesive force-reducing adhesive, an adhesive in a form in which the above-mentioned radiation hardening adhesive is hardened by radiation irradiation can be used. This type of hardened radiation hardening type adhesive can show the adhesion caused by the polymer component by the content of the polymer component even if the adhesive strength of the radiation radiation is reduced due to radiation irradiation, and can be used in a specific use mode It can be used to adhere and maintain the adhesion of the attached body.

於本實施形態之黏著劑層12中,可使用一種黏著力非減少型黏著劑,亦可使用兩種以上之黏著力非減少型黏著劑。又,可利用黏著力非減少型黏著劑形成黏著劑層12之整體,亦可利用黏著力非減少型黏著劑形成黏著劑層12之一部分。例如,於黏著劑層12具有單層構造之情形時,可利用黏著力非減少型黏著劑形成黏著劑層12之整體,可利用黏著力非減少型黏著劑形成黏著劑層12中之特定之部位,亦可利用黏著力減少型黏著劑形成其他部位。又,於黏著劑層12具有積層構造之情形時,可利用黏著力非減少型黏著劑形成構成積層構造之所有層,亦可利用黏著力非減少型黏著劑形成積層構造中之一部分層。In the adhesive layer 12 of the present embodiment, one kind of non-adhesive non-reducing adhesive may be used, or two or more kinds of non-adhesive non-reducing adhesives may be used. In addition, the entire adhesive layer 12 may be formed using a non-reducing adhesive, or a portion of the adhesive layer 12 may be formed using a non-reducing adhesive. For example, in the case where the adhesive layer 12 has a single-layer structure, the entire non-reducing adhesive can be used to form the entire adhesive layer 12, and the non-reducing adhesive can be used to form a specific layer of the adhesive layer 12. Parts can also be used to form other parts using adhesives with reduced adhesion. In addition, when the adhesive layer 12 has a build-up structure, all layers constituting the build-up structure may be formed using a non-reducing adhesive, or a part of the layers in the build-up structure may also be formed using a non-reducing adhesive.

於黏著劑層12或用以構成其之黏著劑中,除上述各成分以外,亦可含有交聯促進劑、或黏著賦予劑、抗老化劑、著色劑等。作為著色劑,可列舉顏料及染料。又,著色劑可為受到放射線照射而著色之化合物。作為此種化合物,例如可列舉隱色染料。The adhesive layer 12 or the adhesive used to constitute it may contain a crosslinking accelerator, an adhesion-imparting agent, an anti-aging agent, a coloring agent, etc. in addition to the above-mentioned components. Examples of the colorant include pigments and dyes. In addition, the colorant may be a compound that is colored by irradiation with radiation. Examples of such compounds include leuco dyes.

黏著劑層12之厚度較佳為1~50 μm,更佳為2~30 μm,更佳為5~25 μm。此種構成例如於黏著劑層12包含放射線硬化性黏著劑之情形時,於取得該黏著劑層12於放射線硬化前後之對於黏著接著劑層20之接著力之平衡性之方面較適宜。The thickness of the adhesive layer 12 is preferably 1-50 μm, more preferably 2-30 μm, still more preferably 5-25 μm. Such a configuration is suitable, for example, in the case where the adhesive layer 12 contains a radiation-curable adhesive, in terms of obtaining a balance between the adhesive force of the adhesive layer 12 to the adhesive adhesive layer 20 before and after radiation curing.

切晶黏晶膜X之黏著接著劑層20兼有作為顯示出黏晶用之熱硬化性之接著劑之功能、及用於保持半導體晶圓等工件與下述環狀框等框構件之黏著功能。於本實施形態中,用以構成黏著接著劑層20之黏著接著劑可具有包含熱硬化性樹脂、與例如作為黏合劑成分之熱塑性樹脂之組成,亦可具有包含帶可與硬化劑反應而產生鍵之熱硬化性官能基之熱塑性樹脂之組成。於用以構成黏著接著劑層20之黏著接著劑具有包含帶熱硬化性官能基之熱塑性樹脂之組成之情形時,該黏著接著劑無需進而包含熱硬化性樹脂(環氧樹脂等)。此種黏著接著劑層20可具有單層構造,亦可具有多層構造。The adhesive bonding layer 20 of the die-bonding film X also functions as an adhesive that exhibits thermosetting properties for crystal bonding, and is used to hold a semiconductor wafer and other workpieces to the frame member such as the following ring frame Features. In this embodiment, the adhesive used to form the adhesive layer 20 may have a composition containing a thermosetting resin and, for example, a thermoplastic resin as an adhesive component, or may include a tape that can react with the curing agent to produce The thermosetting functional group of the thermoplastic resin bond. In the case where the adhesive agent used to form the adhesive agent layer 20 has a composition including a thermoplastic resin with a thermosetting functional group, the adhesive agent does not need to further include a thermosetting resin (epoxy resin, etc.). Such an adhesive layer 20 may have a single-layer structure or a multi-layer structure.

於黏著接著劑層20包含熱硬化性樹脂及熱塑性樹脂之情形時,作為該熱硬化性樹脂,例如可列舉:環氧樹脂、酚系樹脂、胺基樹脂、不飽和聚酯樹脂、聚胺基甲酸酯樹脂、聚矽氧樹脂、及熱硬化性聚醯亞胺樹脂。作為黏著接著劑層20中之熱硬化性樹脂,可使用一種樹脂,亦可使用兩種以上之樹脂。由於存在有可能導致作為黏晶對象之半導體晶片之腐蝕之離子性雜質等之含量較少之傾向,故而作為黏著接著劑層20中所含之熱硬化性樹脂,較佳為環氧樹脂。又,作為環氧樹脂之硬化劑,較佳為酚系樹脂。When the adhesive agent layer 20 contains a thermosetting resin and a thermoplastic resin, examples of the thermosetting resin include epoxy resin, phenol resin, amine-based resin, unsaturated polyester resin, and polyamine-based Formate resin, polysiloxane resin, and thermosetting polyimide resin. As the thermosetting resin in the adhesive layer 20, one resin may be used, or two or more resins may be used. Since there is a tendency for the content of ionic impurities and the like that may cause corrosion of the semiconductor wafer to be bonded to the crystal to be small, the thermosetting resin contained in the adhesive bond layer 20 is preferably epoxy resin. In addition, as the curing agent of the epoxy resin, a phenol resin is preferred.

作為環氧樹脂,例如可列舉: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、茀型、酚系酚醛清漆型、鄰甲酚酚醛清漆型、三羥基苯甲烷型、四酚基乙烷型、乙內醯脲型、三縮水甘油基異氰尿酸酯型、及縮水甘油基胺型之環氧樹脂。酚醛清漆型環氧樹脂、聯苯型環氧樹脂、三羥基苯甲烷型環氧樹脂、及四酚基乙烷型環氧樹脂由於富有與作為硬化劑之酚系樹脂之反應性且耐熱性優異,故而作為黏著接著劑層20中所含之環氧樹脂而較佳。Examples of the epoxy resin include bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol AF type, biphenyl type, naphthalene type, and stilbene. Type, phenolic novolac type, o-cresol novolac type, trihydroxyphenylmethane type, tetraphenol ethane type, hydantoin type, triglycidyl isocyanurate type, and glycidyl amine Type epoxy resin. Novolac-type epoxy resin, biphenyl-type epoxy resin, trihydroxyphenylmethane-type epoxy resin, and tetraphenol-based epoxide-type epoxy resin are rich in reactivity with phenol resin as a curing agent and have excellent heat resistance Therefore, it is preferable as the epoxy resin contained in the adhesive layer 20.

作為可作為環氧樹脂之硬化劑而起作用之酚系樹脂,例如可列舉:酚醛清漆型酚系樹脂、可溶酚醛型酚系樹脂、及聚對羥基苯乙烯等聚氧苯乙烯。作為酚醛清漆型酚系樹脂,例如可列舉:酚系酚醛清漆樹脂、酚系芳烷基樹脂、甲酚酚醛清漆樹脂、第三丁基酚系酚醛清漆樹脂、及壬基酚系酚醛清漆樹脂。作為可作為環氧樹脂之硬化劑而起作用之酚系樹脂,可使用一種酚系樹脂,亦可使用兩種以上之酚系樹脂。酚系酚醛清漆樹脂或酚系芳烷基樹脂於用作作為黏晶用接著劑之環氧樹脂之硬化劑之情形時有可提高該接著劑之連接可靠性之傾向,故而作為黏著接著劑層20中所含之環氧樹脂之硬化劑而較佳。Examples of the phenol resin that can function as a curing agent for epoxy resin include novolac type phenol resin, soluble phenol type phenol resin, and polyoxystyrene such as poly-p-hydroxystyrene. Examples of the novolak type phenol resins include phenol novolak resins, phenol aralkyl resins, cresol novolak resins, tertiary butyl phenol novolak resins, and nonylphenol novolak resins. As the phenol resin that can function as a hardener for the epoxy resin, one phenol resin may be used, or two or more phenol resins may be used. Phenolic novolak resins or phenolic aralkyl resins have a tendency to improve the connection reliability of the adhesive when used as a hardener for epoxy resins used as adhesives for crystal bonding, so they are used as an adhesive adhesive layer The hardener of epoxy resin contained in 20 is preferable.

就充分地進行黏著接著劑層20中之環氧樹脂與酚系樹脂之硬化反應之觀點而言,酚系樹脂係以環氧樹脂成分中之環氧基每1當量,該酚系樹脂中之羥基較佳為成為0.5~2.0當量、更佳為成為0.8~1.2當量之量包含於黏著接著劑層20中。From the viewpoint of sufficiently performing the hardening reaction between the epoxy resin and the phenol resin in the adhesive layer 20, the phenol resin is based on 1 equivalent of epoxy groups in the epoxy resin component. The hydroxyl group is preferably contained in the adhesive layer 20 in an amount of 0.5 to 2.0 equivalents, more preferably 0.8 to 1.2 equivalents.

關於黏著接著劑層20中之熱硬化性樹脂之含有比率,就於黏著接著劑層20中適當地表現出作為熱硬化型接著劑之功能之觀點而言,較佳為5~60質量%,更佳為10~50質量%。The content ratio of the thermosetting resin in the adhesive layer 20 is preferably 5 to 60% by mass from the viewpoint of properly exhibiting the function as a thermosetting adhesive in the adhesive layer 20. It is more preferably 10 to 50% by mass.

作為黏著接著劑層20中所含之熱塑性樹脂,例如可列舉: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-尼龍或6,6-尼龍等聚醯胺樹脂、苯氧基樹脂、丙烯酸系樹脂、PET或PBT等飽和聚酯樹脂、聚醯胺醯亞胺樹脂、及氟樹脂。作為黏著接著劑層20中之熱塑性樹脂,可使用一種樹脂,亦可使用兩種以上之樹脂。作為黏著接著劑層20中所含之熱塑性樹脂,基於由於離子性雜質較少且耐熱性較高故而容易確保利用黏著接著劑層20之接合可靠性之原因,較佳為丙烯酸系樹脂。Examples of the thermoplastic resin contained in the adhesive layer 20 include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid copolymer. Ethylene-acrylate copolymer, polybutadiene resin, polycarbonate resin, thermoplastic polyimide resin, 6-nylon or 6,6-nylon polyamide resin, phenoxy resin, acrylic resin, PET Or PBT and other saturated polyester resin, polyamidoamide imide resin, and fluorine resin. As the thermoplastic resin in the adhesive layer 20, one resin may be used, or two or more resins may be used. As the thermoplastic resin contained in the adhesive layer 20, acrylic resin is preferable because it is easy to ensure the reliability of bonding by the adhesive layer 20 because there are few ionic impurities and high heat resistance.

黏著接著劑層20較佳為包含重量平均分子量800000~2000000且玻璃轉移溫度-10~3℃之聚合物成分作為熱塑性樹脂之主成分。所謂熱塑性樹脂之主成分係設為於熱塑性樹脂成分中占最大之質量比率之樹脂成分。此種構成於謀求黏著接著劑層20於低溫下之割斷性、黏著接著劑層對於框構件20之貼合力、及黏著接著劑層20之剝離時殘渣之防止之平衡性之方面較適宜。就黏著接著劑層20於低溫下之割斷性之確保之觀點或剝離時殘渣之防止之觀點而言,該聚合物之重量平均分子量更佳為900000以上,更佳為1000000以上。就確保黏著接著劑層20之對框構件貼合力之觀點而言,該聚合物之重量平均分子量更佳為1800000以下,更佳為1500000以下。就確保黏著接著劑層20於低溫下之割斷性之觀點而言,該聚合物之玻璃轉移溫度更佳為-8℃以上,更佳為-6.5℃以上。就確保黏著接著劑層20之低溫下之對框構件黏著力之觀點而言,該聚合物之玻璃轉移溫度更佳為0℃以下,更佳為-1.5℃以下。The adhesive layer 20 preferably contains a polymer component having a weight average molecular weight of 800,000 to 2,000,000 and a glass transition temperature of -10 to 3°C as the main component of the thermoplastic resin. The main component of the thermoplastic resin is the resin component that accounts for the largest mass ratio among the thermoplastic resin components. Such a configuration is suitable for achieving balance between the cutoff property of the adhesive agent layer 20 at a low temperature, the adhesive force of the adhesive agent layer to the frame member 20, and the prevention of residues during peeling of the adhesive agent layer 20. From the viewpoint of ensuring the cut-off property of the adhesive layer 20 at low temperatures or the prevention of residues during peeling, the weight average molecular weight of the polymer is more preferably 900,000 or more, and still more preferably 1,000,000 or more. From the viewpoint of ensuring the adhesion of the adhesive layer 20 to the frame member, the weight-average molecular weight of the polymer is preferably 1.8 million or less, and more preferably 1.5 million or less. From the viewpoint of ensuring the cut-off property of the adhesive adhesive layer 20 at a low temperature, the glass transition temperature of the polymer is more preferably -8°C or higher, more preferably -6.5°C or higher. From the viewpoint of ensuring the adhesion to the frame member at a low temperature of the adhesive adhesive layer 20, the glass transition temperature of the polymer is more preferably 0°C or lower, more preferably -1.5°C or lower.

關於聚合物之玻璃轉移溫度,可使用基於下述Fox之式而求出之玻璃轉移溫度(理論值)。Fox之式為聚合物之玻璃轉移溫度Tg、與該聚合物中之每一構成單體之均聚物之玻璃轉移溫度Tgi之關係式。於下述Fox之式中,Tg表示聚合物之玻璃轉移溫度(℃),Wi表示構成該聚合物之單體i之重量分率,Tgi表示單體i之均聚物之玻璃轉移溫度(℃)。關於均聚物之玻璃轉移溫度,可使用文獻值。例如於「新高分子文庫7 塗料用合成樹脂入門」(北岡協三著,高分子刊行會,1995年)或「丙烯酸酯目錄(1997年度版)」(Mitsubishi Rayon股份有限公司)中,列舉有各種均聚物之玻璃轉移溫度。另一方面,關於單體之均聚物之玻璃轉移溫度,亦可藉由日本專利特開2007-51271號公報中具體地記載之方法而求出。Regarding the glass transition temperature of the polymer, a glass transition temperature (theoretical value) determined based on the following Fox formula can be used. The formula of Fox is the relationship between the glass transition temperature Tg of the polymer and the glass transition temperature Tgi of each homopolymer of the monomer in the polymer. In the following Fox formula, Tg represents the glass transition temperature of the polymer (°C), Wi represents the weight fraction of the monomer i constituting the polymer, and Tgi represents the glass transition temperature of the homopolymer of the monomer i (°C ). Regarding the glass transition temperature of the homopolymer, literature values can be used. For example, in the "New Polymer Library 7 Introduction to Synthetic Resins for Coatings" (Sanka Kitaoka, Polymer Press Conference, 1995) or "Acrylate Catalog (1997 Edition)" (Mitsubishi Rayon Co., Ltd.), various examples are listed. The glass transition temperature of the homopolymer. On the other hand, the glass transition temperature of the homopolymer of the monomer can also be determined by the method specifically described in Japanese Patent Laid-Open No. 2007-51271.

Fox之式 1/(273+Tg)=Σ[Wi/(273+Tgi)]Fox's formula 1/(273+Tg)=Σ[Wi/(273+Tgi)]

於黏著接著劑層20中作為熱塑性樹脂而包含之丙烯酸系樹脂較佳為包含源自(甲基)丙烯酸酯之單體單元作為以質量比率計最多之主要單體單元。作為此種(甲基)丙烯酸酯,例如,關於作為黏著劑層12形成用之放射線硬化性黏著劑之一組分之丙烯酸系聚合物,可使用與上述者同樣之(甲基)丙烯酸酯。於黏著接著劑層20中作為熱塑性樹脂而包含之丙烯酸系樹脂可含有源自可與(甲基)丙烯酸酯進行共聚之其他單體之單體單元。作為此種其他單體成分,例如可列舉:含羧基之單體、酸酐單體、含羥基之單體、含縮水甘油基之單體、含磺酸基之單體、含磷酸基之單體、丙烯醯胺、丙烯腈等含官能基之單體、或各種多官能性單體,具體而言,關於作為黏著劑層12形成用之放射線硬化性黏著劑之一組分之丙烯酸系聚合物,作為可與(甲基)丙烯酸酯進行共聚之其他單體,可使用與上述者同樣者。就於黏著接著劑層20中實現較高之凝聚力之觀點而言,黏著接著劑層20中所含之該丙烯酸系樹脂較佳為(甲基)丙烯酸酯、含羧基之單體、含氮原子之單體、及多官能性單體之共聚物。作為該(甲基)丙烯酸酯,較佳為烷基之碳數為4以下之(甲基)丙烯酸烷基酯。作為該多官能性單體,較佳為聚縮水甘油基系多官能單體。黏著接著劑層20中所含之該丙烯酸系樹脂更佳為丙烯酸乙酯、丙烯酸丁酯、丙烯酸、丙烯腈、及聚(甲基)丙烯酸縮水甘油酯之共聚物。The acrylic resin contained in the adhesive layer 20 as a thermoplastic resin preferably contains a monomer unit derived from (meth)acrylate as the main monomer unit in terms of mass ratio. As such (meth)acrylate, for example, as the acrylic polymer as a component of the radiation-curable adhesive for forming the adhesive layer 12, the same (meth)acrylate as described above can be used. The acrylic resin contained in the adhesive layer 20 as a thermoplastic resin may contain monomer units derived from other monomers copolymerizable with (meth)acrylate. Examples of such other monomer components include carboxyl group-containing monomers, acid anhydride monomers, hydroxyl group-containing monomers, glycidyl group-containing monomers, sulfonic acid group-containing monomers, and phosphoric acid group-containing monomers. , Acrylamide, acrylonitrile and other functional group-containing monomers, or various polyfunctional monomers, specifically, an acrylic polymer as a component of a radiation-curable adhesive for forming the adhesive layer 12 As the other monomer copolymerizable with (meth)acrylate, the same ones as mentioned above can be used. From the viewpoint of achieving high cohesion in the adhesive layer 20, the acrylic resin contained in the adhesive layer 20 is preferably (meth)acrylate, a carboxyl group-containing monomer, and a nitrogen atom Copolymers of monomers and multifunctional monomers. The (meth)acrylate is preferably an alkyl (meth)acrylate having 4 or less carbon atoms in the alkyl group. The polyfunctional monomer is preferably a polyglycidyl-based polyfunctional monomer. The acrylic resin contained in the adhesive layer 20 is more preferably a copolymer of ethyl acrylate, butyl acrylate, acrylic acid, acrylonitrile, and polyglycidyl (meth)acrylate.

黏著接著劑層20中之丙烯酸系聚合物等聚合物成分包含源自丙烯腈之構成單元之構成因黏著接著劑層20中之該聚合物成分之源自丙烯腈構成單元內之腈基為高極性,故而於在黏著接著劑層20中,實現對於SUS製環狀框等金屬製框構件之較高之密接性之方面較佳。The polymer component such as an acrylic polymer in the adhesive layer 20 contains a structural unit derived from acrylonitrile because the polymer component in the adhesive layer 20 has a high nitrile group derived from an acrylonitrile structural unit Because of the polarity, it is preferable in the adhesive layer 20 to achieve high adhesion to metal frame members such as ring frames made of SUS.

於黏著接著劑層20包含帶熱硬化性官能基之熱塑性樹脂之情形時,作為該熱塑性樹脂,例如可使用含熱硬化性官能基之丙烯酸系樹脂。用以構成該含熱硬化性官能基之丙烯酸系樹脂之丙烯酸系樹脂較佳為包含源自(甲基)丙烯酸酯之單體單元作為以質量比率計最多之主要單體單元。作為此種(甲基)丙烯酸酯,例如關於作為黏著劑層12形成用之放射線硬化性黏著劑之一組分之丙烯酸系聚合物,可使用與上述者同樣之(甲基)丙烯酸酯。另一方面,作為用以構成含熱硬化性官能基之丙烯酸系樹脂之熱硬化性官能基,例如可列舉:縮水甘油基、羧基、羥基、及異氰酸酯基。該等之中,可適宜地使用縮水甘油基及羧基。即,作為含熱硬化性官能基之丙烯酸系樹脂,可適宜地使用含縮水甘油基之丙烯酸系樹脂或含羧基之丙烯酸系樹脂。又,作為含熱硬化性官能基之丙烯酸系樹脂之硬化劑,例如,作為於作為成為黏著劑層12形成用之放射線硬化性黏著劑之一組分之情形時之某種外部交聯劑可使用上述者。於含熱硬化性官能基之丙烯酸系樹脂中之熱硬化性官能基為縮水甘油基之情形時,作為硬化劑,可適宜地使用多酚系化合物,例如可使用上述各種酚系樹脂。When the adhesive layer 20 contains a thermosetting functional group-containing thermoplastic resin, as the thermoplastic resin, for example, an acrylic resin containing a thermosetting functional group can be used. The acrylic resin used to constitute the thermosetting functional group-containing acrylic resin preferably contains a monomer unit derived from (meth)acrylate as the main monomer unit in terms of mass ratio. As such (meth)acrylate, for example, regarding the acrylic polymer as a component of the radiation-curable adhesive for forming the adhesive layer 12, the same (meth)acrylate as described above can be used. On the other hand, examples of the thermosetting functional group for constituting the acrylic resin containing the thermosetting functional group include glycidyl group, carboxyl group, hydroxyl group, and isocyanate group. Among these, glycidyl group and carboxyl group can be suitably used. That is, as the acrylic resin containing a thermosetting functional group, an acrylic resin containing a glycidyl group or an acrylic resin containing a carboxyl group can be suitably used. Also, as a curing agent for the thermosetting functional group-containing acrylic resin, for example, as an external crosslinking agent when it is used as a component of the radiation curing adhesive for forming the adhesive layer 12 Use the above. In the case where the thermosetting functional group in the thermosetting functional group-containing acrylic resin is a glycidyl group, a polyphenolic compound can be suitably used as a curing agent, and for example, the above-mentioned various phenolic resins can be used.

關於為了黏晶而進行硬化前之黏著接著劑層20,為了實現某程度之交聯度,較佳為例如預先將可與黏著接著劑層20中所含之上述樹脂之分子鏈末端之官能基等反應而進行鍵結之多官能性化合物作為交聯劑調配至黏著接著劑層形成用樹脂組合物中。此種構成於對黏著接著劑層20提高高溫下之接著特性方面,又,於謀求耐熱性之改善之方面較適宜。作為此種交聯劑,例如可列舉聚異氰酸酯化合物。作為聚異氰酸酯化合物,例如可列舉:甲苯二異氰酸酯、二苯甲烷二異氰酸酯、對伸苯基二異氰酸酯、1,5-萘二異氰酸酯、及多元醇與二異氰酸酯之加成物。關於黏著接著劑層形成用樹脂組合物中之交聯劑之含量,相對於具有可與該交聯劑反應而進行鍵結之上述官能基之樹脂100質量份,就所形成之黏著接著劑層20之凝聚力提高之觀點而言,較佳為0.05質量份以上,就所形成之黏著接著劑層20之接著力提高之觀點而言,較佳為7質量份以下。又,作為黏著接著劑層20中之交聯劑,可將環氧樹脂等其他多官能性化合物與聚異氰酸酯化合物併用。In order to achieve a certain degree of cross-linking with respect to the adhesive layer 20 before hardening for crystal bonding, for example, it is preferable to preliminarily connect a functional group at the molecular chain end of the resin contained in the adhesive layer 20 in advance The polyfunctional compound that is bonded by a reaction or the like is blended into the resin composition for forming an adhesive layer as a crosslinking agent. Such a configuration is more suitable for improving the adhesive properties of the adhesive layer 20 at high temperatures, and for improving the heat resistance. Examples of such crosslinking agents include polyisocyanate compounds. Examples of the polyisocyanate compound include toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, and addition products of polyol and diisocyanate. With regard to the content of the crosslinking agent in the resin composition for forming an adhesive layer, the adhesive layer is formed with respect to 100 parts by mass of the resin having the above functional group that can react with the crosslinking agent to bond From the viewpoint of improving the cohesive force of 20, it is preferably 0.05 parts by mass or more, and from the viewpoint of improving the adhesion of the formed adhesive adhesive layer 20, it is preferably 7 parts by mass or less. In addition, as the crosslinking agent in the adhesive layer 20, other polyfunctional compounds such as epoxy resins and polyisocyanate compounds can be used in combination.

黏著接著劑層20中之如上所述之高分子量成分之含有比率較佳為50~100質量%,更佳為50~80質量%。所謂高分子量成分係設為重量平均分子量10000以上之成分。此種構成於謀求同時實現黏著接著劑層20對於下述環狀框等框構件之室溫及其附近之溫度下之貼合性與剝離時殘渣之防止之方面較佳。又,黏著接著劑層20可含有於23℃下為液狀之液狀樹脂。於黏著接著劑層20包含此種液狀樹脂之情形時,黏著接著劑層20中之該液狀樹脂之含有比率較佳為1~10質量%,更佳為1~5質量%。此種構成於謀求同時實現黏著接著劑層20對於下述環狀框等框構件之室溫及其附近之溫度下之貼合性與剝離時殘渣之防止之方面較佳。The content ratio of the high molecular weight component in the adhesive layer 20 as described above is preferably 50 to 100% by mass, more preferably 50 to 80% by mass. The high molecular weight component is a component having a weight average molecular weight of 10,000 or more. Such a configuration is preferable in terms of achieving simultaneous adhesion of the adhesive layer 20 to the frame members such as the ring frame at room temperature and the temperature near it, and prevention of residues during peeling. In addition, the adhesive layer 20 may contain a liquid resin that is liquid at 23°C. When the adhesive layer 20 contains such a liquid resin, the content ratio of the liquid resin in the adhesive layer 20 is preferably 1 to 10% by mass, more preferably 1 to 5% by mass. Such a configuration is preferable in terms of achieving simultaneous adhesion of the adhesive layer 20 to the frame members such as the ring frame at room temperature and the temperature near it, and prevention of residues during peeling.

黏著接著劑層20可含有填料。藉由向黏著接著劑層20中調配填料,可調整黏著接著劑層20之拉伸儲存模數等彈性模數、或導電性、導熱性等物性。作為填料,可列舉無機填料及有機填料,尤佳為無機填料。作為無機填料,例如可列舉:氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、矽酸鈣、矽酸鎂、氧化鈣、氧化鎂、氧化鋁、氮化鋁、硼酸鋁晶鬚、氮化硼、結晶二氧化矽、非晶二氧化矽、此外之鋁、金、銀、銅、鎳等金屬單體、或合金、非晶形碳黑、石墨。填料可具有球狀、針狀、薄片狀等各種形狀。於黏著接著劑層20中可調配一種填料,亦可調配兩種以上之填料。於在黏著接著劑層20中確保下述延伸步驟中之割斷性之方面,黏著接著劑層20之二氧化矽填料含量較佳為10質量%以上。於在黏著接著劑層20中確保凝聚力而防止自框構件剝離時之殘渣之方面,黏著接著劑層20之二氧化矽填料含有比率較佳為40質量%以下,更佳為30質量%以下,更佳為25質量%以下。The adhesive layer 20 may contain a filler. By blending the filler into the adhesive layer 20, the elastic modulus such as the tensile storage modulus of the adhesive layer 20 or the physical properties such as electrical conductivity and thermal conductivity can be adjusted. Examples of fillers include inorganic fillers and organic fillers, and inorganic fillers are particularly preferred. Examples of inorganic fillers include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whiskers, and nitride Boron, crystalline silicon dioxide, amorphous silicon dioxide, in addition to aluminum, gold, silver, copper, nickel and other metal monomers, or alloys, amorphous carbon black, graphite. The filler may have various shapes such as a spherical shape, a needle shape, and a sheet shape. One kind of filler can be blended in the adhesive layer 20, and two or more kinds of fillers can also be blended. In terms of ensuring the cut-off property in the following extension step in the adhesive layer 20, the content of the silica filler in the adhesive layer 20 is preferably 10% by mass or more. In terms of ensuring the cohesive force in the adhesive layer 20 and preventing the residue from peeling off from the frame member, the content ratio of the silica filler in the adhesive layer 20 is preferably 40% by mass or less, more preferably 30% by mass or less, It is more preferably 25% by mass or less.

於黏著接著劑層20含有填料之情形時之該填料之平均粒徑較佳為0.005~10 μm,更佳為0.005~1 μm。該填料之平均粒徑為0.005 μm以上之構成於在黏著接著劑層20中,實現對於半導體晶圓等被接著體之較高之潤濕性或接著性之方面較適宜。該填料之平均粒徑為10 μm以下之構成於在黏著接著劑層20中享受充分之填料添加效果,並且確保耐熱性之方面較適宜。填料之平均粒徑例如可使用光度式之粒度分佈計(商品名「LA-910」、堀場製作所股份有限公司製造)而求出。When the adhesive layer 20 contains a filler, the average particle size of the filler is preferably 0.005 to 10 μm, more preferably 0.005 to 1 μm. The filler having an average particle size of 0.005 μm or more is suitable for the adhesive layer 20 to achieve high wettability or adhesiveness for adherends such as semiconductor wafers. The average particle diameter of the filler is 10 μm or less, which is suitable for enjoying sufficient filler addition effect in the adhesive layer 20 and ensuring heat resistance. The average particle diameter of the filler can be obtained, for example, using a photometric particle size distribution meter (trade name "LA-910", manufactured by Horiba Manufacturing Co., Ltd.).

黏著接著劑層20視需要可含有一種或兩種以上之其他成分。作為該其他成分,例如可列舉:阻燃劑、矽烷偶合劑、及離子捕捉劑。作為阻燃劑,例如可列舉:三氧化銻、五氧化銻、及溴化環氧樹脂。作為矽烷偶合劑,例如可列舉: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、及γ-縮水甘油氧基丙基甲基二乙氧基矽烷。作為離子捕捉劑,例如可列舉:水滑石類、氫氧化鉍、含氫氧化銻(例如東亞合成股份有限公司製造之「IXE-300」)、特定結構之磷酸鋯(例如東亞合成股份有限公司製造之「IXE-100」)、矽酸鎂(例如協和化學工業股份有限公司製造之「Kyoword 600」)、及矽酸鋁(例如協和化學工業股份有限公司製造之「Kyoword 700」)。可於與金屬離子之間形成錯合物之化合物亦可用作離子捕捉劑。作為此種化合物,例如可列舉:三唑系化合物、四唑系化合物、及聯吡啶系化合物。該等之中,就於與金屬離子之間形成之錯合物之穩定性之觀點而言,較佳為三唑系化合物。作為此種三唑系化合物,例如可列舉:1,2,3-苯并三唑、1-{N,N-雙(2-乙基己基)胺基甲基}苯并三唑、羧基苯并三唑、2-(2-羥基-5-甲基苯基)苯并三唑、2-(2-羥基 -3,5-二-第三丁基苯基)-5-氯苯并三唑、2-(2-羥基-3-第三丁基-5-甲基苯基)-5-氯苯并三唑、2-(2-羥基-3,5-二-第三戊基苯基)苯并三唑、2-(2-羥基-5-第三辛基苯基)苯并三唑、6-(2-苯并三唑基)-4-第三辛基-6'-第三丁基 -4'-甲基-2,2'-亞甲基雙酚、1-(2,3-二羥丙基)苯并三唑、1-(1,2-二羧基二乙基)苯并三唑、1-(2-乙基己基胺基甲基)苯并三唑、2,4-二-第三戊基-6-{(H-苯并三唑-1-基)甲基}苯酚、2-(2-羥基-5-第三丁基苯基)-2H-苯并三唑、3-[3-第三丁基-4-羥基-5-(5-氯-2H-苯并三唑-2-基)苯基]丙酸辛酯、3-[3-第三丁基-4-羥基-5-(5-氯-2H-苯并三唑-2-基)苯基]丙酸-2-乙基己酯、2-(2H-苯并三唑-2-基)-6-(1-甲基-1-苯基乙基)-4-(1,1,3,3-四甲基丁基)苯酚、2-(2H-苯并三唑-2-基)-4-第三丁基苯酚、2-(2-羥基-5-甲基苯基)苯并三唑、2-(2-羥基-5-第三辛基苯基)-苯并三唑、2-(3-第三丁基-2-羥基-5-甲基苯基)-5-氯苯并三唑、2-(2-羥基-3,5-二-第三戊基苯基)苯并三唑、2-(2-羥基-3,5-二-第三丁基苯基)-5-氯-苯并三唑、2-[2-羥基-3,5-二(1,1-二甲基苄基)苯基]-2H-苯并三唑、2,2'-亞甲基雙[6-(2H-苯并三唑-2-基]-4-(1,1,3,3-四甲基丁基)苯酚]、2-[2-羥基-3,5-雙(α,α-二甲基苄基)苯基]-2H-苯并三唑、及3-[3-(2H-苯并三唑-2-基)-5-第三丁基-4-羥基苯基]丙酸甲酯。又,對苯二酚化合物、或羥基蒽醌化合物、多酚化合物等特定之含羥基之化合物亦可用作離子捕捉劑。作為此種含羥基之化合物,例如可列舉:1,2-苯二醇、茜素、蒽絳酚、單寧、沒食子酸、沒食子酸甲酯、及鄰苯三酚。The adhesive layer 20 may contain one or more other components as needed. Examples of the other components include flame retardants, silane coupling agents, and ion trapping agents. Examples of the flame retardant include antimony trioxide, antimony pentoxide, and brominated epoxy resin. Examples of the silane coupling agent include β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyl Methyl diethoxysilane. Examples of the ion trapping agent include hydrotalcite, bismuth hydroxide, antimony hydroxide-containing (for example, "IXE-300" manufactured by East Asia Synthesizer Co., Ltd.), and zirconium phosphate of a specific structure (for example manufactured by East Asia Synthesizer Co., Ltd.) "IXE-100"), magnesium silicate (such as "Kyoword 600" manufactured by Kyowa Chemical Industry Co., Ltd.), and aluminum silicate (such as "Kyoword 700" manufactured by Kyowa Chemical Industry Co., Ltd.). Compounds that can form complexes with metal ions can also be used as ion trapping agents. Examples of such compounds include triazole-based compounds, tetrazole-based compounds, and bipyridine-based compounds. Among these, from the viewpoint of the stability of the complex formed with the metal ion, a triazole-based compound is preferred. Examples of such triazole compounds include 1,2,3-benzotriazole, 1-{N,N-bis(2-ethylhexyl)aminomethyl}benzotriazole, and carboxybenzene Pyrogallazole, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole Azole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-pentylbenzene Group) benzotriazole, 2-(2-hydroxy-5-third octylphenyl) benzotriazole, 6-(2-benzotriazolyl)-4-third octyl-6'- Third butyl-4'-methyl-2,2'-methylenebisphenol, 1-(2,3-dihydroxypropyl)benzotriazole, 1-(1,2-dicarboxydiethyl Group) benzotriazole, 1-(2-ethylhexylaminomethyl) benzotriazole, 2,4-di-third pentyl-6-{(H-benzotriazol-1-yl )Methyl)phenol, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 3-[3-t-butyl-4-hydroxy-5-(5-chloro -2H-benzotriazol-2-yl)phenyl]octyl propionate, 3-[3-tertiarybutyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl )Phenyl]propionic acid-2-ethylhexyl ester, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1, 1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazol-2-yl)-4-third butylphenol, 2-(2-hydroxy-5-methylphenyl ) Benzotriazole, 2-(2-hydroxy-5-third octylphenyl)-benzotriazole, 2-(3-third butyl-2-hydroxy-5-methylphenyl)- 5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-third pentylphenyl) benzotriazole, 2-(2-hydroxy-3,5-di-third butyl Phenyl)-5-chloro-benzotriazole, 2-[2-hydroxy-3,5-bis(1,1-dimethylbenzyl)phenyl]-2H-benzotriazole, 2,2 '-Methylenebis[6-(2H-benzotriazol-2-yl]-4-(1,1,3,3-tetramethylbutyl)phenol], 2-[2-hydroxy-3 ,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, and 3-[3-(2H-benzotriazol-2-yl)-5-third butane Methyl-4-hydroxyphenyl] methyl propionate. In addition, specific hydroxyl-containing compounds such as hydroquinone compounds, hydroxyanthraquinone compounds, and polyphenol compounds can also be used as ion trapping agents. As such hydroxyl-containing compounds Examples of the compounds include 1,2-benzenediol, alizarin, anthracenol, tannin, gallic acid, methyl gallate, and pyrogallol.

黏著接著劑層20之厚度例如處於1~200 μm之範圍內,較佳為7~30 μm。黏著接著劑層20之厚度為7 μm以上之構成於貼附有框構件之黏著接著劑層20追隨該框構件表面之微細凹凸而發揮出良好之框構件貼合性之方面較佳。黏著接著劑層20之厚度為30 μm以下之構成於在黏著接著劑層20中確保下述延伸步驟中之割斷性之方面較佳。The thickness of the adhesive layer 20 is, for example, in the range of 1 to 200 μm, preferably 7 to 30 μm. It is preferable that the adhesive layer 20 having a thickness of 7 μm or more, which is formed on the frame member to which the frame member is attached, follows the fine irregularities on the surface of the frame member to exhibit good frame member adhesion. The structure in which the thickness of the adhesive layer 20 is 30 μm or less is preferable in terms of ensuring the cut-off property in the following extension step in the adhesive layer 20.

黏著接著劑層20對寬度10 mm及厚度160 μm之黏著接著劑層試樣片於初始夾頭間距離22.5 mm、頻率1 Hz、動態應變0.005%、及升溫速度10℃/min之條件下測定之25℃下之拉伸儲存模數(第1拉伸儲存模數)為5~120 MPa。該第1拉伸儲存模數較佳為6 MPa以上,更佳為7 MPa以上,且較佳為110 MPa以下,更佳為100 MPa以下。The adhesive layer 20 was measured under the conditions of an initial chuck distance of 22.5 mm, a frequency of 1 Hz, a dynamic strain of 0.005%, and a heating rate of 10°C/min for a 10 mm wide and 160 μm thick adhesive layer sample piece The tensile storage modulus (the first tensile storage modulus) at 25°C is 5 to 120 MPa. The first tensile storage modulus is preferably 6 MPa or more, more preferably 7 MPa or more, and preferably 110 MPa or less, more preferably 100 MPa or less.

黏著接著劑層20對寬度5 mm及厚度80 μm之黏著接著劑層試樣片於初始夾頭間距離10 mm、頻率900 Hz、動態應變0.005%、及升溫速度5℃/min之條件下測定之-15℃下之拉伸儲存模數(第2拉伸儲存模數)為3000~6000 MPa。該第2拉伸儲存模數較佳為3200 MPa以上,更佳為3500 MPa以上,且較佳為5800 MPa以下,更佳為5500 MPa以下。The adhesive agent layer 20 was measured under the conditions of the distance between the initial chuck 10 mm, the frequency 900 Hz, the dynamic strain 0.005%, and the heating rate of 5 ℃/min for a sample piece of the adhesive agent layer with a width of 5 mm and a thickness of 80 μm. The tensile storage modulus (the second tensile storage modulus) at -15°C is 3000 to 6000 MPa. The second tensile storage modulus is preferably 3200 MPa or more, more preferably 3500 MPa or more, and preferably 5800 MPa or less, more preferably 5500 MPa or less.

對於黏著接著劑層20中之SUS平面之-15℃下之剪切黏著力較佳為66 N/cm2 以上,更佳為68 N/cm2 以上,更佳為70 N/cm2 以上。剪切黏著力係設為藉由關於實施例而於下文中所說明之剪切黏著力測定方法所測定之值。與剪切黏著力相關之該構成於確保利用-15℃及其附近之低溫下之切晶黏晶膜X之框構件之保持之方面較適宜。The shear adhesion at -15°C of the SUS plane in the adhesive layer 20 is preferably 66 N/cm 2 or more, more preferably 68 N/cm 2 or more, and even more preferably 70 N/cm 2 or more. The shear adhesion is set to the value measured by the shear adhesion measurement method described below with respect to the examples. The structure related to the shear adhesion is more suitable for ensuring the retention of the frame member of the die-cut adhesive film X at a low temperature of -15°C and its vicinity.

於本實施形態中,於切晶黏晶膜X之面內方向D,黏著接著劑層20之外周端20e距切晶帶10中之基材11之外周端11e及黏著劑層12之外周端12e位於1000 μm以內、較佳為700 μm以內、更佳為500 μm以內、更佳為300 μm以內之距離。即,黏著接著劑層20之外周端20e遍及整周,或於膜面內方向D,相對於基材11及黏著劑層12之外周端11e、12e位於內側1000 μm至外側1000 μm之間,較佳為位於內側700 μm至外側700 μm之間,更佳為位於內側500 μm至外側500 μm之間,更佳為位於內側300 μm至外側300 μm之間。於切晶帶10或其黏著劑層12與其上之黏著接著劑層20於面內方向D具有實質上相同之尺寸之該構成中,黏著接著劑層20如上所述,於面20a側除包含工件貼合用區域以外,且包含框構件貼合用區域。In this embodiment, in the in-plane direction D of the die-cut adhesive film X, the outer peripheral end 20e of the adhesive layer 20 is away from the outer peripheral end 11e of the substrate 11 in the dicing tape 10 and the outer peripheral end of the adhesive layer 12 12e is within a distance of within 1000 μm, preferably within 700 μm, more preferably within 500 μm, more preferably within 300 μm. That is, the outer peripheral end 20e of the adhesive layer 20 extends over the entire circumference, or in the direction D in the film plane, with respect to the outer peripheral ends 11e and 12e of the base material 11 and the adhesive layer 12 between 1000 μm on the inside and 1000 μm on the outside. Preferably, it is between 700 μm on the inside and 700 μm on the outside, more preferably between 500 μm on the inside and 500 μm on the outside, and more preferably between 300 μm on the inside and 300 μm on the outside. In the structure in which the dicing tape 10 or its adhesive layer 12 and the adhesive adhesive layer 20 thereon have substantially the same size in the in-plane direction D, the adhesive adhesive layer 20 is as described above except that the surface 20a side The area outside the workpiece bonding area and including the frame member bonding area.

於切晶黏晶膜X中,於切晶帶10之黏著劑層12為放射線硬化型黏著劑層之情形時,於23℃及剝離速度300 mm/min之條件下之T型剝離試驗中之放射線硬化前之黏著劑層12與黏著接著劑層20之間之剝離力較佳為0.5 N/20 mm以上,更佳為0.6 N/20 mm以上。關於此種T型剝離試驗,可使用拉伸試驗機(商品名「Autograph AGS-J」、島津製作所股份有限公司製造)而進行。供於該試驗之試樣片例如係藉由在向切晶黏晶膜X之黏著接著劑層20側貼合加襯帶(商品名「BT-315」、日東電工股份有限公司製造)後,切割寬度50 mm×長度120 mm之尺寸之試樣片而製作。In the die-cut die-bonding film X, when the adhesive layer 12 of the die-cut tape 10 is a radiation hardening type adhesive layer, in the T-type peeling test under the conditions of 23°C and a peeling speed of 300 mm/min The peeling force between the adhesive layer 12 and the adhesive adhesive layer 20 before radiation hardening is preferably 0.5 N/20 mm or more, and more preferably 0.6 N/20 mm or more. Such a T-type peeling test can be performed using a tensile testing machine (trade name "Autograph AGS-J", manufactured by Shimadzu Corporation). The sample piece used for this test is, for example, by attaching a tape (trade name "BT-315", manufactured by Nitto Denko Co., Ltd.) to the adhesive adhesive layer 20 side of the tangential die-bonding film X. The test piece with a width of 50 mm and a length of 120 mm is cut to make it.

切晶黏晶膜X如圖2所示,可帶隔片S。具體而言,每一切晶黏晶膜X可採用帶隔片S之片狀之形態,亦可隔片S為長條狀,於其上配置複數個切晶黏晶膜X且該隔片S被捲繞而設為輥之形態。隔片S係用於被覆切晶黏晶膜X之黏著接著劑層20之表面而進行保護之要素,於使用切晶黏晶膜X時,自該膜剝離。作為隔片S,例如可列舉利用聚對苯二甲酸乙二酯(PET)膜、聚乙烯膜、聚丙烯膜、氟系剝離劑或長鏈烷基丙烯酸酯系剝離劑等剝離劑進行了表面塗佈之塑膠膜或紙類等。隔片S之厚度例如為5~200 μm。The die-cut crystal bonding film X is shown in FIG. 2 and may have a spacer S. Specifically, each crystal bonding film X may adopt a sheet shape with a spacer S, or the spacer S may be in a strip shape, and a plurality of slicing crystal bonding films X are arranged on the spacer S It is wound into a roll form. The spacer S is an element for covering and protecting the surface of the adhesive bond layer 20 of the die-bonding film X. When the die-bonding film X is used, it is peeled from the film. As the separator S, for example, a surface prepared with a release agent such as polyethylene terephthalate (PET) film, polyethylene film, polypropylene film, fluorine-based release agent, or long-chain alkyl acrylate-based release agent can be cited. Coated plastic film or paper, etc. The thickness of the spacer S is, for example, 5 to 200 μm.

具有如上所述之構成之切晶黏晶膜X例如能夠以如下方式製造。The die-cut die-bonding film X having the above-mentioned structure can be manufactured as follows, for example.

首先,如圖3(a)所示,於長條狀之隔片S上形成黏著接著劑組合物層C1。黏著接著劑組合物層C1可藉由將黏著接著劑層20形成用中所製備之黏著接著劑組合物塗敷於隔片S上而形成。作為黏著接著劑組合物之塗敷方法,例如可列舉:輥塗敷、網版塗敷、及凹版塗敷。First, as shown in FIG. 3( a ), an adhesive composition layer C1 is formed on the long separator S. The adhesive composition layer C1 can be formed by applying the adhesive composition prepared in the formation of the adhesive layer 20 on the separator S. Examples of the coating method of the adhesive composition include roll coating, screen coating, and gravure coating.

其次,如圖3(b)所示,於黏著接著劑組合物層C1上形成黏著劑組合物層C2。黏著劑組合物層C2可藉由將黏著劑層12形成用中所製備之黏著劑組合物塗敷於黏著接著劑組合物層C1上而形成。作為黏著劑組合物之塗敷方法,例如可列舉:輥塗敷、網版塗敷、及凹版塗敷。Next, as shown in FIG. 3(b), an adhesive composition layer C2 is formed on the adhesive composition layer C1. The adhesive composition layer C2 can be formed by applying the adhesive composition prepared in the formation of the adhesive layer 12 on the adhesive composition layer C1. Examples of the coating method of the adhesive composition include roll coating, screen coating, and gravure coating.

其次,藉由經過隔片S上之黏著接著劑組合物層C1及黏著劑組合物層C2之一次性之加熱處理,如圖3(c)所示,形成黏著接著劑層20'及黏著劑層12'。於該加熱處理中,視需要使兩層乾燥,又,於兩層中視需要產生交聯反應。加熱溫度例如為60~175℃,加熱時間例如為0.5~5分鐘。黏著接著劑層20'係加工形成為上述黏著接著劑層20者。黏著劑層12'係加工形成為上述黏著劑層12者。Next, by a one-time heat treatment through the adhesive composition layer C1 and the adhesive composition layer C2 on the separator S, as shown in FIG. 3(c), an adhesive layer 20' and an adhesive are formed Floor 12'. In this heat treatment, the two layers are dried as needed, and a crosslinking reaction occurs in the two layers as needed. The heating temperature is, for example, 60 to 175°C, and the heating time is, for example, 0.5 to 5 minutes. The adhesive layer 20' is processed into the above-mentioned adhesive layer 20. The adhesive layer 12' is processed into the above-mentioned adhesive layer 12.

其次,如圖3(d)所示,將基材11'壓接而貼合於黏著劑層12'上。基材11'係加工形成為上述基材11者。樹脂製造之基材11'可藉由壓延製膜法、於有機溶劑中之澆鑄法、於密閉系統中之吹脹擠出法、T模擠出法、共擠壓法、乾式層壓法等製膜方法而製作。對製膜後之膜或基材11'視需要實施特定之表面處理。於本步驟中,貼合溫度例如為30~50℃,較佳為35~45℃。貼合壓力(線壓)例如為0.1~20 kgf/cm,較佳為1~10 kgf/cm。藉由本步驟,可獲得具有隔片S、黏著接著劑層20'、黏著劑層12'及基材11'之積層構造之長條狀之積層片材體。Next, as shown in FIG. 3(d), the base material 11' is pressure-bonded and bonded to the adhesive layer 12'. The base material 11' is processed into the base material 11 described above. The substrate 11' made of resin can be produced by calendering, casting in organic solvents, inflation extrusion in a closed system, T-die extrusion, co-extrusion, dry lamination, etc. Manufactured by the film production method. The film or substrate 11' after film formation is subjected to a specific surface treatment as necessary. In this step, the bonding temperature is, for example, 30 to 50°C, preferably 35 to 45°C. The bonding pressure (linear pressure) is, for example, 0.1 to 20 kgf/cm, preferably 1 to 10 kgf/cm. By this step, an elongated laminated sheet body having a laminated structure of the separator S, the adhesive layer 20', the adhesive layer 12', and the substrate 11' can be obtained.

其次,如圖4(a)所示,對上述積層片材體,實施將加工刀自基材11'之側插入至隔片S之加工(圖4(a)中模式性地以粗線表示切斷部位)。例如,一面使積層片材體沿一方向F以一定速度流動,一面對圍繞著與該方向F正交之軸心可旋轉地配置且衝壓加工用之加工刀,使伴隨輥表面之附有加工刀之旋轉輥(圖示略)之附有加工刀之表面帶特定之推壓力地抵接於積層片材體之基材11'側。藉此,切晶帶10(基材11、黏著劑層12)與黏著接著劑層20一次性地加工形成。分別包含切晶帶10與黏著接著劑層20之複數個積層體以上述方式於隔片S上經加工形成後,如圖4(b)所示,各積層體(切晶帶10、黏著接著劑層20)之周圍之材料積層部自隔片S上被去除。Next, as shown in FIG. 4(a), the above-mentioned laminated sheet body is processed by inserting a processing blade from the side of the base material 11' into the separator S (in FIG. 4(a), the cut is schematically indicated by a thick line). Broken parts). For example, while making the laminated sheet body flow at a constant speed in a direction F, and facing a processing knife rotatably arranged around the axis orthogonal to the direction F and used for stamping, the accompanying surface of the roller is attached The surface of the rotating roll (not shown) of the processing blade with the processing blade abuts against the base material 11' side of the laminated sheet body with a specific pushing force. In this way, the dicing tape 10 (the base material 11 and the adhesive layer 12) and the adhesive adhesive layer 20 are processed at once. After a plurality of laminates including the dicing tape 10 and the adhesive bond layer 20 are processed and formed on the spacer S in the above manner, as shown in FIG. 4(b), each laminate (dicing tape 10, adhesive bonding) The material accumulation part around the agent layer 20) is removed from the separator S.

能夠以如上方式製造切晶黏晶膜X。The die-cut die-bonding film X can be manufactured in the above manner.

於半導體裝置之製造過程中,存在於如上所述般獲得附有黏晶膜之半導體晶片後,實施使用切晶黏晶膜而進行之延伸步驟、即,用於割斷之延伸步驟之情形。於該延伸步驟中,需要半導體晶圓等工件與環狀框等框構件均保持於切晶黏晶膜,並且黏晶膜可藉由切晶帶10之延伸而割斷。In the manufacturing process of a semiconductor device, after obtaining a semiconductor wafer to which a die-bonding film is attached as described above, an extension step performed using a dicing die-bonding film, that is, an extension step for severing, is performed. In this extension step, it is required that both the workpiece such as a semiconductor wafer and the frame member such as a ring frame are held in the die-bonding die-bonding film, and the die-bonding film can be cut by the extension of the die-cutting tape 10.

上述實施形態之切晶黏晶膜X之作為黏晶膜之黏著接著劑層20係如上所述,於25℃下之上述第1拉伸儲存模數為5~120 MPa。此種構成於在切晶黏晶膜X或其黏著接著劑層20中確保常溫下對於環狀框等框構件之貼合力之方面上較適宜。具體而言,該構成於在常溫下將框構件適當地貼附於切晶黏晶膜X或其黏著接著劑層20之方面較適宜。又,該構成於在延伸步驟之前後處於常溫之黏著接著劑層20中實現良好之黏著力之方面上較適宜。對於切晶黏晶膜X要求於自貼附於其之框構件剝離時於該框構件上不會產生糊劑殘留(剝離時殘渣之防止),結果就於切晶黏晶膜X中之黏著接著劑層20中防止於常溫下之剝離時殘渣之觀點而言,於25℃下之第1拉伸儲存模數較佳為6 MPa以上,更佳為7 MPa以上。就於黏著接著劑層20中實現常溫下對於框構件之較高之貼合力之觀點而言,於25℃下之第1拉伸儲存模數較佳為110 MPa以下,更佳為100 MPa以下。The adhesive bonding agent layer 20 as the die-bonding film of the dicing die-bonding film X of the above embodiment is as described above, and the first tensile storage modulus at 25° C. is 5 to 120 MPa. Such a configuration is more suitable in terms of ensuring the bonding force to the frame member such as a ring frame at normal temperature in the die-cut die-bonding film X or its adhesive adhesive layer 20. Specifically, this configuration is suitable in that the frame member is appropriately attached to the die-bonding film X or its adhesive adhesive layer 20 at normal temperature. In addition, this configuration is preferable in terms of achieving good adhesion in the adhesive adhesive layer 20 at normal temperature before and after the stretching step. The die-cut die-bonding film X requires that no paste remains on the frame member when it is peeled off from the frame member attached to it (prevention of residues during peeling), resulting in adhesion in the die-cut die-bonding film X From the viewpoint of preventing residue during peeling at normal temperature in the adhesive layer 20, the first tensile storage modulus at 25°C is preferably 6 MPa or more, and more preferably 7 MPa or more. From the viewpoint of achieving higher adhesion to the frame member at normal temperature in the adhesive layer 20, the first tensile storage modulus at 25°C is preferably 110 MPa or less, more preferably 100 MPa or less .

並且,切晶黏晶膜X之黏著接著劑層20如上所述,於-15℃下之第2拉伸儲存模數為3000~6000 MPa。此種構成適合於在-15℃及其附近之低溫下實施之延伸步驟中割斷黏著接著劑層20,並且於在黏著接著劑層20中確保低溫下對於框構件之貼合力之方面上較適宜。就於黏著接著劑層20中實現低溫下之良好之割斷性之觀點而言,於-15℃下之第2拉伸儲存模數較佳為3200 MPa以上,更佳為3500 MPa以上。就於黏著接著劑層20中實現低溫下之較高之貼合力之觀點而言,於-15℃下之第2拉伸儲存模數較佳為5800 MPa以下,更佳為5500 MPa以下。有於延伸步驟實施溫度下之對框構件貼合力越高,該延伸步驟中之黏著接著劑層20或切晶黏晶膜X自框構件之剝離越得到抑制之傾向。In addition, as described above, the adhesive bond layer 20 of the die-cut adhesive film X has a second tensile storage modulus at -15°C of 3000 to 6000 MPa. Such a structure is suitable for cutting off the adhesive layer 20 in the extension step performed at a low temperature of -15°C and its vicinity, and is more suitable in terms of ensuring the adhesion force to the frame member at low temperature in the adhesive layer 20 . From the viewpoint of achieving good cleavage at low temperature in the adhesive layer 20, the second tensile storage modulus at -15°C is preferably 3200 MPa or more, and more preferably 3500 MPa or more. From the viewpoint of achieving higher adhesion at low temperature in the adhesive layer 20, the second tensile storage modulus at -15°C is preferably 5800 MPa or less, and more preferably 5500 MPa or less. The higher the adhesion force to the frame member at the temperature of the extension step, the more the peeling of the adhesive adhesive layer 20 or the die-cut adhesive film X from the frame member in the extension step is suppressed.

如上所述,切晶黏晶膜X於該黏著接著劑層20中,適合於確保延伸步驟中之割斷性,並且實現對於環狀框等框構件之良好之貼合性。As described above, the die-bonding film X in the adhesive layer 20 is suitable for ensuring the cutting property in the extending step and achieving good adhesion to frame members such as ring frames.

又,切晶帶10或其黏著劑層12與其上之黏著接著劑層20於膜面內方向上具有實質上相同之設計尺寸之切晶黏晶膜X如上所述,適合於以一次衝壓加工等加工來一次性地實施如下加工而製作,即用以形成具有基材11與黏著劑層12之積層構造之一個切晶帶10之加工;及用以形成一個黏著接著劑層20之加工。此種切晶黏晶膜X適合於在黏著接著劑層20中確保延伸步驟中之割斷性,並且實現對於框構件之良好之黏著力,而且就製造步驟數削減或製造成本抑制之方面等而言,適合於有效率地進行製造。In addition, the dicing tape 10 or its adhesive layer 12 and the adhesive adhesive layer 20 thereon have substantially the same design dimensions of the dicing adhesive film X in the in-plane direction of the film, as described above, suitable for one-time stamping The processing is performed by performing the following processes at once, that is, a process for forming a dicing tape 10 having a laminated structure of the base material 11 and the adhesive layer 12; and a process for forming an adhesive layer 20. Such a die-cut die-bonding film X is suitable for ensuring the cutting property in the extension step in the adhesive adhesive layer 20, and achieving good adhesion to the frame member, and in terms of reduction of the number of manufacturing steps or suppression of manufacturing cost, etc. It is suitable for efficient manufacturing.

對於切晶黏晶膜X之黏著接著劑層20中之SUS平面之-15℃下之剪切黏著力如上所述,較佳為66 N/cm2 以上,更佳為68 N/cm2 以上,更佳為70 N/cm2 以上。與剪切黏著力相關之此種構成於確保利用-15℃及其附近之低溫下之切晶黏晶膜X來保持框構件之方面上較適宜。The shear adhesion at -15°C of the SUS plane in the adhesive layer 20 of the die-bonding film X is as described above, preferably 66 N/cm 2 or more, more preferably 68 N/cm 2 or more , More preferably 70 N/cm 2 or more. Such a configuration related to shear adhesive force is more suitable for ensuring that the frame-cutting crystal film X at a low temperature of -15°C and its vicinity is used to hold the frame member.

切晶黏晶膜X之黏著接著劑層20如上所述,較佳為包含重量平均分子量800000~2000000且玻璃轉移溫度-10~3℃之聚合物成分。此種構成於謀求黏著接著劑層20於低溫下之割斷性、黏著接著劑層對於框構件20之貼合力、及黏著接著劑層20之剝離時殘渣之防止之平衡性的方面上較適宜。如上所述,就確保黏著接著劑層20於低溫下之割斷性之觀點或防止剝離時殘渣之觀點而言,該聚合物之重量平均分子量更佳為900000以上,更佳為1000000以上。如上所述,就確保黏著接著劑層20之對框構件貼合力之觀點而言,該聚合物之重量平均分子量更佳為1800000以下,更佳為1500000以下。如上所述,就確保黏著接著劑層20於低溫下之割斷性之觀點而言,該聚合物之玻璃轉移溫度更佳為-8℃以上,更佳為-6.5℃以上。如上所述,就確保黏著接著劑層20之低溫下之對框構件黏著力之觀點而言,該聚合物之玻璃轉移溫度更佳為0℃以下,更佳為-1.5℃以下。The adhesive layer 20 of the die-bonding film X is as described above, and preferably contains a polymer component having a weight average molecular weight of 800,000 to 2,000,000 and a glass transition temperature of -10 to 3°C. Such a configuration is preferable in terms of striking the cut-off property of the adhesive adhesive layer 20 at a low temperature, the adhesion force of the adhesive adhesive layer to the frame member 20, and the balance of the prevention of residues during peeling of the adhesive adhesive layer 20. As described above, from the viewpoint of ensuring the cut-off property of the adhesive layer 20 at a low temperature or the viewpoint of preventing residue during peeling, the weight average molecular weight of the polymer is more preferably 900,000 or more, and still more preferably 1,000,000 or more. As described above, from the viewpoint of ensuring the adhesion of the adhesive layer 20 to the frame member, the weight-average molecular weight of the polymer is preferably 1.8 million or less, and more preferably 1.5 million or less. As described above, from the viewpoint of ensuring the cut-off property of the adhesive layer 20 at a low temperature, the glass transition temperature of the polymer is more preferably -8°C or higher, more preferably -6.5°C or higher. As described above, from the viewpoint of ensuring the adhesion to the frame member at a low temperature of the adhesive layer 20, the glass transition temperature of the polymer is more preferably 0°C or lower, and more preferably -1.5°C or lower.

切晶黏晶膜X之切晶帶10之黏著劑層12較佳為放射線硬化型黏著劑層。於切晶帶10之黏著劑層12為放射線硬化型黏著劑層之情形時,於切晶黏晶膜X中,於23℃及剝離速度300 mm/min之條件下之T型剝離試驗中之放射線硬化前之黏著劑層12與黏著接著劑層20之間之剝離力如上所述,較佳為0.5 N/20 mm以上,更佳為0.6 N/20 mm以上。與剝離黏著力相關之此種構成於在黏著接著劑層20中確保對框構件貼合力之方面較佳。The adhesive layer 12 of the dicing tape 10 of the dice bonding film X is preferably a radiation hardening type adhesive layer. In the case where the adhesive layer 12 of the dicing tape 10 is a radiation hardening type adhesive layer, in the T-shaped peeling test of the dicing adhesive film X under the conditions of 23° C. and a peeling speed of 300 mm/min The peeling force between the adhesive layer 12 and the adhesive adhesive layer 20 before radiation hardening is as described above, preferably 0.5 N/20 mm or more, and more preferably 0.6 N/20 mm or more. Such a configuration related to peeling adhesion is preferable in terms of ensuring the adhesion force to the frame member in the adhesive layer 20.

圖5至圖10表示本發明之一實施形態之半導體裝置製造方法。5 to 10 show a method of manufacturing a semiconductor device according to an embodiment of the present invention.

於本半導體裝置製造方法中,首先,如圖5(a)及圖5(b)所示,於半導體晶圓W上形成分割槽30a(分割槽形成步驟)。半導體晶圓W具有第1面Wa及第2面Wb。於半導體晶圓W中之第1面Wa之側已製作有各種半導體元件(圖示略),且該半導體元件所需之配線構造等(圖示略)已形成於第1面Wa上。於本步驟中,於將具有黏著面T1a之晶圓加工用膠帶T1貼合於半導體晶圓W之第2面Wb側後,於將半導體晶圓W保持於晶圓加工用膠帶T1之狀態下,於半導體晶圓W之第1面Wa側使用切晶裝置等之旋轉刀片而形成特定深度之分割槽30a。分割槽30a係用以將半導體晶圓W分離為半導體晶片單位之空隙(於圖5至圖7中,模式性地以粗線表示分割槽30a)。In the method for manufacturing a semiconductor device, first, as shown in FIGS. 5(a) and 5(b), a dividing groove 30a is formed on a semiconductor wafer W (a dividing groove forming step). The semiconductor wafer W has a first surface Wa and a second surface Wb. Various semiconductor elements (not shown) have been fabricated on the side of the first surface Wa in the semiconductor wafer W, and wiring structures etc. (not shown) required for the semiconductor elements have been formed on the first surface Wa. In this step, after the wafer processing tape T1 having the adhesive surface T1a is attached to the second surface Wb side of the semiconductor wafer W, the semiconductor wafer W is held in the state of the wafer processing tape T1 On the first surface Wa side of the semiconductor wafer W, a rotary blade of a crystal cutting device or the like is used to form a dividing groove 30a of a specific depth. The dividing groove 30a is used to separate the semiconductor wafer W into a gap of a semiconductor wafer unit (in FIGS. 5 to 7, the dividing groove 30a is schematically indicated by a thick line).

其次,如圖5(c)所示,進行具有黏著面T2a之晶圓加工用膠帶T2向半導體晶圓W之第1面Wa側之貼合、與晶圓加工用膠帶T1自半導體晶圓W之剝離。Next, as shown in FIG. 5(c), the wafer processing tape T2 having the adhesive surface T2a is attached to the first surface Wa side of the semiconductor wafer W, and the wafer processing tape T1 is removed from the semiconductor wafer W Of stripping.

其次,如圖5(d)所示,於將半導體晶圓W保持於晶圓加工用膠帶T2之狀態下,藉由自第2面Wb之研削加工將半導體晶圓W薄化至特定之厚度(晶圓薄化步驟)。研削加工可使用具備研削磨石之研削加工裝置而進行。藉由該晶圓薄化步驟,於本實施形態中,形成可單片化為複數個半導體晶片31之半導體晶圓30A。具體而言,半導體晶圓30A具有於第2面Wb側連結於該晶圓中單片化為複數個半導體晶片31之部位之部位(連結部)。半導體晶圓30A中之連結部之厚度、即,半導體晶圓30A之第2面Wb與分割槽30a之第2面Wb側前端之間之距離例如為1~30 μm,較佳為3~20 μm。Next, as shown in FIG. 5(d), with the semiconductor wafer W held in the wafer processing tape T2, the semiconductor wafer W is thinned to a specific thickness by grinding processing from the second surface Wb (Wafer thinning step). Grinding processing can be performed using a grinding processing device equipped with grinding stones. Through this wafer thinning step, in this embodiment, a semiconductor wafer 30A that can be singulated into a plurality of semiconductor wafers 31 is formed. Specifically, the semiconductor wafer 30A has a portion (connection portion) connected to a portion of the wafer singulated into a plurality of semiconductor wafers 31 on the second surface Wb side. The thickness of the connecting portion in the semiconductor wafer 30A, that is, the distance between the second surface Wb of the semiconductor wafer 30A and the front end on the second surface Wb side of the dividing groove 30a is, for example, 1 to 30 μm, preferably 3 to 20 μm.

其次,如圖6(a)所示,保持於晶圓加工用膠帶T2之半導體晶圓30A係對切晶黏晶膜X之黏著接著劑層20進行貼合。其後,如圖6(b)所示,自半導體晶圓30A將晶圓加工用膠帶T2剝離。於切晶黏晶膜X中之黏著劑層12為放射線硬化性黏著劑層之情形時,代替切晶黏晶膜X之製造過程中之上述放射線照射,可於半導體晶圓30A向黏著接著劑層20之貼合後,自基材11之側對黏著劑層12照射紫外線等放射線。照射量例如為50~500 mJ/cm2 ,較佳為100~300 mJ/cm2 。於切晶黏晶膜X中進行作為黏著劑層12之黏著力減少措施之照射之區域(圖1所示之照射區域R)例如為黏著劑層12中之黏著接著劑層20貼合區域內之除其周緣部以外之區域。Next, as shown in FIG. 6( a ), the semiconductor wafer 30A held on the wafer processing tape T2 is bonded to the adhesive adhesive layer 20 of the die-bonding film X. Thereafter, as shown in FIG. 6( b ), the wafer processing tape T2 is peeled from the semiconductor wafer 30A. In the case where the adhesive layer 12 in the diced die bonding film X is a radiation hardening adhesive layer, the adhesive can be applied to the semiconductor wafer 30A instead of the above-mentioned radiation irradiation during the manufacturing process of the diced die bonding film X After the layer 20 is bonded, the adhesive layer 12 is irradiated with ultraviolet rays or the like from the side of the base material 11. The irradiation dose is, for example, 50 to 500 mJ/cm 2 , preferably 100 to 300 mJ/cm 2 . The irradiation area (irradiation area R shown in FIG. 1) in the dicing die-bonding film X as a measure for reducing the adhesive force of the adhesive layer 12 is, for example, in the bonding area of the adhesive layer 20 in the adhesive layer 12 The area other than its periphery.

其次,於在切晶黏晶膜X中之黏著接著劑層20上貼附環狀框41後,如圖7(a)所示,帶半導體晶圓30A之該切晶黏晶膜X被固定於延伸裝置之保持具42。Next, after the ring frame 41 is attached to the adhesive adhesive layer 20 in the die-bonding film X, as shown in FIG. 7(a), the die-bonding film X with the semiconductor wafer 30A is fixed于Extender's retainer 42.

其次,相對低溫之條件下之第1延伸步驟(冷卻延伸步驟)係如圖7(b)所示般進行,將半導體晶圓30A單片化為複數個半導體晶片31,並且將切晶黏晶膜X之黏著接著劑層20割斷為小片之黏著接著劑層21,而獲得附有黏著接著劑層之半導體晶片31。於本步驟中,延伸裝置所具備之中空圓柱形狀之頂起構件43於切晶黏晶膜X之圖中下側抵接於切晶帶10而上升,貼合有半導體晶圓30A之切晶黏晶膜X之切晶帶10係以向包含半導體晶圓30A之徑向及圓周方向之二維方向延長之方式延伸。該延伸於切晶帶10中係於產生較佳為15~32 MPa、更佳為20~32 MPa之範圍內之拉伸應力之條件下進行。冷卻延伸步驟中之溫度條件例如為0℃以下,較佳為-20~-5℃,更佳為-15~-5℃,更佳為-15℃。冷卻延伸步驟中之延伸速度(頂起構件43上升之速度)較佳為0.1~100 mm/sec。又,冷卻延伸步驟中之延伸量較佳為3~16 mm。Next, the first stretching step (cooling stretching step) under relatively low temperature conditions is performed as shown in FIG. 7(b), the semiconductor wafer 30A is singulated into a plurality of semiconductor wafers 31, and the die-cut crystal is bonded The adhesive layer 20 of the film X is cut into small pieces of the adhesive layer 21 to obtain a semiconductor wafer 31 with an adhesive layer. In this step, the hollow cylinder-shaped lifting member 43 of the stretching device rises in contact with the dicing tape 10 at the lower side in the figure of the dicing die-bonding film X, and the dicing of the semiconductor wafer 30A is bonded The dicing tape 10 of the die-bonding film X extends in a two-dimensional direction including the radial direction and the circumferential direction of the semiconductor wafer 30A. The stretching in the dicing tape 10 is performed under the condition that a tensile stress within a range of preferably 15 to 32 MPa, more preferably 20 to 32 MPa is generated. The temperature condition in the cooling and extending step is, for example, 0°C or lower, preferably -20 to -5°C, more preferably -15 to -5°C, and even more preferably -15°C. The extending speed (the speed at which the jacking member 43 rises) in the cooling and extending step is preferably 0.1 to 100 mm/sec. In addition, the stretching amount in the cooling stretching step is preferably 3 to 16 mm.

於本步驟中,於半導體晶圓30A中於薄壁且容易破裂之部位發生割斷而產生向半導體晶片31之單片化。並且,於本步驟中,於在與所延伸之切晶帶10之黏著劑層12密接之黏著接著劑層20中於各半導體晶片31所密接之各區域中抑制變形,另一方面,於與半導體晶片31間之分割槽對向之部位未產生此種變形抑制作用之狀態下,於切晶帶10中產生之拉伸應力起作用。其結果為,於黏著接著劑層20中與半導體晶片31間之分割槽對向之部位被割斷。於本步驟後,如圖7(c)所示,頂起構件43下降而解除切晶帶10之延伸狀態。In this step, the thin-walled and easily broken portion of the semiconductor wafer 30A is severed, resulting in singulation of the semiconductor wafer 31. In addition, in this step, deformation is suppressed in each region where each semiconductor wafer 31 is in close contact with the adhesive layer 20 in close contact with the adhesive layer 12 of the extended dicing tape 10, and on the other hand, The tensile stress generated in the dicing tape 10 acts in a state where the divisional groove between the semiconductor wafers 31 does not produce such a deformation suppression effect. As a result, the portion of the adhesive layer 20 facing the dividing groove between the semiconductor wafers 31 is cut. After this step, as shown in FIG. 7(c), the lifting member 43 is lowered to release the extended state of the dicing tape 10.

其次,相對高溫之條件下之第2延伸步驟係如圖8(a)所示般進行,擴大附有黏著接著劑層之半導體晶片31間之距離(相隔距離)。於本步驟中,延伸裝置所具備之中空圓柱形狀之頂起構件43再次上升,切晶黏晶膜X之切晶帶10進行延伸。第2延伸步驟中之溫度條件例如為10℃以上,較佳為15~30℃。第2延伸步驟中之延伸速度(頂起構件43上升之速度)例如為0.1~10 mm/sec,較佳為0.3~1 mm/sec。又,第2延伸步驟中之延伸量例如為3~16 mm。於本步驟中,附有黏著接著劑層之半導體晶片31之相隔距離被擴大至於下述拾取步驟中可適當地自切晶帶10拾取附有黏著接著劑層之半導體晶片31之程度。於本步驟後,如圖8(b)所示,頂起構件43下降而解除切晶帶10中之延伸狀態。於抑制於延伸狀態解除後切晶帶10上之附有黏著接著劑層之半導體晶片31之相隔距離縮小之方面,較佳為先於解除延伸狀態,對切晶帶10中之較半導體晶片31保持區域更靠外側之部分進行加熱而使之收縮。Secondly, the second extension step under relatively high temperature conditions is performed as shown in FIG. 8(a) to increase the distance (separation distance) between the semiconductor wafers 31 to which the adhesive layer is attached. In this step, the hollow cylindrical lifting member 43 of the stretching device is raised again, and the dicing tape 10 of the dicing die-bonding film X is extended. The temperature condition in the second extending step is, for example, 10°C or higher, preferably 15-30°C. The extension speed (the speed at which the jack 43 is lifted) in the second extension step is, for example, 0.1 to 10 mm/sec, preferably 0.3 to 1 mm/sec. In addition, the extension amount in the second extension step is, for example, 3 to 16 mm. In this step, the separation distance of the semiconductor wafer 31 with the adhesive layer is enlarged to the extent that the semiconductor wafer 31 with the adhesive layer can be properly picked up from the dicing tape 10 in the following pickup step. After this step, as shown in FIG. 8(b), the lifting member 43 is lowered to release the extended state in the dicing tape 10. In order to suppress the reduction in the distance between the semiconductor wafers 31 with an adhesive layer attached to the dicing tape 10 after the extended state is released, it is preferable that the diced tape 10 is better than the semiconductor wafer 31 before the extended state is released. The part of the holding area further outside is heated to shrink it.

其次,於視需要經過對帶附有黏著接著劑層之半導體晶片31之切晶帶10中之半導體晶片31側使用水等洗淨液進行洗淨之清潔步驟後,如圖9所示般,自切晶帶10拾取附有黏著接著劑層之半導體晶片31(拾取步驟)。例如,對拾取對象之附有黏著接著劑層之半導體晶片31,於切晶帶10之圖中下側使拾取機構之銷44上升,經由切晶帶10頂起後,利用吸附治具45進行吸附保持。於拾取步驟中,銷44之頂起速度例如為1~100 mm/sec,銷44之頂起量例如為50~3000 μm。Secondly, after going through the cleaning step of cleaning the semiconductor wafer 31 side of the dicing tape 10 with the semiconductor wafer 31 with the adhesive layer attached thereto, if necessary, using a cleaning solution such as water, as shown in FIG. 9, The dicing tape 10 picks up the semiconductor wafer 31 with the adhesive layer attached (pickup step). For example, for the semiconductor wafer 31 with an adhesive layer attached to the object to be picked up, the pins 44 of the pickup mechanism are raised on the lower side of the dicing tape 10 in the figure, and after being lifted through the dicing tape 10, the suction jig 45 is used. Adsorption and retention. In the pickup step, the jacking speed of the pin 44 is, for example, 1 to 100 mm/sec, and the jacking amount of the pin 44 is, for example, 50 to 3000 μm.

其次,如圖10(a)所示,所拾取之附有黏著接著劑層之半導體晶片31係經由黏著接著劑層21而暫時固著於特定之被接著體51。作為被接著體51,例如可列舉:引線框架、TAB(Tape Automated Bonding,捲帶式自動接合)膜、配線基板、及另外製作之半導體晶片。關於黏著接著劑層21於暫時固著時之25℃下之剪切黏著力,相對於被接著體51較佳為0.2 MPa以上,更佳為0.2~10 MPa。黏著接著劑層21之該剪切黏著力為0.2 MPa以上之構成適合於在下述打線接合步驟中,抑制因超音波振動或加熱而於黏著接著劑層21與半導體晶片31或被接著體51之接著面產生剪切變形,並適當地進行打線接合。Next, as shown in FIG. 10( a ), the picked up semiconductor wafer 31 with the adhesive layer attached is temporarily fixed to the specific adherend 51 via the adhesive layer 21. As the adherend 51, for example, a lead frame, a TAB (Tape Automated Bonding) film, a wiring board, and a semiconductor wafer manufactured separately are mentioned. The shear adhesive force at 25° C. when the adhesive layer 21 is temporarily fixed is preferably 0.2 MPa or more and more preferably 0.2 to 10 MPa with respect to the adherend 51. The structure of the adhesive layer 21 with the shear adhesive force of 0.2 MPa or more is suitable for suppressing the adhesion between the adhesive layer 21 and the semiconductor chip 31 or the adherend 51 due to ultrasonic vibration or heating in the following wire bonding step Then the surface is shear deformed and wire bonding is performed appropriately.

其次,如圖10(b)所示,經由接合線52電性連接半導體晶片31之電極墊(圖示略)與被接著體51所具有之端子部(圖示略)(打線接合步驟)。半導體晶片31之電極墊或被接著體51之端子部與接合線52之接線係利用伴隨加熱之超音波焊接而實現,且係以不使黏著接著劑層21熱硬化之方式進行。作為接合線52,例如可使用金線、鋁線、或銅線。打線接合中之導線加熱溫度例如為80~250℃,較佳為80~220℃。又,其加熱時間為數秒~數分鐘。Next, as shown in FIG. 10(b), the electrode pad (not shown) of the semiconductor wafer 31 and the terminal portion (not shown) of the adherend 51 are electrically connected via a bonding wire 52 (wire bonding step). The connection between the electrode pad of the semiconductor chip 31 or the terminal portion of the adherend 51 and the bonding wire 52 is realized by ultrasonic welding with heating, and is performed in such a manner that the adhesive layer 21 is not thermally hardened. As the bonding wire 52, for example, a gold wire, an aluminum wire, or a copper wire can be used. The heating temperature of the wire in wire bonding is, for example, 80 to 250°C, preferably 80 to 220°C. In addition, the heating time is several seconds to several minutes.

其次,如圖10(c)所示,利用用以保護被接著體51上之半導體晶片31或接合線52之密封樹脂53將半導體晶片31密封(密封步驟)。於本步驟中,黏著接著劑層21之熱硬化進行。於本步驟中,例如,藉由使用模具而進行之轉注成形技術形成密封樹脂53。作為密封樹脂53之構成材料,例如可使用環氧系樹脂。於本步驟中,用以形成密封樹脂53之加熱溫度例如為165~185℃,加熱時間例如為60秒~數分鐘。於在本步驟(密封步驟)中密封樹脂53之硬化未充分地進行之情形時,於本步驟後進行用以使密封樹脂53完全硬化之後硬化步驟。於密封步驟中即便於黏著接著劑層21未完全熱硬化之情形時,亦可於後硬化步驟中使密封樹脂53與黏著接著劑層21一併進行完全之熱硬化。於後硬化步驟中,加熱溫度例如為165~185℃,加熱時間例如為0.5~8小時。Next, as shown in FIG. 10(c), the semiconductor wafer 31 is sealed with a sealing resin 53 for protecting the semiconductor wafer 31 or the bonding wire 52 on the adherend 51 (sealing step). In this step, thermal curing of the adhesive layer 21 is performed. In this step, for example, the sealing resin 53 is formed by a transfer molding technique using a mold. As a constituent material of the sealing resin 53, for example, epoxy resin can be used. In this step, the heating temperature for forming the sealing resin 53 is, for example, 165 to 185°C, and the heating time is, for example, 60 seconds to several minutes. In the case where the hardening of the sealing resin 53 is not sufficiently performed in this step (sealing step), a hardening step is performed after this step to completely harden the sealing resin 53. In the sealing step, even when the adhesive layer 21 is not completely thermally cured, the sealing resin 53 and the adhesive layer 21 can be completely thermally cured together in the post-curing step. In the post-hardening step, the heating temperature is, for example, 165 to 185°C, and the heating time is, for example, 0.5 to 8 hours.

能夠以如上方式製造半導體裝置。The semiconductor device can be manufactured in the above manner.

於本實施形態中,如上所述,於將附有黏著接著劑層之半導體晶片31暫時固著於被接著體51後,不使黏著接著劑層21進行完全之熱硬化而進行打線接合步驟。亦可代替此種構成,於將附有黏著接著劑層之半導體晶片31暫時固著於被接著體51後,於黏著接著劑層21進行熱硬化後進行打線接合步驟。In this embodiment, as described above, after temporarily fixing the semiconductor wafer 31 with the adhesive layer to the adherend 51, the wire bonding step is performed without completely thermally hardening the adhesive layer 21. Instead of this configuration, after temporarily fixing the semiconductor wafer 31 with the adhesive layer to the adherend 51, the wire bonding step is performed after the adhesive layer 21 is thermally hardened.

於半導體裝置製造方法中,可於參照圖5(c)而經過上述過程後,參照圖5(d)而進行如圖11所示之晶圓薄化步驟以代替上述晶圓薄化步驟。於圖11所示之晶圓薄化步驟中,於將半導體晶圓W保持於晶圓加工用膠帶T2之狀態下,藉由自第2面Wb之研削加工將該晶圓薄化至特定之厚度,形成含有複數個半導體晶片31並保持於晶圓加工用膠帶T2之半導體晶圓分割體30B。於本步驟中,分割槽30a其本身可採用對晶圓進行研削直至露出至第2面Wb側之方法(第1方法),亦可採用自第2面Wb側對晶圓進行研削直至較分割槽30a更靠前,其後,利用自旋轉磨石向晶圓之推壓力之作用使分割槽30a與第2面Wb之間產生龜裂而形成半導體晶圓分割體30B之方法(第2方法)。根據所採用之方法,適當地決定參照圖5(a)及圖5(b)如上所述般形成之分割槽30a距第1面Wa之深度。於圖11中,對經過第1方法之分割槽30a、或經過第2方法之分割槽30a及與其相連之龜裂,係模式性地以粗線表示。於本實施形態中,可於代替上述半導體晶圓30A將以上述方式製作之半導體晶圓分割體30B貼合於切晶黏晶膜X後,參照圖6至圖10而進行上述各步驟。In the method of manufacturing a semiconductor device, the wafer thinning step shown in FIG. 11 may be performed with reference to FIG. 5(d) after referring to FIG. 5(c) and after the above process, instead of the wafer thinning step. In the wafer thinning step shown in FIG. 11, with the semiconductor wafer W held in the wafer processing tape T2, the wafer is thinned to a specific level by grinding processing from the second surface Wb In the thickness, a semiconductor wafer divided body 30B including a plurality of semiconductor wafers 31 and held by the wafer processing tape T2 is formed. In this step, the dicing groove 30a itself may adopt a method of grinding the wafer until it is exposed to the second surface Wb side (first method), or it may use a method of grinding the wafer from the second surface Wb side until it is more divided The groove 30a is further forward, and thereafter, a method of forming a semiconductor wafer divided body 30B by generating a crack between the dividing groove 30a and the second surface Wb by the pressing force of the rotating grindstone against the wafer (second method). According to the method used, the depth of the dividing groove 30a formed as described above with reference to FIGS. 5(a) and 5(b) from the first surface Wa is appropriately determined. In FIG. 11, the dividing groove 30a passing through the first method or the dividing groove 30a passing through the second method and the cracks connected thereto are schematically indicated by thick lines. In this embodiment, instead of the semiconductor wafer 30A, the semiconductor wafer division 30B produced in the above manner is bonded to the die-bonding film X, and then the above steps can be performed with reference to FIGS. 6 to 10.

圖12(a)及圖12(b)表示於將半導體晶圓分割體30B貼合於切晶黏晶膜X後進行之第1延伸步驟(冷卻延伸步驟)。於本步驟中,延伸裝置所具備之中空圓柱形狀之頂起構件43於切晶黏晶膜X之圖中下側抵接於切晶帶10而上升,貼合有半導體晶圓分割體30B之切晶黏晶膜X之切晶帶10以向包含半導體晶圓分割體30B之徑向及圓周方向之二維方向延長之方式延伸。該延伸係於切晶帶10中,於產生例如為1~100 MPa、較佳為5~40 MPa之範圍內之拉伸應力之條件下進行。本步驟中之溫度條件例如為0℃以下,較佳為-20~-5℃,更佳為-15~-5℃,更佳為-15℃。本步驟中之延伸速度(頂起構件43上升之速度)較佳為1~500 mm/sec。又,本步驟中之延伸量較佳為50~200 mm。藉由此種冷卻延伸步驟,切晶黏晶膜X之黏著接著劑層20被割斷為小片之黏著接著劑層21而獲得附有黏著接著劑層之半導體晶片31。具體而言,於本步驟中,於在與延伸之切晶帶10之黏著劑層12密接之黏著接著劑層20中,於半導體晶圓分割體30B之各半導體晶片31所密接之各區域中抑制變形,另一方面,於與半導體晶片31間之分割槽30a對向之部位未產生此種變形抑制作用之狀態下,於切晶帶10中產生之拉伸應力起作用。其結果為,於黏著接著劑層20中與半導體晶片31間之分割槽30a對向之部位被割斷。FIGS. 12( a) and 12 (b) show the first stretching step (cooling stretching step) performed after bonding the semiconductor wafer division 30B to the die-bonding film X. In this step, the hollow cylinder-shaped lifting member 43 provided in the stretching device rises in contact with the dicing tape 10 at the lower side of the die-bonding film X in the figure, and the semiconductor wafer split body 30B is bonded The dicing tape 10 of the dicing die-bonding film X extends in a two-dimensional direction including the radial direction and the circumferential direction of the semiconductor wafer division 30B. This stretching is performed in the dicing tape 10 under the condition that a tensile stress in the range of, for example, 1 to 100 MPa, preferably 5 to 40 MPa is generated. The temperature condition in this step is, for example, 0°C or lower, preferably -20 to -5°C, more preferably -15 to -5°C, and even more preferably -15°C. The extension speed (the speed at which the jacking member 43 rises) in this step is preferably 1 to 500 mm/sec. In addition, the extension amount in this step is preferably 50 to 200 mm. By this cooling and extending step, the adhesive bond layer 20 of the diced die bonding film X is cut into small pieces of the adhesive bond layer 21 to obtain the semiconductor wafer 31 with the adhesive bond layer. Specifically, in this step, in the adhesive adhesive layer 20 that is in close contact with the adhesive layer 12 of the extended dicing tape 10, in each region where the semiconductor chips 31 of the semiconductor wafer division body 30B are in close contact To suppress the deformation, on the other hand, the tensile stress generated in the dicing tape 10 acts in a state where such a deformation suppression effect does not occur at the portion facing the dividing groove 30a between the semiconductor wafers 31. As a result, the portion of the adhesive layer 20 that faces the dividing groove 30a between the semiconductor wafer 31 is cut.

於本實施形態之半導體裝置製造方法中,可對切晶黏晶膜X貼合以如下方式製作之半導體晶圓30C而代替對切晶黏晶膜X貼合半導體晶圓30A或半導體晶圓分割體30B之上述構成。In the semiconductor device manufacturing method of this embodiment, the semiconductor wafer 30C produced as follows may be bonded to the die-bonding film X instead of bonding the semiconductor wafer 30A or dividing the semiconductor wafer to the die-bonding film X The above structure of the body 30B.

如圖13(a)及圖13(b)所示,首先,於半導體晶圓W上形成改質區域30b。半導體晶圓W具有第1面Wa及第2面Wb。於半導體晶圓W中之第1面Wa之側已製作有各種半導體元件(圖示略),且該半導體元件所需之配線構造等(圖示略)已形成於第1面Wa上。於本步驟中,於將具有黏著面T3a之晶圓加工用膠帶T3貼合於半導體晶圓W之第1面Wa側後,於將半導體晶圓W保持於晶圓加工用膠帶T3之狀態下,自與晶圓加工用膠帶T3相反之側對半導體晶圓W沿著分割預定線照射使聚光點對準晶圓內部之雷射光,藉由利用多光子吸收之切割而於半導體晶圓W內形成改質區域30b。改質區域30b係用於將半導體晶圓W分離為半導體晶片單位之脆弱化區域。關於在半導體晶圓中藉由雷射光照射而於分割預定線上形成改質區域30b之方法,例如係於日本專利特開2002-192370號公報中詳細說明。於該方法中,本實施形態中之雷射光照射條件例如係於以下之條件之範圍內適當加以調整。 <雷射光照射條件> (A)雷射光 雷射光源 半導體雷射激發Nd:YAG雷射 波長 1064 nm 雷射光點截面積 3.14×10-8 cm2 振盪形態 Q開關脈衝 重複頻率 100 kHz以下 脈衝寬度 1 μs以下 輸出 1 mJ以下 雷射光品質 TEM00 偏光特性 直線偏光 (B)聚光用透鏡 倍率 100倍以下 NA 0.55 對於雷射光波長之透過率 100%以下 (C)供載置半導體基板之載置台之移動速度 280 mm/sec以下As shown in FIGS. 13(a) and 13(b), first, a modified region 30b is formed on the semiconductor wafer W. The semiconductor wafer W has a first surface Wa and a second surface Wb. Various semiconductor elements (not shown) have been fabricated on the side of the first surface Wa in the semiconductor wafer W, and wiring structures etc. (not shown) required for the semiconductor elements have been formed on the first surface Wa. In this step, after the wafer processing tape T3 having the adhesive surface T3a is attached to the first surface Wa side of the semiconductor wafer W, the semiconductor wafer W is held in the state of the wafer processing tape T3 , Irradiating the semiconductor wafer W from the side opposite to the wafer processing tape T3 along the planned dividing line to align the condensing point with the laser light inside the wafer, and cutting the semiconductor wafer W by cutting by multiphoton absorption The modified region 30b is formed inside. The modified region 30b is used to separate the semiconductor wafer W into a fragile region per semiconductor wafer unit. The method of forming the modified region 30b on the planned dividing line by laser light irradiation in the semiconductor wafer is described in detail in Japanese Patent Laid-Open No. 2002-192370, for example. In this method, the laser light irradiation conditions in this embodiment are appropriately adjusted within the range of the following conditions, for example. <Laser light irradiation conditions> (A) Laser light laser light source semiconductor laser excitation Nd: YAG laser wavelength 1064 nm Laser light spot cross-sectional area 3.14×10 -8 cm 2 Oscillation form Q switching pulse repetition frequency 100 kHz pulse width 1 μs or less Output 1 mJ or less Laser quality TEM00 Polarization characteristics Linear polarized light (B) Condensing lens magnification 100 times or less NA 0.55 Transmittance for laser light wavelength 100% or less (C) Mounting table for mounting semiconductor substrates Moving speed below 280 mm/sec

其次,於將半導體晶圓W保持於晶圓加工用膠帶T3之狀態下,藉由自第2面Wb之研削加工將半導體晶圓W薄化至特定之厚度,如圖13(c)所示,形成可單片化為複數個半導體晶片31之半導體晶圓30C(晶圓薄化步驟)。於本實施形態中,可代替半導體晶圓30A將以如上方式而製作之半導體晶圓30C貼合於切晶黏晶膜X後,參照圖6至圖10而進行上述各步驟。Next, with the semiconductor wafer W held in the wafer processing tape T3, the semiconductor wafer W is thinned to a specific thickness by grinding processing from the second surface Wb, as shown in FIG. 13(c) To form a semiconductor wafer 30C that can be singulated into a plurality of semiconductor wafers 31 (wafer thinning step). In this embodiment, instead of the semiconductor wafer 30A, the semiconductor wafer 30C fabricated as described above may be bonded to the die-bonding film X, and then the above steps are performed with reference to FIGS. 6 to 10.

圖14(a)及圖14(b)表示於對切晶黏晶膜X貼合半導體晶圓30C後進行之第1延伸步驟(冷卻延伸步驟)。於本步驟中,延伸裝置所具備之中空圓柱形狀之頂起構件43於切晶黏晶膜X之圖中下側抵接於切晶帶10而上升,貼合有半導體晶圓30C之切晶黏晶膜X之切晶帶10係以向包含半導體晶圓30C之徑向及圓周方向之二維方向延長之方式延伸。該延伸係於切晶帶10中,例如於產生1~100 MPa、較佳為5~40 MPa之範圍內之拉伸應力之條件下進行。本步驟中之溫度條件例如為0℃以下,較佳為-20~-5℃,更佳為-15~-5℃,更佳為-15℃。本步驟中之延伸速度(頂起構件43上升之速度)較佳為1~500 mm/sec。又,本步驟中之延伸量較佳為50~200 mm。藉由此種冷卻延伸步驟,切晶黏晶膜X之黏著接著劑層20被割斷為小片之黏著接著劑層21而獲得附有黏著接著劑層之半導體晶片31。具體而言,於本步驟中,於半導體晶圓30C中於脆弱之改質區域30b形成龜裂而產生向半導體晶片31之單片化。並且,於本步驟中,於在與延伸之切晶帶10之黏著劑層12密接之黏著接著劑層20中,於半導體晶圓30C之各半導體晶片31所密接之各區域抑制變形,另一方面,於與晶圓之龜裂形成部位對向之部位未產生此種變形抑制作用之狀態下,於切晶帶10中產生之拉伸應力起作用。其結果為,於黏著接著劑層20中與半導體晶片31間之龜裂形成部位對向之部位被割斷。FIGS. 14(a) and 14(b) show the first stretching step (cooling stretching step) performed after bonding the semiconductor wafer 30C to the die-bonding film X. In this step, the hollow cylinder-shaped lifting member 43 of the stretching device rises in contact with the dicing tape 10 at the lower side of the dicing die-bonding film X in the figure, and the dicing of the semiconductor wafer 30C is bonded The dicing tape 10 of the die-bonding film X extends in a two-dimensional direction including the radial direction and the circumferential direction of the semiconductor wafer 30C. The stretching is performed in the dicing tape 10, for example, under the condition that a tensile stress in the range of 1 to 100 MPa, preferably 5 to 40 MPa is generated. The temperature condition in this step is, for example, 0°C or lower, preferably -20 to -5°C, more preferably -15 to -5°C, and even more preferably -15°C. The extension speed (the speed at which the jacking member 43 rises) in this step is preferably 1 to 500 mm/sec. In addition, the extension amount in this step is preferably 50 to 200 mm. By this cooling and extending step, the adhesive bond layer 20 of the diced die bonding film X is cut into small pieces of the adhesive bond layer 21 to obtain the semiconductor wafer 31 with the adhesive bond layer. Specifically, in this step, a crack is formed in the fragile modified region 30b in the semiconductor wafer 30C, and singulation of the semiconductor wafer 31 occurs. In addition, in this step, in the adhesive adhesive layer 20 that is in close contact with the adhesive layer 12 of the extended dicing tape 10, deformation is suppressed in each area where the semiconductor wafers 31 of the semiconductor wafer 30C are in close contact with each other. On the other hand, the tensile stress generated in the dicing tape 10 acts in a state where such a deformation suppression effect does not occur at a portion opposed to the crack formation portion of the wafer. As a result, the portion of the adhesive layer 20 facing the crack formation portion between the semiconductor wafers 31 is cut.

如上所述,切晶黏晶膜X可用於獲得附有黏著接著劑層之半導體晶片。又,切晶黏晶膜X亦可用於獲得積層複數個半導體晶片而進行三維封裝之情形時之附有黏著接著劑層之半導體晶片。於此種三維封裝中之半導體晶片31間可介存黏著接著劑層21及間隔件,亦可不介存間隔件。 [實施例]As described above, the die-bonding film X can be used to obtain a semiconductor wafer with an adhesive layer. In addition, the die-bonding film X can also be used to obtain a semiconductor wafer with an adhesive layer attached when a plurality of semiconductor wafers are stacked for three-dimensional packaging. The adhesive layer 21 and the spacer may be interposed between the semiconductor chips 31 in such a three-dimensional package, or the spacer may not be interposed. [Example]

<切晶帶之製作> 於具備冷凝管、氮氣導入管、溫度計、及攪拌裝置之反應容器內,將包含丙烯酸十二烷基酯100莫耳份、丙烯酸2-羥基乙酯(2HEA)20莫耳份、相對於該等單體成分100質量份為0.2質量份之作為聚合起始劑之過氧化苯甲醯、及作為聚合溶劑之甲苯之混合物於60℃下,於氮氣環境下攪拌10小時(聚合反應)。藉此,獲得含有丙烯酸系聚合物P1 之聚合物溶液。該聚合物溶液中之丙烯酸系聚合物P1 之重量平均分子量(Mw)為450000。其次,將包含含有該丙烯酸系聚合物P1 之聚合物溶液、2-甲基丙烯醯氧乙基異氰酸酯(MOI)、及作為加成反應觸媒之二月桂酸二丁基錫之混合物於室溫下且於空氣環境下攪拌48小時(加成反應)。於該反應溶液中,MOI調配量相對於源自丙烯酸系聚合物P1 中之2HEA之單元或其羥基之總量之莫耳比率為0.2。又,於該反應溶液中,二月桂酸二丁基錫之調配量相對於丙烯酸系聚合物P1 100質量份為0.03質量份。藉由該加成反應,獲得含有於側鏈具有甲基丙烯醯基之丙烯酸系聚合物P2 之聚合物溶液。其次,向該聚合物溶液中添加相對於丙烯酸系聚合物P2 100質量份為0.75質量份之聚異氰酸酯化合物(商品名「Coronate L」、Tosoh股份有限公司製造)、2質量份之光聚合起始劑(商品名「Irgacure 184」、BASF公司製造)並進行混合,且以該混合物於室溫下之黏度成為500 mPa・s之方式對該混合物添加甲苯以進行稀釋,而獲得黏著劑溶液。其次,於具有實施過聚矽氧脫模處理之面之PET隔片(厚度38 μm)之聚矽氧脫模處理面上使用敷料器塗佈黏著劑溶液而形成塗膜,對該塗膜於130℃下進行2分鐘之加熱乾燥,而於PET隔片上形成厚度10 μm之黏著劑層。其次,使用貼合機,於室溫下於該黏著劑層之露出面貼合乙烯-乙酸乙烯酯共聚物(EVA)製之基材(商品名「RB-0103」,厚度125 μm,倉敷紡織股份有限公司製造)。以如上方式製作切晶帶。<Preparation of crystal cutting belt> In a reaction vessel equipped with a condenser tube, a nitrogen gas introduction tube, a thermometer, and a stirring device, 100 moles of dodecyl acrylate and 20 moles of 2-hydroxyethyl acrylate (2HEA) A mixture of ear parts, 0.2 parts by mass relative to 100 parts by mass of these monomer components as a polymerization initiator, benzoyl peroxide as a polymerization initiator, and toluene as a polymerization solvent was stirred at 60°C under a nitrogen atmosphere for 10 hours (Polymerization). By this, a polymer solution containing the acrylic polymer P 1 was obtained. The weight average molecular weight (Mw) of the acrylic polymer P 1 in this polymer solution was 450,000. Next, the mixture containing the polymer solution containing the acrylic polymer P 1 , 2-methacryl oxyethyl isocyanate (MOI), and dibutyltin dilaurate as an addition reaction catalyst at room temperature And stirred for 48 hours in an air environment (addition reaction). In this reaction solution, the molar ratio of the MOI formulation amount to the total amount of units derived from 2HEA in the acrylic polymer P 1 or the total number of its hydroxyl groups was 0.2. In this reaction solution, the amount of dibutyltin dilaurate blended was 0.03 parts by mass with respect to 100 parts by mass of the acrylic polymer P 1 . By this addition reaction, a polymer solution containing an acrylic polymer P 2 having a methacryloyl group in the side chain is obtained. Next, to this polymer solution, a polyisocyanate compound (trade name "Coronate L", manufactured by Tosoh Co., Ltd.), 0.75 parts by mass relative to 100 parts by mass of acrylic polymer P 2 , and 2 parts by mass of photopolymerization were added The starting agent (trade name "Irgacure 184", manufactured by BASF) was mixed, and toluene was added to the mixture so that the viscosity of the mixture at room temperature became 500 mPa·s for dilution to obtain an adhesive solution. Next, apply an adhesive solution to the silicone separator release surface of the PET separator (thickness 38 μm) with the silicone release release surface applied to form a coating film. Heat and dry at 130°C for 2 minutes to form an adhesive layer with a thickness of 10 μm on the PET separator. Next, using a laminating machine, a substrate made of ethylene-vinyl acetate copolymer (EVA) (trade name "RB-0103", thickness 125 μm, Kurabo textile) was attached to the exposed surface of the adhesive layer at room temperature Co., Ltd.). The dicing tape is produced as above.

<黏著接著劑層之形成> 將丙烯酸系樹脂A1 (丙烯酸乙酯、丙烯酸丁酯、丙烯腈及甲基丙烯酸縮水甘油酯之共聚物,重量平均分子量為1000000,玻璃轉移溫度為-1.5℃)60質量份、固體酚系樹脂(商品名「MEH-7851SS」,於23℃下為固體,明和化成股份有限公司製造)15質量份、及二氧化矽填料(商品名「SO-E2」,平均粒徑為0.5 μm,Admatechs股份有限公司製造)25質量份添加至甲基乙基酮中並進行混合,以於室溫下之黏度成為1000 mPa・s之方式調整濃度,而獲得黏著接著劑組合物。其次,於具有實施過脫模處理之面之PET隔片(厚度38 μm)之脫模處理面上使用敷料器塗佈黏著接著劑組合物而形成塗膜,對該塗膜於130℃下進行2分鐘之加熱乾燥,而於PET隔片上形成厚度10 μm之作為黏晶膜之黏著接著劑層。<Formation of adhesive layer> Acrylic resin A 1 (copolymer of ethyl acrylate, butyl acrylate, acrylonitrile and glycidyl methacrylate, weight average molecular weight 1,000,000, glass transition temperature -1.5°C) 60 parts by mass, solid phenol resin (trade name "MEH-7851SS", solid at 23°C, manufactured by Minghe Chemical Co., Ltd.)) 15 parts by mass, and silica filler (trade name "SO-E2", average The particle size is 0.5 μm, manufactured by Admatechs Co., Ltd.) 25 parts by mass is added to methyl ethyl ketone and mixed, and the concentration is adjusted so that the viscosity at room temperature becomes 1000 mPa·s to obtain an adhesive bonding agent combination Thing. Next, on the release-treated surface of the PET separator (thickness 38 μm) having the surface subjected to the release treatment, an adhesive agent composition was applied using an applicator to form a coating film, and the coating film was applied at 130° C. After 2 minutes of heating and drying, a 10 μm thick adhesive layer as a viscous film was formed on the PET separator.

<切晶黏晶膜之製作> 於自PET隔片將上述切晶帶剝離後,使用貼合機於室溫下貼合於切晶帶中露出之黏著劑層、及帶PET隔片之上述黏著接著劑層,而獲得積層片材體。其次,對該積層片材體,進行將加工刀自切晶帶之EVA基材之側插入至隔片之衝壓加工。具體而言,一面使積層片材體沿一方向以10 m/min之速度流動,一面使圍繞著與該方向正交之軸心可旋轉地配置且圓形衝壓加工用之湯姆生刀捲繞於輥表面之附有加工刀之旋轉輥之附有加工刀之表面帶特定之推壓力地抵接於積層片材體之EVA基材側,而進行衝壓加工。該衝壓加工中所使用之旋轉輥之圓周長度即周長為378.9 mm。又,捲繞於旋轉輥表面之湯姆生刀為SUS製,以可衝壓加工直徑370 mm之圓之方式配置於輥表面,刀之高度為0.3 mm,刀尖所成之刃角為50°。藉由此種衝壓加工,將切晶帶與黏著接著劑層一次性地加工形成為圓盤形狀,於隔片上形成切晶黏晶膜。其後,自隔片上將所形成之切晶黏晶膜之周圍之材料積層部去除。以如上方式製作包含具有切晶帶與作為黏晶膜之黏著接著劑層之積層構造之實施例1之切晶黏晶膜。將實施例1中之黏著接著劑層之組成與其他實施例及比較例之黏著接著劑層組成一併揭示於表1中(於表1中,與黏著接著劑層組成相關之各數值之單位為於該層內之相對之"質量份")。<Fabrication of crystal-cut adhesive film> After peeling the above dicing tape from the PET separator, the adhesive layer exposed on the dicing tape and the above-mentioned adhesive adhesive layer with PET separator are bonded together at room temperature using a laminating machine to obtain a laminated sheet Wood body. Next, the laminated sheet body is subjected to a punching process in which a processing knife is inserted into the separator from the side of the EVA substrate of the dicing tape. Specifically, the laminated sheet body is flowed at a speed of 10 m/min in one direction, and the Thomson knife for circular stamping is rotatably arranged around an axis orthogonal to the direction on the one side The surface of the rotating roller with the processing blade attached to the surface of the roller is pressed against the EVA base material side of the laminated sheet body with a specific pushing force with a specific pushing force. The circumferential length of the rotating roller used in this stamping process is 378.9 mm. In addition, the Thomson knife wound on the surface of the rotating roller is made of SUS, and is arranged on the surface of the roller in such a way that a circle with a diameter of 370 mm can be stamped, the height of the knife is 0.3 mm, and the blade angle formed by the blade tip is 50°. By this stamping process, the dicing tape and the adhesive layer are processed into a disk shape at a time, and the dicing adhesive film is formed on the separator. After that, the material accumulation part around the formed die-cut adhesive film is removed from the separator. The die-cut die-bonding film of Example 1 including the laminated structure having the die-cut tape and the adhesive layer as the die-bonding film was produced in the above manner. The composition of the adhesive adhesive layer in Example 1 and the composition of the adhesive adhesive layer in other examples and comparative examples are disclosed in Table 1 (in Table 1, the unit of each value related to the composition of the adhesive adhesive layer It is the relative "mass part" in this layer).

[實施例2] 將丙烯酸系樹脂A1 之調配量設為48質量份代替60質量份,將固體酚系樹脂(商品名「MEH-78511SS」、明和化成股份有限公司製造)之調配量設為12質量份代替15質量份,及將二氧化矽填料(商品名「SO-E2」、Admatechs股份有限公司製造)之調配量設為40質量份代替25質量份,除此以外,以與實施例1之黏著接著劑層同樣之方式,於PET隔片上製作實施例2中之黏著接著劑層(厚度10 μm)。並且,使用實施例2中之該黏著接著劑層代替實施例1中之黏著接著劑層,除此以外,以與實施例1之切晶黏晶膜同樣之方式,製作實施例2之切晶黏晶膜。[Example 2] The blending amount of the acrylic resin A 1 was set to 48 parts by mass instead of 60 parts by mass, and the blending amount of the solid phenol resin (trade name "MEH-78511SS", manufactured by Meiwa Chemical Industry Co., Ltd.) was set to 12 parts by mass instead of 15 parts by mass, and the amount of silicon dioxide filler (trade name "SO-E2", manufactured by Admatechs Co., Ltd.) is set to 40 parts by mass instead of 25 parts by mass. In the same manner as the adhesive layer of 1, the adhesive layer (thickness of 10 μm) in Example 2 was prepared on the PET separator. In addition, the adhesive adhesive layer in Example 2 was used instead of the adhesive adhesive layer in Example 1, except that the die-cut crystal of Example 2 was produced in the same manner as the die-cut adhesive film of Example 1. Mucous membrane.

[實施例3] 使用丙烯酸系樹脂A2 (丙烯酸乙酯、丙烯酸丁酯、丙烯腈及甲基丙烯酸縮水甘油酯之共聚物,重量平均分子量為1000000,玻璃轉移溫度為 -6.5℃)60質量份代替丙烯酸系樹脂A1 60質量份,除此以外,以與實施例1之黏著接著劑層同樣之方式,於PET隔片上製作實施例3中之黏著接著劑層(厚度10 μm)。並且,使用實施例3中之該黏著接著劑層代替實施例1中之黏著接著劑層,除此以外,以與實施例1之切晶黏晶膜同樣之方式,製作實施例3之切晶黏晶膜。[Example 3] 60 parts by mass of acrylic resin A 2 (copolymer of ethyl acrylate, butyl acrylate, acrylonitrile and glycidyl methacrylate, weight average molecular weight 1,000,000, glass transition temperature -6.5°C) Instead of 60 parts by mass of acrylic resin A 1 , in the same manner as the adhesive adhesive layer of Example 1, an adhesive adhesive layer (thickness of 10 μm) in Example 3 was produced on the PET separator. In addition, the adhesive adhesive layer in Example 3 was used instead of the adhesive adhesive layer in Example 1, except that the die-cut crystal of Example 3 was produced in the same manner as the die-cut adhesive film of Example 1. Mucous membrane.

[實施例4] 使用丙烯酸系樹脂A2 (丙烯酸乙酯、丙烯酸丁酯、丙烯腈及甲基丙烯酸縮水甘油酯之共聚物,重量平均分子量為1000000,玻璃轉移溫度為 -6.5℃)48質量份代替丙烯酸系樹脂A1 60質量份,將固體酚系樹脂(商品名「MEH-78511SS」、明和化成股份有限公司製造)之調配量設為12質量份代替15質量份,及將二氧化矽填料(商品名「SO-E2」、Admatechs股份有限公司製造)之調配量設為40質量份代替25質量份,除此以外,以與實施例1之黏著接著劑層同樣之方式,於PET隔片上製作實施例4中之黏著接著劑層(厚度10 μm)。並且,使用實施例4中之該黏著接著劑層代替實施例1中之黏著接著劑層,除此以外,以與實施例1之切晶黏晶膜同樣之方式,製作實施例4之切晶黏晶膜。[Example 4] 48 parts by mass of acrylic resin A 2 (copolymer of ethyl acrylate, butyl acrylate, acrylonitrile and glycidyl methacrylate, weight average molecular weight 1,000,000, glass transition temperature -6.5°C) Instead of 60 parts by mass of acrylic resin A 1 , the amount of solid phenol resin (trade name "MEH-78511SS", manufactured by Meiwa Chemical Co., Ltd.) was set to 12 parts by mass instead of 15 parts by mass, and the silica filler (The trade name "SO-E2", manufactured by Admatechs Co., Ltd.) is 40 parts by mass instead of 25 parts by mass, except that it is on the PET separator in the same manner as the adhesive layer of Example 1. An adhesive layer (thickness 10 μm) in Example 4 was produced. In addition, the adhesive adhesive layer in Example 4 was used instead of the adhesive adhesive layer in Example 1, except that the die-cut crystal of Example 4 was produced in the same manner as the die-cut adhesive film of Example 1. Mucous membrane.

[比較例1] 使用丙烯酸系樹脂A3 (丙烯酸乙酯、丙烯酸丁酯、丙烯腈及甲基丙烯酸縮水甘油酯之共聚物,重量平均分子量為1000000,玻璃轉移溫度為4℃)42.4質量份代替丙烯酸系樹脂A1 60質量份,將固體酚系樹脂(商品名「MEH-78511SS」、明和化成股份有限公司製造)之調配量設為10.6質量份代替15質量份,及將二氧化矽填料(商品名「SO-E2」、Admatechs股份有限公司製造)之調配量設為47質量份代替25質量份,除此以外,以與實施例1之黏著接著劑層同樣之方式,於PET隔片上製作比較例1中之黏著接著劑層(厚度10 μm)。並且,使用比較例1中之該黏著接著劑層代替實施例1中之黏著接著劑層,除此以外,以與實施例1之切晶黏晶膜同樣之方式,製作比較例1之切晶黏晶膜。[Comparative Example 1] 42.4 parts by mass of acrylic resin A 3 (copolymer of ethyl acrylate, butyl acrylate, acrylonitrile and glycidyl methacrylate, weight average molecular weight 1,000,000, glass transition temperature 4°C) was used instead 60 parts by mass of acrylic resin A 1 , the amount of solid phenol resin (trade name "MEH-78511SS", manufactured by Meiwa Chemical Co., Ltd.) is set to 10.6 parts by mass instead of 15 parts by mass, and the silica filler ( The product name "SO-E2", manufactured by Admatechs Co., Ltd.) was prepared on a PET separator in the same manner as the adhesive layer of Example 1 except that the amount of preparation was set to 47 parts by mass instead of 25 parts by mass. The adhesive layer in Comparative Example 1 (thickness 10 μm). In addition, the adhesive adhesive layer in Comparative Example 1 was used instead of the adhesive adhesive layer in Example 1, except that the die cut of Comparative Example 1 was produced in the same manner as the die cut adhesive film of Example 1. Mucous membrane.

[比較例2] 使用丙烯酸系樹脂A2 (丙烯酸乙酯、丙烯酸丁酯、丙烯腈及甲基丙烯酸縮水甘油酯之共聚物,重量平均分子量為1000000,玻璃轉移溫度為 -6.5℃)80質量份代替丙烯酸系樹脂A1 60質量份,將固體酚系樹脂(商品名「MEH-78511SS」、明和化成股份有限公司製造)之調配量設為20質量份代替15質量份,及未使用二氧化矽填料,除此以外,以與實施例1之黏著接著劑層同樣之方式,於PET隔片上製作比較例2中之黏著接著劑層(厚度10 μm)。並且,使用比較例2中之該黏著接著劑層代替實施例1中之黏著接著劑層,除此以外,以與實施例1之切晶黏晶膜同樣之方式,製作比較例2之切晶黏晶膜。[Comparative Example 2] 80 parts by mass of acrylic resin A 2 (copolymer of ethyl acrylate, butyl acrylate, acrylonitrile and glycidyl methacrylate, weight average molecular weight 1,000,000, glass transition temperature -6.5°C) Instead of 60 parts by mass of acrylic resin A 1 , the amount of solid phenol resin (trade name "MEH-78511SS", manufactured by Meiwa Chemical Co., Ltd.) was set to 20 parts by mass instead of 15 parts by mass, and silica was not used Except for the filler, in the same manner as the adhesive adhesive layer of Example 1, an adhesive adhesive layer (thickness of 10 μm) in Comparative Example 2 was produced on the PET separator. In addition, the adhesive adhesive layer in Comparative Example 2 was used instead of the adhesive adhesive layer in Example 1, except that the die cut of Comparative Example 2 was produced in the same manner as the die cut adhesive film of Example 1. Mucous membrane.

[第1拉伸儲存模數(25℃)] 對實施例1~4及比較例1、2中之各黏著接著劑層,基於使用動態黏彈性測定裝置(商品名「RSAIII」、TA Instruments公司製造)而進行之動態黏彈性測定,調查於25℃下之拉伸儲存模數(第1拉伸儲存模數)。供於動態黏彈性測定之試樣片係於形成以厚度160 μm積層各黏著接著劑層所得之積層體後,以寬度10 mm×長度30 mm之尺寸自該積層體切下而準備。又,於本測定中,將試樣片保持用夾頭之初始夾頭間距離設為22.5 mm,將測定模式設為拉伸模式,將測定溫度範圍設為-30℃~100℃,將頻率設為1 Hz,將動態應變設為0.005%,將升溫速度設為10℃/min。將所求出之25℃下之拉伸儲存模數(MPa)揭示於表1中。[The first tensile storage modulus (25℃)] For each of the adhesive layers in Examples 1 to 4 and Comparative Examples 1 and 2, based on dynamic viscoelasticity measurement using a dynamic viscoelasticity measuring device (trade name "RSAIII", manufactured by TA Instruments), the investigation was conducted on 25 The tensile storage modulus at ℃ (the first tensile storage modulus). The sample piece for dynamic viscoelasticity measurement was prepared by forming a laminated body obtained by laminating each adhesive layer with a thickness of 160 μm and cutting it from the laminated body with a width of 10 mm × a length of 30 mm. In this measurement, the initial chuck distance of the chuck for holding the sample piece is set to 22.5 mm, the measurement mode is set to the stretch mode, the measurement temperature range is set to -30°C to 100°C, and the frequency Set to 1 Hz, set the dynamic strain to 0.005%, and set the heating rate to 10°C/min. Table 1 shows the calculated tensile storage modulus (MPa) at 25°C.

[第2拉伸儲存模數(-15℃)] 對實施例1~4及比較例1、2中之各黏著接著劑層,基於使用動態黏彈性測定裝置(商品名「Rheogel-E4000」、UBM公司製造)而進行之動態黏彈性測定,調查於-15℃下之拉伸儲存模數(第2拉伸儲存模數)。供於動態黏彈性測定之試樣片係於形成以厚度80 μm積層各黏著接著劑層所得之積層體後,以寬度5 mm×長度25 mm之尺寸自該積層體切下而準備。又,於本測定中,將試樣片保持用夾頭之初始夾頭間距離設為10 mm,將測定模式設為拉伸模式,將測定溫度範圍設為-30℃~100℃,將頻率設為900 Hz,將動態應變設為0.005%,將升溫速度設為5℃/min。將所求出之-15℃下之第2拉伸儲存模數(MPa)揭示於表1中。[Second tensile storage modulus (-15℃)] The adhesive adhesive layers in Examples 1 to 4 and Comparative Examples 1 and 2 were investigated based on dynamic viscoelasticity measurement using a dynamic viscoelasticity measuring device (trade name "Rheogel-E4000", manufactured by UBM). Tensile storage modulus at -15°C (second tensile storage modulus). The sample piece for dynamic viscoelasticity measurement was prepared by forming a laminate obtained by laminating each adhesive layer with a thickness of 80 μm and cutting it from the laminate with a width of 5 mm × a length of 25 mm. In this measurement, the initial chuck distance of the chuck for holding the sample piece is set to 10 mm, the measurement mode is set to the stretch mode, the measurement temperature range is set to -30°C to 100°C, and the frequency Set to 900 Hz, set the dynamic strain to 0.005%, and set the heating rate to 5°C/min. Table 2 shows the calculated second tensile storage modulus (MPa) at -15°C.

<剪切黏著力> 對實施例1~4及比較例1、2之各切晶黏晶膜,測定對SUS板之-15℃下之剪切黏著力。供於本測定之試樣片係以如下方式製作。首先,於切晶黏晶膜中,自切晶帶將黏著接著劑層剝離。其次,於該黏著接著劑層中於貼合於切晶帶之側之面貼合加襯帶(商品名「BT-315」、日東電工股份有限公司製造)。然後,自所獲得之襯底黏著接著劑層,切下寬度10 mm×長度100 mm之尺寸之試樣片。<Shear adhesion> For each of the crystal-cut adhesive films of Examples 1 to 4 and Comparative Examples 1 and 2, the shear adhesion at -15°C to the SUS plate was measured. The sample piece for this measurement was produced as follows. First, in the die-cut crystal bonding film, the self-cut crystal tape strips the adhesive layer. Next, a liner tape (trade name "BT-315", manufactured by Nitto Denko Co., Ltd.) was bonded to the surface of the adhesive layer that was bonded to the side of the dicing tape. Then, an adhesive layer was adhered from the obtained substrate, and a sample piece having a size of 10 mm in width×100 mm in length was cut out.

於室溫下對SUS板貼合所製作之試樣片。該SUS板係經過藉由利用滲入有甲苯之不織布擦拭布之擦拭、及利用滲入有甲醇之不織布擦拭布之擦拭進行之表面清潔化處理者。於貼合作業中,對試樣片端部之10 mm×10 mm之區域SUS板之端部,以利用2 kg輥往返一次之荷重進行壓接。並且,對該試樣片及SUS板,於在室溫下放置30分鐘後,使用拉伸試驗機(商品名「Autograph AGS-J」、島津製作所製造)而測定剪切黏著力。於本測定中,測定溫度為-15℃,拉伸速度為1000 mm/min,將所獲得之最大應力值設為剪切黏著力(N/cm2 )。The prepared sample piece was attached to the SUS plate at room temperature. The SUS plate was subjected to surface cleaning treatment by wiping with a non-woven cloth infiltrated with toluene and wiping with a non-woven cloth infiltrated with methanol. In the bonding industry, the end of the SUS plate in the area of 10 mm × 10 mm at the end of the sample piece is crimped with a load of 2 kg rollers back and forth once. Then, after leaving the sample piece and the SUS plate at room temperature for 30 minutes, the shear adhesion was measured using a tensile tester (trade name "Autograph AGS-J", manufactured by Shimadzu Corporation). In this measurement, the measurement temperature is -15°C, the stretching speed is 1000 mm/min, and the maximum stress value obtained is set as the shear adhesive force (N/cm 2 ).

<於23℃下之框架保持性> 對實施例1~4及比較例1、2之各切晶黏晶膜,以如下方式調查對於環狀框之貼合性或保持性。首先,使用貼合裝置(MΑ-3000II,日東精機股份有限公司製造),將直徑12英吋之SUS製環狀框(DISCO股份有限公司製造)貼合於切晶黏晶膜之黏著接著劑層側。該貼合係於貼合速度10 mm/sec及溫度60℃之條件下進行。其後,於水平狀態下保管於盒體內,並於室溫下進行1週之放置。並且,確認環狀框自黏著接著劑層源之剝離之有無。將未產生環狀框自切晶黏晶膜或其黏著接著劑層之剝離之情形評價為"良",將產生環狀框之剝離之情形評價為"不良"。將其評價結果揭示於表1中。<Frame retention at 23℃> For each of the die-cut adhesive films of Examples 1 to 4 and Comparative Examples 1 and 2, the adhesion or retention to the ring frame was investigated as follows. First, using a bonding device (MA-3000II, manufactured by Nitto Seiki Co., Ltd.), a 12-inch diameter SUS ring frame (manufactured by DISCO Co., Ltd.) was bonded to the adhesive layer of the die-cut adhesive film. side. The bonding is performed under the conditions of a bonding speed of 10 mm/sec and a temperature of 60°C. Thereafter, it was stored in the case in a horizontal state, and left at room temperature for 1 week. Also, check whether the ring frame is peeled off from the adhesive layer source. The case where no peeling of the ring-shaped frame self-cut crystal adhesive film or its adhesive layer was evaluated as "good", and the case where the peeling of the ring-shaped frame was evaluated as "bad". The evaluation results are shown in Table 1.

[冷卻延伸步驟(-15℃)中之割斷性] 使用實施例1~4及比較例1、4之各切晶黏晶膜,而進行如下所述之貼合步驟、用於割斷之第1延伸步驟(冷卻延伸步驟)、及用於相隔之第2延伸步驟(常溫延伸步驟)。[Cut-off in cooling extension step (-15℃)] Using the dicing die-bonding films of Examples 1 to 4 and Comparative Examples 1 and 4, the following bonding step, the first stretching step for cutting (cooling stretching step), and the first 2 Extension step (normal temperature extension step).

於貼合步驟中,對切晶黏晶膜之黏著接著劑層貼合保持於晶圓加工用膠帶(商品名「UB-3083D」、日東電工股份有限公司製造)之半導體晶圓分割體,其後,自半導體晶圓分割體將晶圓加工用膠帶剝離。於貼合中,使用貼合機,將貼合速度設為10 mm/sec,將溫度條件設為60℃,將壓力條件設為0.15 MPa。又,半導體晶圓分割體係以如下方式形成而準備者。首先,對處於與環狀框一併保持於晶圓加工用膠帶(商品名「V12S-R2-P」、日東電工股份有限公司製造)之狀態之裸晶圓(直徑12英吋,厚度780 μm,東京化工股份有限公司製造),自其一面之側,使用切晶裝置(商品名「DFD6260」、DISCO股份有限公司製造),利用其旋轉刀片形成單片化用之分割槽(寬度25 μm,深度50 μm,呈現一組分6 mm×12 mm之晶格狀)。其次,於向分割槽形成面貼合晶圓加工用膠帶(商品名「UB-3083D」、日東電工股份有限公司製造)後,將上述晶圓加工用膠帶(商品名「V12S-R2-P」)自晶圓剝離。其後,使用背面研磨裝置(商品名「DGP8760」、DISCO股份有限公司製造),藉由自晶圓之另一面(未形成分割槽之面)之側之研削將該晶圓薄化至厚度20 μm,繼而,藉由使用相同裝置而進行之乾式拋光對該研削面實施鏡面拋光。以如上方式形成半導體晶圓分割體(處於保持於晶圓加工用膠帶之狀態)。於該半導體晶圓分割體中包含複數個半導體晶片(6 mm×12 mm)。In the bonding step, the semiconductor wafer division of the wafer adhesive tape (trade name "UB-3083D", manufactured by Nitto Denko Co., Ltd.) is bonded to the adhesive adhesive layer of the die-cut adhesive film, which After that, the wafer processing tape is peeled from the semiconductor wafer division. For bonding, a bonding machine was used, the bonding speed was set to 10 mm/sec, the temperature condition was set to 60°C, and the pressure condition was set to 0.15 MPa. In addition, a semiconductor wafer division system is prepared as follows. First, for bare wafers (diameter 12 inches, thickness 780 μm) in a state of being held together with the ring frame by wafer processing tape (trade name "V12S-R2-P", manufactured by Nitto Denko Corporation) , Manufactured by Tokyo Chemical Industry Co., Ltd.), using a crystal cutting device (trade name "DFD6260", manufactured by DISCO Co., Ltd.) from one side, using its rotating blade to form a dividing groove for monolithization (width 25 μm, Depth 50 μm, showing a group of 6 mm × 12 mm lattice-like). Next, after attaching a wafer processing tape (trade name "UB-3083D", manufactured by Nitto Denko Co., Ltd.) to the dividing groove forming surface, apply the wafer processing tape (trade name "V12S-R2-P" ) Peel off from the wafer. Thereafter, using a back-grinding device (trade name "DGP8760", manufactured by DISCO Co., Ltd.), the wafer was thinned to a thickness of 20 by grinding from the side of the other surface of the wafer (the surface where the dividing groove was not formed) [mu]m, and then, the dry polishing using the same device was subjected to mirror polishing on the ground surface. The semiconductor wafer split body is formed as described above (in a state of being held by the wafer processing tape). The semiconductor wafer divided body includes a plurality of semiconductor chips (6 mm×12 mm).

冷卻延伸步驟係使用晶片分離裝置(商品名「Die Separator DDS3200」、DISCO股份有限公司製造),利用其冷卻延伸單元而進行。具體而言,首先,於帶半導體晶圓分割體之上述切晶黏晶膜中之黏著接著劑層之框架貼合用區域(工件貼合用區域之周圍),於室溫下貼附直徑12英吋之SUS製環狀框(DISCO股份有限公司製造)。其次,將該切晶黏晶膜設置於裝置內,利用相同裝置之冷卻延伸單元,使帶半導體晶圓分割體之切晶黏晶膜之切晶帶延伸。於該冷卻延伸步驟中,溫度為-15℃,延伸速度為300 mm/sec,延伸量為15 mm。The cooling and stretching step is performed using a wafer separation device (trade name "Die Separator DDS3200", manufactured by DISCO Co., Ltd.) and cooling the stretching unit using the same. Specifically, first, the frame bonding area (around the work bonding area) of the adhesive bonding agent layer in the diced die-bonding film with the semiconductor wafer division is attached at a diameter of 12 at room temperature Inch ring frame made of SUS (made by DISCO Corporation). Next, the dicing die-bonding film is installed in the device, and the dicing tape of the dicing die-bonding film with the semiconductor wafer division is extended by the cooling and stretching unit of the same device. In this cooling and stretching step, the temperature is -15°C, the stretching speed is 300 mm/sec, and the stretching amount is 15 mm.

常溫延伸步驟係使用晶片分離裝置(商品名「Die Separator DDS3200」、DISCO股份有限公司製造),並利用其常溫延伸單元而進行。具體而言,利用相同裝置之常溫延伸單元使經過上述冷卻延伸步驟之帶半導體晶圓分割體之切晶黏晶膜之切晶帶延伸。於該常溫延伸步驟中,溫度為23℃,延伸速度為1 mm/sec,延伸量為10 mm。其後,對經過常溫延伸之切晶黏晶膜實施加熱收縮處理。其處理溫度為200℃,處理時間為20秒。The normal temperature stretching step is performed using a wafer separation device (trade name "Die Separator DDS3200", manufactured by DISCO Co., Ltd.) and using its normal temperature stretching unit. Specifically, the normal-temperature stretching unit of the same device is used to extend the dicing tape of the dicing die-bonding film with the semiconductor wafer division after the cooling and stretching step. In the normal temperature stretching step, the temperature is 23°C, the stretching speed is 1 mm/sec, and the stretching amount is 10 mm. Thereafter, the die-cut crystal film stretched at room temperature is subjected to heat shrinkage treatment. The treatment temperature is 200°C and the treatment time is 20 seconds.

於經過使用實施例1~4及比較例1、2之各切晶黏晶膜而進行之如上所述之過程之階段中,調查帶割斷之黏著接著劑層之半導體晶片之總數相對於半導體晶圓分割體中所含之半導體晶片之總數之比率。並且,對黏著接著劑層之割斷性,將該比率為80%以上之情形評價為"良",將該比率未達80%之情形評價為"不良"。將該評價結果揭示於表1中。At the stage of the above-mentioned process performed by using each of the die-cut adhesive films of Examples 1 to 4 and Comparative Examples 1 and 2, the total number of semiconductor wafers with a cut adhesive bond layer was investigated relative to the semiconductor crystal The ratio of the total number of semiconductor wafers contained in the circular segment. In addition, for the cutting property of the adhesive layer, the case where the ratio is 80% or more is evaluated as "good", and the case where the ratio is less than 80% is evaluated as "bad". The evaluation results are shown in Table 1.

[評價] 關於實施例1~4之切晶黏晶膜之框架保持性、以及冷卻延伸步驟 (-15℃)中之割斷性,均獲得良好之結果。相對於此,比較例1之切晶黏晶膜由於其黏著接著劑層之拉伸儲存模數過高,故而於該黏著接著劑層中無法保持環狀框。因此,無法實施使用比較例1之切晶黏晶膜之冷卻延伸步驟。又,比較例2之切晶黏晶膜中,由於其黏著接著劑層之拉伸儲存模數過低,故而於冷卻延伸步驟中無法充分地割斷該黏著接著劑層。[Evaluation] Good results were obtained with respect to the frame retention of the die-cut adhesive films of Examples 1 to 4 and the cutability in the cooling and stretching step (-15°C). In contrast, in the die-cut adhesive film of Comparative Example 1, the tensile storage modulus of the adhesive layer is too high, so the ring frame cannot be maintained in the adhesive layer. Therefore, the cooling and extending step using the die-bonding film of Comparative Example 1 cannot be performed. In addition, in the die-cut adhesive film of Comparative Example 2, since the tensile storage modulus of the adhesive layer is too low, the adhesive layer cannot be sufficiently cut during the cooling and stretching step.

[表1]

Figure 108115440-A0304-0001
[Table 1]
Figure 108115440-A0304-0001

10:切晶帶 11:基材 11':基材 11e:外周端 12:黏著劑層 12':黏著劑層 12a:黏著面 12e:外周端 20:黏著接著劑層 20':接著劑層 20a:面 20e:外周端 21:黏著接著劑層 30A:半導體晶圓 30a:分割槽 30B:半導體晶圓分割體 30b:改質區域 30C:半導體晶圓 31:半導體晶片 41:環狀框 42:保持具 43:頂起構件 44:銷 45:吸附治具 51:被接著體 52:接合線 53:密封樹脂 60:切晶帶 61:基材 62:黏著劑層 62e:外周端 70:黏晶膜 70e:外周端 81:半導體晶圓 82:環狀框 83:隔片 C1:黏著接著劑組合物層 C2:黏著接著劑組合物層 D:面內方向 F:方向 R:照射區域 S:隔片 T1:晶圓加工用膠帶 T1a:黏著面 T2:晶圓加工用膠帶 T2a:黏著面 T3:晶圓加工用膠帶 T3a:黏著面 W:半導體晶圓 Wa:第1面 Wb:第2面 X:切晶黏晶膜 Y:切晶黏晶膜10: Cutting crystal belt 11: substrate 11': substrate 11e: outer peripheral end 12: Adhesive layer 12': Adhesive layer 12a: Adhesive surface 12e: outer peripheral end 20: Adhesive layer 20': Adhesive layer 20a: noodles 20e: outer peripheral end 21: Adhesive layer 30A: Semiconductor wafer 30a: Split groove 30B: Semiconductor wafer segment 30b: modified area 30C: Semiconductor wafer 31: Semiconductor chip 41: ring frame 42: Retainer 43: jacking member 44: Pin 45: Adsorption fixture 51: Attached body 52: Bonding wire 53: Sealing resin 60: crystal cutting belt 61: substrate 62: Adhesive layer 62e: outer peripheral end 70: Crystal film 70e: outer peripheral end 81: Semiconductor wafer 82: ring frame 83: Separator C1: Adhesive composition layer C2: Adhesive composition layer D: In-plane direction F: direction R: Irradiated area S: Separator T1: tape for wafer processing T1a: Adhesive surface T2: tape for wafer processing T2a: Adhesive surface T3: tape for wafer processing T3a: Adhesive surface W: Semiconductor wafer Wa: Face 1 Wb: Face 2 X: crystal cutting film Y: Crystal cut film

圖1為本發明之一實施形態之切晶黏晶膜之剖面模式圖。 圖2表示圖1所示之切晶黏晶膜帶隔片之情形時之一例。 圖3(a)~(d)表示圖1所示之切晶黏晶膜之製造方法之一例中之一部分步驟。 圖4(a)、(b)表示繼圖3所示之步驟之後之步驟。 圖5(a)~(d)表示使用圖1所示之切晶黏晶膜之半導體裝置製造方法中之一部分步驟。 圖6(a)、(b)表示繼圖5所示之步驟之後之步驟。 圖7(a)~(c)表示繼圖6所示之步驟之後之步驟。 圖8(a)、(b)表示繼圖7所示之步驟之後之步驟。 圖9表示繼圖8所示之步驟之後之步驟。 圖10(a)~(c)表示繼圖9所示之步驟之後之步驟。 圖11表示使用圖1所示之切晶黏晶膜之半導體裝置製造方法之變化例中之一部分步驟。 圖12(a)、(b)表示使用圖1所示之切晶黏晶膜之半導體裝置製造方法之變化例中之一部分步驟。 圖13(a)~(c)表示使用圖1所示之切晶黏晶膜之半導體裝置製造方法之變化例中之一部分步驟。 圖14(a)、(b)表示使用圖1所示之切晶黏晶膜之半導體裝置製造方法之變化例中之一部分步驟。 圖15為先前之切晶黏晶膜之剖面模式圖。 圖16表示圖15所示之切晶黏晶膜之使用態樣。 圖17表示圖15所示之切晶黏晶膜之一供給形態。FIG. 1 is a schematic cross-sectional view of a die-cut adhesive film according to an embodiment of the present invention. FIG. 2 shows an example of the case of the dicing die-bonding film shown in FIG. 1 with a separator. 3(a) to (d) show a part of the steps in an example of the manufacturing method of the die-cut adhesive film shown in FIG. 4(a) and (b) show steps following the step shown in FIG. 3. 5(a) to (d) show a part of the steps in the method of manufacturing a semiconductor device using the die-bonding film shown in FIG. 6(a) and (b) show steps following the step shown in FIG. 7(a) to (c) show steps following the step shown in FIG. 6. 8(a) and (b) show steps following the step shown in FIG. 7. FIG. 9 shows steps following the step shown in FIG. 8. Fig. 10 (a) to (c) show steps following the step shown in Fig. 9. FIG. 11 shows a part of the steps in a variation of the manufacturing method of the semiconductor device using the die-bonding film shown in FIG. 1. 12(a) and (b) show a part of the steps in a modification of the method for manufacturing a semiconductor device using the die-bonding film shown in FIG. 13(a) to (c) show a part of the steps in a modified example of the semiconductor device manufacturing method using the die-bonding film shown in FIG. 14(a) and (b) show a part of the steps in a variation of the method for manufacturing a semiconductor device using the die-bonding film shown in FIG. 15 is a schematic cross-sectional view of the previous die-cut crystal bonding film. FIG. 16 shows a usage state of the die-bonding film shown in FIG. 15. Fig. 17 shows one supply form of the die-cut die-bonding film shown in Fig. 15.

10:切晶帶 10: Cutting crystal belt

11:基材 11: substrate

11e:外周端 11e: outer peripheral end

12:黏著劑層 12: Adhesive layer

12a:黏著面 12a: Adhesive surface

12e:外周端 12e: outer peripheral end

20:黏著接著劑層 20: Adhesive layer

20a:面 20a: noodles

20e:外周端 20e: outer peripheral end

D:面內方向 D: In-plane direction

R:照射區域 R: Irradiated area

X:切晶黏晶膜 X: crystal cutting film

Claims (10)

一種切晶黏晶膜,其具備:切晶帶,其具有包含基材與黏著劑層之積層構造;及 黏著接著劑層,其可剝離地密接於上述切晶帶中之上述黏著劑層;且 關於上述黏著接著劑層,針對寬度10 mm及厚度160 μm之黏著接著劑層試樣片,於初始夾頭間距離22.5 mm、頻率1 Hz、動態應變0.005%、及升溫速度10℃/min之條件下所測定之25℃下之拉伸儲存模數為5~120 MPa,且 關於上述黏著接著劑層,針對寬度5 mm及厚度80 μm之黏著接著劑層試樣片,於初始夾頭間距離10 mm、頻率900 Hz、動態應變0.005%、及升溫速度5℃/min之條件下所測定之-15℃下之拉伸儲存模數為3000~6000 MPa。A crystal-cut crystal bonding film comprising: a crystal-cutting tape having a layered structure including a base material and an adhesive layer; and An adhesive layer, which is peelably adhered to the adhesive layer in the dicing tape; and Regarding the above-mentioned adhesive adhesive layer, for an adhesive adhesive layer sample piece with a width of 10 mm and a thickness of 160 μm, the distance between the initial chucks is 22.5 mm, the frequency is 1 Hz, the dynamic strain is 0.005%, and the heating rate is 10 °C/min. The tensile storage modulus measured at 25°C under the conditions is 5 to 120 MPa, and Regarding the above-mentioned adhesive adhesive layer, for an adhesive adhesive layer sample piece with a width of 5 mm and a thickness of 80 μm, the distance between the initial chuck is 10 mm, the frequency is 900 Hz, the dynamic strain is 0.005%, and the heating rate is 5°C/min. The tensile storage modulus measured at -15°C under the conditions is 3000-6000 MPa. 如請求項1之切晶黏晶膜,其中上述黏著接著劑層之外周端於膜面內方向上處於距上述黏著劑層之外周端1000 μm以內之距離內。The diced die-bonding film of claim 1, wherein the outer peripheral end of the adhesive layer is within a distance of 1000 μm from the outer peripheral end of the adhesive layer in the in-plane direction of the film. 如請求項1之切晶黏晶膜,其對於上述黏著接著劑層中之SUS平面之 -15℃下之剪切黏著力為66 N/cm2 以上。The diced die-bonding film according to claim 1 has a shear adhesion at -15°C of SUS of the SUS plane in the above-mentioned adhesive adhesive layer of 66 N/cm 2 or more. 如請求項2之切晶黏晶膜,其對於上述黏著接著劑層中之SUS平面之 -15℃下之剪切黏著力為66 N/cm2 以上。The diced die-bonding film according to claim 2 has a shear adhesive force at -15°C of SUS of SUS plane in the above-mentioned adhesive adhesive layer of 66 N/cm 2 or more. 如請求項1之切晶黏晶膜,其中上述黏著劑層為放射線硬化型黏著劑層,且 於23℃及剝離速度300 mm/min之條件下之T型剝離試驗中之放射線硬化前之上述黏著劑層與上述黏著接著劑層之間的剝離力為0.5 N/20 mm以上。The die-cut adhesive film according to claim 1, wherein the adhesive layer is a radiation hardening adhesive layer, and The peeling force between the above-mentioned adhesive layer and the above-mentioned adhesive adhesive layer before radiation curing in the T-type peeling test under the conditions of 23° C. and a peeling speed of 300 mm/min is 0.5 N/20 mm or more. 如請求項1之切晶黏晶膜,其中上述黏著接著劑層具有7~30 μm之厚度。The die-cut die-bonding film according to claim 1, wherein the above adhesive layer has a thickness of 7-30 μm. 如請求項1至6中任一項之切晶黏晶膜,其中上述黏著接著劑層包含重量平均分子量800000~2000000且玻璃轉移溫度-10~3℃之聚合物成分。The die-cut adhesive film according to any one of claims 1 to 6, wherein the adhesive adhesive layer includes a polymer component having a weight average molecular weight of 800,000 to 2,000,000 and a glass transition temperature of -10 to 3°C. 如請求項7之切晶黏晶膜,其中上述聚合物成分包含源自丙烯腈之構成單元。The crystalline die-bonding film according to claim 7, wherein the polymer component contains a structural unit derived from acrylonitrile. 如請求項1至6中任一項之切晶黏晶膜,其中上述黏著接著劑層以10~40質量%之比率含有二氧化矽填料。The die-cut die-bonding film according to any one of claims 1 to 6, wherein the adhesive bonding agent layer contains a silica filler at a ratio of 10 to 40% by mass. 如請求項7之切晶黏晶膜,其中上述黏著接著劑層以10~40質量%之比率含有二氧化矽填料。The die-cut die-bonding film according to claim 7, wherein the above-mentioned adhesive layer contains a silica filler at a ratio of 10 to 40% by mass.
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