TW202035604A - Method for evaluating photocurable adhesive, dicing/die attach film, method for manufacturing same, and method for manufacturing semiconductor device - Google Patents

Method for evaluating photocurable adhesive, dicing/die attach film, method for manufacturing same, and method for manufacturing semiconductor device Download PDF

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TW202035604A
TW202035604A TW108147291A TW108147291A TW202035604A TW 202035604 A TW202035604 A TW 202035604A TW 108147291 A TW108147291 A TW 108147291A TW 108147291 A TW108147291 A TW 108147291A TW 202035604 A TW202035604 A TW 202035604A
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adhesive layer
photocurable adhesive
photocurable
dicing
meth
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TW108147291A
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TWI816004B (en
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彼谷美千子
尾崎義信
大久保恵介
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日商日立化成股份有限公司
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N19/00Investigating materials by mechanical methods
    • G01N19/04Measuring adhesive force between materials, e.g. of sealing tape, of coating
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/50Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/52Mounting semiconductor bodies in containers
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    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836Wafer tapes, e.g. grinding or dicing support tapes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
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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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68327Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
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    • H01L2221/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
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    • H01L2221/683Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68381Details of chemical or physical process used for separating the auxiliary support from a device or wafer
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    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321Disposition
    • H01L2224/32151Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32225Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
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    • H01ELECTRIC ELEMENTS
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    • H01L2224/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42Wire connectors; Manufacturing methods related thereto
    • H01L2224/47Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805Shape
    • H01L2224/4809Loop shape
    • H01L2224/48091Arched
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    • H01L2224/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42Wire connectors; Manufacturing methods related thereto
    • H01L2224/47Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481Disposition
    • H01L2224/48151Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48225Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H01L2224/48227Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation connecting the wire to a bond pad of the item
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    • H01L2224/73Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
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    • H01L2224/83Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
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    • H01L2924/153Connection portion
    • H01L2924/1531Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface
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    • H01L2924/181Encapsulation

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  • Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
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  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Immunology (AREA)
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  • Dicing (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Die Bonding (AREA)

Abstract

Disclosed is a method for evaluating a photocurable adhesive used for a dicing/die attach film. Additionally disclosed are: a dicing/die attach film based on such a method for evaluating a photocurable adhesive; and a method for manufacturing the film. Further disclosed is a method for manufacturing a semiconductor device using such a dicing/die attach film.

Description

光硬化性黏著劑的評價方法、切割-黏晶一體型膜及其製造方法、以及半導體裝置的製造方法Evaluation method of photocurable adhesive, dicing-bonding integrated film and manufacturing method thereof, and manufacturing method of semiconductor device

本發明是有關於一種光硬化性黏著劑的評價方法、切割-黏晶一體型膜及其製造方法、以及半導體裝置的製造方法。The present invention relates to an evaluation method of a photocurable adhesive, a dicing-bonding integrated film and a manufacturing method thereof, and a manufacturing method of a semiconductor device.

在半導體晶片的製造中,通常具備將半導體晶圓單片化為各個半導體晶片的切割步驟、以及將單片化後的半導體晶片接著在引線框架、封裝基板等上的黏晶步驟。在此種半導體晶片的製造中,主要使用將切割膜與黏晶膜組合而得的切割-黏晶一體型膜,所述切割膜具備包含用於將切割步驟中的半導體晶圓固定的光硬化性黏著劑的光硬化性黏著劑層,所述黏晶膜具備用於半導體晶片與引線框架、封裝基板等的接著的接著劑層。The manufacturing of semiconductor wafers generally includes a dicing step of singulating the semiconductor wafer into individual semiconductor wafers, and a die bonding step of attaching the singulated semiconductor wafer to a lead frame, a package substrate, and the like. In the manufacture of such semiconductor wafers, a dicing-bonding integrated film obtained by combining a dicing film and a die-attach film is mainly used, and the dicing film is provided with a photocuring method for fixing the semiconductor wafer in the dicing step. A light-curable adhesive layer of an adhesive, and the die-attach film includes an adhesive layer for bonding a semiconductor chip, a lead frame, a package substrate, etc.

近年來,作為將薄型半導體晶圓單片化來製造半導體晶片的方法的一個例子,提出了不完全切斷半導體晶圓而對切斷預定線上的半導體晶圓內部照射雷射光來形成改質層,使切割膜擴張,藉此割斷半導體晶圓的所謂的隱形(stealth)切割(例如,專利文獻1)。藉由隱形切割被單片化的半導體晶片自防止在之後的拾取步驟中的破損的觀點出發,要求以更小的力剝離黏晶膜與切割膜。但是,如果用小的力剝離,剝離時間會變長,生產率有惡化的傾向。因此,在薄型半導體晶片的製造中使用的切割-黏晶一體型膜中,要求能夠提高拾取的成功率以及能夠縮短拾取的剝離時間,從而構成光硬化性黏著劑層的光硬化性黏著劑的選定變得重要。 [現有技術文獻]In recent years, as an example of a method of manufacturing semiconductor wafers by singulating thin semiconductor wafers, it has been proposed to incompletely cut the semiconductor wafers and irradiate the inside of the semiconductor wafers on the planned cutting line with laser light to form a modified layer. , The so-called stealth dicing of the semiconductor wafer by expanding the dicing film (for example, Patent Document 1). From the viewpoint of preventing breakage in the subsequent pick-up step by stealth dicing of the singulated semiconductor wafer, it is required to peel off the adhesive film and the dicing film with a smaller force. However, if it is peeled with a small force, the peeling time will be longer and the productivity will tend to deteriorate. Therefore, in the dicing-bonding integrated film used in the manufacture of thin semiconductor wafers, it is required to improve the success rate of picking and shorten the peeling time of picking, thereby forming the photocurable adhesive of the photocurable adhesive layer. Selection becomes important. [Prior Art Literature]

專利文獻1:日本專利特開2003-338467號公報 專利文獻2:日本專利特開2004-017639號公報 專利文獻3:日本專利特開2006-089521號公報 專利文獻4:日本專利特開2006-266798號公報 專利文獻5:日本專利特開2014-055250號公報 專利文獻6:日本專利特開2014-181258號公報 專利文獻7:日本專利特開2015-028146號公報Patent Document 1: Japanese Patent Laid-Open No. 2003-338467 Patent Document 2: Japanese Patent Laid-Open No. 2004-017639 Patent Document 3: Japanese Patent Laid-Open No. 2006-089521 Patent Document 4: Japanese Patent Laid-Open No. 2006-266798 Patent Document 5: Japanese Patent Laid-Open No. 2014-055250 Patent Document 6: Japanese Patent Laid-Open No. 2014-181258 Patent Document 7: Japanese Patent Laid-Open No. 2015-028146

但是,在半導體晶片的製造中,難以提前預測預計用作切割-黏晶一體型膜的光硬化性黏著劑層的光硬化性黏著劑是否具有優異的拾取性,多數情況下只有在實際使用時才知道。However, in the manufacture of semiconductor wafers, it is difficult to predict in advance whether the photocurable adhesive that is expected to be used as the photocurable adhesive layer of the dicing-bonding integrated film has excellent pick-up properties. In most cases, it is only in actual use. just got it.

本發明是鑒於此種情況而完成者,其主要目的在於提供一種用於切割-黏晶一體型膜的光硬化性黏著劑的新穎的評價方法。The present invention was made in view of this situation, and its main purpose is to provide a novel evaluation method of a photocurable adhesive for a dicing-bonding integrated film.

作為被接著體與黏著劑的剝離性的影響因素,可以舉出黏著劑的黏著力(黏著劑的總體特性)、被接著體與黏著劑的界面處的相互作用(黏著劑的表面特性)等。一般來說,已知總體特性對剝離性的貢獻大於表面特性,有藉由調整總體特性來控制剝離性的傾向。但是,認為關於薄型半導體晶片的拾取性,亦無法忽視表面特性的影響,例如,被接著體與黏著劑之間的黏著劑的變形形態,例如剝離被接著體與黏著劑時,黏著劑根據狀況在與被接著體之間不斷裂而如絲、有時如壁般大變形的拉絲亦對剝離性產生大的影響。在以往的產業領域中,拉絲現象的產生被認為是黏著劑的不良現象,藉由減少或抑制拉絲的產生,實現了剝離性的提高(例如,參照上述專利文獻2~7等)。在此種狀況下,本發明者等人進行了努力研究,結果發現在剝離被接著體與黏著劑時,與未觀測到拉絲現象的情況相比,觀測到特定的拉絲現象的情況下,由於拉絲的斷裂衝擊的傳播,剝離進展變快,剝離速度提高,從而完成了本發明。As the factors affecting the peelability between the adherend and the adhesive, the adhesive strength of the adhesive (the overall characteristics of the adhesive), the interaction at the interface between the adherend and the adhesive (the surface characteristics of the adhesive), etc. . Generally speaking, it is known that the overall characteristics contribute more to the peelability than the surface characteristics, and there is a tendency to control the peelability by adjusting the overall characteristics. However, regarding the pick-up of thin semiconductor wafers, the influence of surface characteristics cannot be ignored. For example, the deformed form of the adhesive between the adherend and the adhesive, such as peeling off the adherend and the adhesive, the adhesive depends on the situation. The wire drawing that does not break between the body and the adherend, but deforms like a silk or sometimes like a wall, also has a great influence on the peelability. In the conventional industrial field, the occurrence of wire drawing is considered to be a defective phenomenon of the adhesive. By reducing or suppressing the occurrence of wire drawing, the peelability has been improved (for example, refer to Patent Documents 2 to 7 mentioned above). Under such circumstances, the inventors of the present invention conducted diligent studies and found that when peeling the adherend and the adhesive, compared with the case where no stringing phenomenon was observed, when a specific stringing phenomenon was observed, With the propagation of the breaking impact of the wire drawing, the peeling progresses faster and the peeling speed is improved, thereby completing the present invention.

本發明的一個方面提供一種用於切割-黏晶一體型膜的光硬化性黏著劑的評價方法。該光硬化性黏著劑的評價方法包括:第一步驟,準備依次積層有基材層、包含光硬化性黏著劑的光硬化性黏著劑層、以及接著劑層的切割-黏晶一體型膜,在下述照射條件下對光硬化性黏著劑層照射紫外線,形成光硬化性黏著劑層的硬化物,測定在下述剝離條件下剝離接著劑層和光硬化性黏著劑層的硬化物時的剝離力;第二步驟,準備依次積層有基材層、包含光硬化性黏著劑的光硬化性黏著劑層、以及接著劑層的切割-黏晶一體型膜,在下述加熱冷卻條件下對光硬化性黏著劑層進行處理,並在下述照射條件下對光硬化性黏著劑層照射紫外線,形成光硬化性黏著劑層的硬化物,在下述剝離條件下剝離接著劑層與光硬化性黏著劑層的硬化物,利用掃描型探針顯微鏡觀察接著劑層被剝離後的光硬化性黏著劑層的硬化物的表面,測量表面的拉絲痕跡的痕跡數及痕跡寬度;以及第三步驟,基於剝離力及拉絲痕跡的痕跡數及痕跡寬度,判定光硬化性黏著劑是否良好, (照射條件) 照射強度:70 mW/cm2 累計光量:150 mJ/cm2 (剝離條件) 溫度:25±5℃ 濕度:55±10% 剝離角度:30° 剝離速度:600 mm/分鐘 (加熱冷卻條件) 加熱處理:65℃、15分鐘 冷卻處理:空冷靜置30分鐘,直至25±5℃。One aspect of the present invention provides a method for evaluating a photocurable adhesive for a dicing-bonding integrated film. The evaluation method of the photocurable adhesive includes: a first step of preparing a dicing-bonding integrated film in which a substrate layer, a photocurable adhesive layer containing a photocurable adhesive, and an adhesive layer are sequentially laminated, Under the following irradiation conditions, irradiate the photo-curable adhesive layer with ultraviolet rays to form a cured product of the photo-curable adhesive layer, and measure the peeling force when the adhesive layer and the cured product of the photo-curable adhesive layer are peeled off under the following peeling conditions; The second step is to prepare a dicing-bonding integrated film in which a substrate layer, a photocurable adhesive layer containing a photocurable adhesive, and an adhesive layer are sequentially laminated, and the photocurable adhesive is adhered under the following heating and cooling conditions The adhesive layer is processed, and ultraviolet rays are irradiated to the photo-curable adhesive layer under the following irradiation conditions to form a cured product of the photo-curable adhesive layer, and the adhesive layer and the photo-curable adhesive layer are cured under the following peeling conditions Use a scanning probe microscope to observe the surface of the cured product of the photocurable adhesive layer after the adhesive layer has been peeled off, and measure the number and width of the wire drawing traces on the surface; and the third step is based on the peeling force and wire drawing The number of traces and the width of traces are used to determine whether the photocurable adhesive is good (irradiation conditions) Irradiation intensity: 70 mW/cm 2 Cumulative light quantity: 150 mJ/cm 2 (Peeling conditions) Temperature: 25±5℃ Humidity: 55 ±10% Peeling angle: 30° Peeling speed: 600 mm/min (heating and cooling conditions) Heat treatment: 65°C, 15 minutes Cooling treatment: Leave it in a cool place for 30 minutes, until 25±5°C.

此種光硬化性黏著劑的評價方法對於提前預測預計用作切割-黏晶一體型膜的光硬化性黏著劑層的光硬化性黏著劑是否具有優異拾取性而言是有用的。Such a photocurable adhesive evaluation method is useful for predicting in advance whether the photocurable adhesive, which is expected to be used as the photocurable adhesive layer of the dicing-die-bonding integrated film, has excellent pickup properties.

第三步驟可以是根據剝離力以及拉絲痕跡的痕跡數、及痕跡寬度是否滿足下述條件(a)及下述條件(b)來判定光硬化性黏著劑是否良好的步驟。 條件(a):剝離力為0.70 N/25 mm以下。 條件(b):在剝離接著劑層後的光硬化性黏著劑層的硬化物的表面存在拉絲痕跡的痕跡數為15以上的25 μm×25 μm的區域,區域內的拉絲痕跡的痕跡寬度的中位數為120 nm~200 nm。The third step may be a step of judging whether the photocurable adhesive is good or not based on whether the peeling force, the number of traces of wire drawing, and the width of the trace satisfy the following condition (a) and the following condition (b). Condition (a): The peel force is 0.70 N/25 mm or less. Condition (b): On the surface of the cured product of the photocurable adhesive layer after peeling off the adhesive layer, there is a 25 μm×25 μm area where the number of traces of drawing marks is 15 or more, and the width of the drawing marks in the area The median is 120 nm to 200 nm.

光硬化性黏著劑可含有:具有反應性官能基的(甲基)丙烯酸共聚物、光聚合起始劑、及具有2個以上能夠與反應性官能基反應的官能基的交聯劑。(甲基)丙烯酸共聚物可更含有(甲基)丙烯酸單體單元。The photocurable adhesive may contain a (meth)acrylic copolymer having a reactive functional group, a photopolymerization initiator, and a crosslinking agent having two or more functional groups that can react with the reactive functional group. The (meth)acrylic copolymer may further contain (meth)acrylic monomer units.

接著劑層可含有環氧樹脂、環氧樹脂硬化劑、及具有環氧基的(甲基)丙烯酸共聚物。The adhesive layer may contain an epoxy resin, an epoxy resin hardener, and a (meth)acrylic copolymer having an epoxy group.

本發明的另一個方面提供一種切割-黏晶一體型膜的製造方法,其具備:在基材層上形成光硬化性黏著劑層的步驟,所述光硬化性黏著劑層包含藉由所述光硬化性黏著劑的評價方法而判定為良好的光硬化性黏著劑;以及在光硬化性黏著劑層上形成接著劑層的步驟。Another aspect of the present invention provides a method of manufacturing a dicing-bonding integrated film, which includes a step of forming a photocurable adhesive layer on a substrate layer, the photocurable adhesive layer including The evaluation method of the photocurable adhesive is judged to be a good photocurable adhesive; and the step of forming an adhesive layer on the photocurable adhesive layer.

本發明的另一個方面提供一種半導體裝置的製造方法,其具備:將藉由所述製造方法得到的切割-黏晶一體型膜的接著劑層貼附到半導體晶圓的步驟;藉由切割將半導體晶圓、接著劑層、及光硬化性黏著劑層單片化的步驟;對光硬化性黏著劑層照射紫外線,形成光硬化性黏著劑層的硬化物的步驟;自光硬化性黏著劑層的硬化物拾取附著有接著劑層的半導體元件的步驟;以及經由接著劑層將半導體元件接著於半導體元件搭載用的支撐基板的步驟。Another aspect of the present invention provides a method of manufacturing a semiconductor device, comprising: attaching an adhesive layer of a dicing-bonding integrated film obtained by the manufacturing method to a semiconductor wafer; and dicing The step of singulating the semiconductor wafer, the adhesive layer, and the photo-curable adhesive layer; the step of irradiating the photo-curable adhesive layer with ultraviolet rays to form a cured product of the photo-curing adhesive layer; self-photo-curing adhesive The step of picking up the semiconductor element to which the adhesive layer is attached by the cured product of the layer; and the step of attaching the semiconductor element to the supporting substrate for mounting the semiconductor element via the adhesive layer.

半導體晶圓的厚度可以在35 μm以下。切割可以應用隱形切割。The thickness of the semiconductor wafer can be below 35 μm. Invisible cutting can be used for cutting.

本發明的另一方面提供一種切割-黏晶一體型膜,其依次具備基材層、包含藉由所述光硬化性黏著劑的評價方法被判定為良好的光硬化性黏著劑的光硬化性黏著劑層、以及接著劑層。Another aspect of the present invention provides a dicing-bonding integrated film, which sequentially includes a substrate layer and includes a photocurable adhesive judged to be good by the photocurable adhesive evaluation method. Adhesive layer, and adhesive layer.

根據本發明,提供一種用於切割-黏晶一體型膜的光硬化性黏著劑的新穎的評價方法。另外,根據本發明,提供一種基於此種光硬化性黏著劑的評價方法的切割-黏晶一體型膜及其製造方法。進而,根據本發明,提供一種使用此種切割-黏晶一體型膜的半導體裝置的製造方法。According to the present invention, a novel evaluation method of a photocurable adhesive for a dicing-bonding integrated film is provided. In addition, according to the present invention, a dicing-bonding integrated film based on such a photocurable adhesive evaluation method and a manufacturing method thereof are provided. Furthermore, according to the present invention, there is provided a method of manufacturing a semiconductor device using such a dicing-bonding integrated film.

以下,一邊適宜參照圖式,一邊對本發明的實施方式進行說明。其中,本發明並不限定於以下的實施方式。於以下的實施方式中,除特別注明的情況外,所述構成要素(亦包括步驟等)並非必需。各圖中的構成要素的大小為概念性者,構成要素間的大小的相對關係並不限定於各圖所示者。Hereinafter, the embodiments of the present invention will be described while referring to the drawings as appropriate. However, the present invention is not limited to the following embodiments. In the following embodiments, unless otherwise noted, the constituent elements (including steps, etc.) are not essential. The size of the component elements in each figure is conceptual, and the relative size of the component elements is not limited to that shown in each figure.

關於本說明書中的數值及其範圍,亦同樣如此,且並不限制本發明。於本說明書中,使用「~」所表示的數值範圍表示包含「~」的前後所記載的數值分別作為最小值及最大值的範圍。於本說明書中階段性地記載的數值範圍內,一數值範圍所記載的上限值或下限值亦可替換成另一階段記載的數值範圍的上限值或下限值。另外,於本說明書中所記載的數值範圍內,該數值範圍的上限值或下限值亦可替換成實施例中所示的值。The same applies to the numerical values and ranges in this specification, and the present invention is not limited. In this specification, the numerical range indicated by "~" means a range that includes the numerical values described before and after "~" as the minimum and maximum values, respectively. Within the numerical range described in this specification step by step, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of the numerical range described in another step. In addition, within the numerical range described in this specification, the upper limit or lower limit of the numerical range may be replaced with the values shown in the examples.

於本說明書中,(甲基)丙烯酸酯是指丙烯酸酯或與其相對應的甲基丙烯酸酯。關於(甲基)丙烯醯基、(甲基)丙烯酸共聚物等其他的類似表述,亦同樣如此。In this specification, (meth)acrylate refers to acrylate or methacrylate corresponding thereto. The same applies to other similar expressions such as (meth)acrylic acid group and (meth)acrylic acid copolymer.

在本說明書中,所謂「拉絲」是被接著體與黏著劑之間的黏著劑的變形形態,在剝離被接著體與黏著劑時,黏著劑在與被接著體之間不發生斷裂而如絲般大變形。「拉絲痕跡」是指藉由在拉絲發生後黏著劑斷裂而部分收縮、大變形後部分收縮、或者黏著劑被不可逆地拉伸或者大變形後自被接著體剝離而部分收縮,從而在黏著劑的表面觀測到呈痕跡(突起)的形式。In this specification, the so-called "drawing" refers to the deformed form of the adhesive between the adherend and the adhesive. When the adherend and the adhesive are peeled off, the adhesive does not break between the adherend and the adherend but is silky As large as deformed. "Drawing traces" refers to the partial shrinkage of the adhesive after the wire drawing occurs, partial shrinkage after large deformation, or partial shrinkage of the adhesive after being irreversibly stretched or large deformation after peeling from the adherend, so that the adhesive The surface was observed in the form of traces (protrusions).

[光硬化性黏著劑的評價方法] 一實施方式的切割-黏晶一體型膜所使用的光硬化性黏著劑的評價方法包括:第一步驟,準備依次積層有基材層、包含光硬化性黏著劑的光硬化性黏著劑層、以及接著劑層的切割-黏晶一體型膜,在特定的照射條件下對光硬化性黏著劑層照射紫外線,形成光硬化性黏著劑層的硬化物,測定在特定的剝離條件下剝離接著劑層和光硬化性黏著劑層的硬化物時的剝離力;第二步驟,準備依次積層有基材層、包含光硬化性黏著劑的光硬化性黏著劑層、以及接著劑層的切割-黏晶一體型膜,在特定的加熱冷卻條件下對光硬化性黏著劑層進行處理,並在特定的照射條件下對光硬化性黏著劑層照射紫外線,形成光硬化性黏著劑層的硬化物,在特定的剝離條件下剝離接著劑層與光硬化性黏著劑層的硬化物,利用掃描型探針顯微鏡觀察接著劑層被剝離後的光硬化性黏著劑層的硬化物的表面,測量表面的拉絲痕跡的痕跡數及痕跡寬度;以及第三步驟,基於剝離力及拉絲痕跡的痕跡數及痕跡寬度,判定光硬化性黏著劑是否良好。[Evaluation method of light-curing adhesive] The evaluation method of the photocurable adhesive used in the dicing-bonding integrated film of one embodiment includes: a first step of preparing a substrate layer, a photocurable adhesive layer containing a photocurable adhesive, and And the dicing-bonding integrated film of the adhesive layer, irradiating ultraviolet rays to the photo-curing adhesive layer under specific irradiation conditions to form a cured product of the photo-curing adhesive layer, and measuring the peeling of the adhesive under the specific peeling conditions The peeling force of the hardened product of the light-curing adhesive layer and the photocurable adhesive layer; the second step is to prepare a substrate layer, a photocurable adhesive layer containing a photocurable adhesive, and a cutting-bonding die of the adhesive layer. One-piece film, the photo-curable adhesive layer is processed under specific heating and cooling conditions, and ultraviolet rays are irradiated to the photo-curable adhesive layer under specific irradiation conditions to form a cured product of the photo-curable adhesive layer. Peel off the cured product of the adhesive layer and the photocurable adhesive layer under specific peeling conditions, observe the surface of the cured product of the photocurable adhesive layer after the adhesive layer has been peeled off with a scanning probe microscope, and measure the stringiness of the surface The number of traces and the width of the trace; and the third step, based on the peeling force and the number of traces of the drawing trace, and the width of the trace, determine whether the photocurable adhesive is good.

以下,首先說明作為評價對象的光硬化性黏著劑、以及具備包括光硬化性黏著劑的光硬化性黏著劑層的切割-黏晶一體型膜及其製造方法,接著,考察拉絲現象的影響因素,最後對各步驟進行說明。In the following, firstly, the photocurable adhesive as the evaluation object, the dicing-bonding integrated film with a photocurable adhesive layer including the photocurable adhesive and its manufacturing method will be described, and then the factors affecting the wire drawing phenomenon will be investigated. , And finally explain each step.

<光硬化性黏著劑> 在本實施方式的光硬化性黏著劑的評價方法中,藉由紫外線的照射而硬化的光硬化性黏著劑可成為評價對象。以下,作為成為評價對象的光硬化性黏著劑的一個例子,對含有具有反應性官能基的(甲基)丙烯酸共聚物、光聚合起始劑、及具有2個以上能夠與反應性官能基反應的官能基的交聯劑的光硬化性黏著劑進行說明。<Light-curing adhesive> In the evaluation method of the photocurable adhesive of the present embodiment, the photocurable adhesive cured by the irradiation of ultraviolet rays can be the object of evaluation. Hereinafter, as an example of a photocurable adhesive to be evaluated, a (meth)acrylic copolymer containing a reactive functional group, a photopolymerization initiator, and two or more reactive functional groups capable of reacting with The functional group of the crosslinking agent of the photocurable adhesive will be described.

(具有反應性官能基的(甲基)丙烯酸共聚物) 具有反應性官能基的(甲基)丙烯酸共聚物例如可藉由將一種或兩種以上的(甲基)丙烯酸酯單體(a1)或(甲基)丙烯酸、與具有反應性官能基的一種或兩種以上的聚合性化合物(a2)共聚而得到。((Meth)acrylic copolymer with reactive functional group) The (meth)acrylic copolymer having a reactive functional group can be obtained by combining one or two or more (meth)acrylate monomers (a1) or (meth)acrylic acid with one having a reactive functional group. Or obtained by copolymerizing two or more polymerizable compounds (a2).

(甲基)丙烯酸酯單體(a1)例如可為選自由(甲基)丙烯酸直鏈或分支烷基酯、脂環式(甲基)丙烯酸酯、芳香族(甲基)丙烯酸酯、(甲基)丙烯酸烷氧基烷基酯、烷氧基(聚)烷二醇(甲基)丙烯酸酯、(甲基)丙烯酸烷氧基烷氧基烷基酯、及(甲基)丙烯酸二烷基胺基烷基酯所組成的組群的至少一種。The (meth)acrylate monomer (a1) may be selected from, for example, linear or branched (meth)acrylate alkyl esters, alicyclic (meth)acrylates, aromatic (meth)acrylates, (meth)acrylates, Base) alkoxyalkyl acrylate, alkoxy (poly)alkylene glycol (meth)acrylate, alkoxy alkoxyalkyl (meth)acrylate, and dialkyl (meth)acrylate At least one of the group consisting of amino alkyl esters.

作為(甲基)丙烯酸直鏈或分支烷基酯,例如可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、2-(甲基)丙烯酸乙基己酯、(甲基)丙烯酸硬脂基酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十三烷基酯。Examples of linear or branched (meth)acrylate alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and n-butyl (meth)acrylate. Esters, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, ethylhexyl 2-(meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate , Tridecyl (meth)acrylate.

作為脂環式(甲基)丙烯酸酯,例如可列舉:(甲基)丙烯酸環己酯、(甲基)丙烯酸異冰片酯、及(甲基)丙烯酸二環戊酯。As alicyclic (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentyl (meth)acrylate are mentioned, for example.

作為芳香族(甲基)丙烯酸酯,例如可列舉:(甲基)丙烯酸苯氧基乙酯等。As an aromatic (meth)acrylate, phenoxyethyl (meth)acrylate etc. are mentioned, for example.

作為(甲基)丙烯酸烷氧基烷基酯,例如可列舉:(甲基)丙烯酸乙氧基乙酯、(甲基)丙烯酸丁氧基乙酯等。Examples of the alkoxyalkyl (meth)acrylate include ethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, and the like.

作為烷氧基(聚)烷二醇(甲基)丙烯酸酯,例如可列舉:甲氧基二乙二醇(甲基)丙烯酸酯、乙氧基二乙二醇(甲基)丙烯酸酯、甲氧基三乙二醇(甲基)丙烯酸酯、丁氧基三乙二醇(甲基)丙烯酸酯、及甲氧基二丙二醇(甲基)丙烯酸酯等。As the alkoxy (poly)alkylene glycol (meth)acrylate, for example, methoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methacrylate Oxytriethylene glycol (meth)acrylate, butoxytriethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, etc.

作為(甲基)丙烯酸烷氧基烷氧基烷基酯,例如可列舉:(甲基)丙烯酸2-甲氧基乙氧基乙酯、及(甲基)丙烯酸2-乙氧基乙氧基乙酯。Examples of (meth)acrylic acid alkoxyalkoxyalkyl esters include: (meth)acrylic acid 2-methoxyethoxyethyl and (meth)acrylic acid 2-ethoxyethoxy Ethyl ester.

作為(甲基)丙烯酸二烷基胺基烷基酯,例如可列舉:(甲基)丙烯酸N,N-二甲基胺基乙酯、及(甲基)丙烯酸N,N-二乙基胺基乙酯。Examples of the dialkylaminoalkyl (meth)acrylate include N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylamine (meth)acrylate Ethyl ester.

聚合性化合物(a2)可具有選自由羥基及環氧基所組成的群組中的至少一種反應性官能基。羥基及環氧基與具有異氰酸酯基等的化合物(b)的反應性良好,因此可以適當使用。聚合性化合物(a2)較佳為具有羥基。The polymerizable compound (a2) may have at least one reactive functional group selected from the group consisting of a hydroxyl group and an epoxy group. Since the hydroxyl group and epoxy group have good reactivity with the compound (b) having an isocyanate group or the like, they can be used appropriately. The polymerizable compound (a2) preferably has a hydroxyl group.

就具有羥基作為反應性官能基的聚合性化合物(a2)而言,例如可列舉:(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸2-羥基丙酯等(甲基)丙烯酸羥基烷基酯等。The polymerizable compound (a2) having a hydroxyl group as a reactive functional group includes, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and (meth)acrylic acid 2 -Hydroxypropyl (meth)acrylate and other hydroxyalkyl esters.

就具有環氧基作為反應性官能基的聚合性化合物(a2)而言,例如可列舉:(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧環己酯等具有環氧基的(甲基)丙烯酸酯等。The polymerizable compound (a2) having an epoxy group as a reactive functional group includes, for example, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate and the like. (Meth)acrylate of oxy group, etc.

(甲基)丙烯酸共聚物可含有(甲基)丙烯酸作為單體單元。另外,除了(甲基)丙烯酸酯單體(a1)及聚合性化合物(a2)以外,可含有其他聚合性化合物作為單體單元。作為其它聚合性化合物,例如可列舉苯乙烯、乙烯基甲苯等芳香族乙烯基化合物等。The (meth)acrylic copolymer may contain (meth)acrylic acid as a monomer unit. In addition, in addition to the (meth)acrylate monomer (a1) and the polymerizable compound (a2), other polymerizable compounds may be contained as monomer units. Examples of other polymerizable compounds include aromatic vinyl compounds such as styrene and vinyl toluene.

具有反應性官能基的(甲基)丙烯酸共聚物可更具有能夠鏈聚合的官能基。即,可具有:包含具有反應性官能基的(甲基)丙烯酸共聚物的主鏈、及鍵結於主鏈且包含聚合性雙鍵的側鏈。包含聚合性雙鍵的側鏈可以是(甲基)丙烯醯基,但不限於此。具有能夠鏈聚合的官能基的(甲基)丙烯酸共聚物可藉由以下方式而獲得,即,使包括與具有反應性官能基的(甲基)丙烯酸共聚物的反應性官能基反應的官能基、及能夠鏈聚合的官能基的一種或兩種以上的化合物(b)反應,在(甲基)丙烯酸共聚物的側鏈導入可鏈聚合的官能基。The (meth)acrylic copolymer having a reactive functional group may further have a functional group capable of chain polymerization. That is, it may have a main chain including a (meth)acrylic copolymer having a reactive functional group and a side chain bonded to the main chain and including a polymerizable double bond. The side chain containing the polymerizable double bond may be a (meth)acryloyl group, but is not limited thereto. The (meth)acrylic copolymer having a functional group capable of chain polymerization can be obtained by including a functional group that reacts with the reactive functional group of the (meth)acrylic copolymer having a reactive functional group , And one or two or more compounds (b) of functional groups capable of chain polymerization are reacted to introduce a chain polymerizable functional group into the side chain of the (meth)acrylic copolymer.

作為與反應性官能基(環氧基、羥基等)反應的官能基,例如可以舉出異氰酸酯基等。As a functional group which reacts with a reactive functional group (epoxy group, hydroxyl group etc.), an isocyanate group etc. are mentioned, for example.

作為具有異氰酸酯基的化合物(b)的具體例子,可以舉出2-甲基丙烯醯氧基乙基異氰酸酯(例如昭和電工股份有限公司製、商品名「卡萊茲(Karenz)MOI」)。As a specific example of the compound (b) having an isocyanate group, 2-methacryloxyethyl isocyanate (for example, a product made by Showa Denko Co., Ltd., trade name "Karenz MOI") can be given.

相對於具有反應性官能基的(甲基)丙烯酸共聚物,化合物(b)的含量可為0.3 mmol/g~1.5 mmol/g。The content of the compound (b) may be 0.3 mmol/g to 1.5 mmol/g relative to the (meth)acrylic copolymer having a reactive functional group.

具有反應性官能基的(甲基)丙烯酸共聚物的酸值例如可為0 mgKOH/g~150 mgKOH/g。具有反應性官能基的(甲基)丙烯酸共聚物的羥基值例如可為0 mgKOH/g~150 mgKOH/g。酸值及羥基值按照日本工業標準(Japanese Industrial Standards,JIS)K0070來測定。The acid value of the (meth)acrylic copolymer having a reactive functional group can be, for example, 0 mgKOH/g to 150 mgKOH/g. The hydroxyl value of the (meth)acrylic copolymer having a reactive functional group can be, for example, 0 mgKOH/g to 150 mgKOH/g. The acid value and hydroxyl value are measured in accordance with Japanese Industrial Standards (JIS) K0070.

具有反應性官能基的(甲基)丙烯酸共聚物的重量平均分子量(Mw)可為10萬~100萬、20萬~80萬或30萬~70萬。重量平均分子量是利用凝膠滲透層析法(Gel Permeation Chromatography,GPC)並使用根據標準聚苯乙烯的標準曲線而得的聚苯乙烯換算值。The weight average molecular weight (Mw) of the (meth)acrylic copolymer having a reactive functional group may be 100,000 to 1 million, 200,000 to 800,000, or 300,000 to 700,000. The weight average molecular weight is a polystyrene conversion value obtained by using a gel permeation chromatography (Gel Permeation Chromatography, GPC) method based on a standard curve of standard polystyrene.

(光聚合起始劑) 作為光聚合起始劑,只要是藉由紫外線的照射而開始聚合的光聚合起始劑,就沒有特別限制,例如可舉出光自由基聚合起始劑等。作為光自由基聚合起始劑,例如可列舉:2,2-二甲氧基-1,2-二苯基乙烷-1-酮等安息香縮酮;1-羥基環己基苯基酮等α-羥基酮;2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁烷-1-酮等α-胺基酮;1-[4-(苯硫基)苯基]-1,2-辛二酮-2-(苯甲醯基)肟等肟酯;雙(2,4,6-三甲基苯甲醯基)苯基氧化膦等氧化膦;2-(鄰氯苯基)-4,5-二苯基咪唑二聚體等2,4,5-三芳基咪唑二聚體;二苯甲酮、N,N,N',N'-四甲基-4,4'-二胺基二苯甲酮等二苯甲酮化合物;2-乙基蒽醌等醌化合物;安息香甲醚等安息香醚;安息香等安息香化合物;苄基二甲基縮酮等苄基化合物;9-苯基吖啶等吖啶化合物;N-苯基甘胺酸、香豆素等。該些可單獨使用一種,亦可與適當的增感劑組合使用。(Photopolymerization initiator) The photopolymerization initiator is not particularly limited as long as it is a photopolymerization initiator that starts polymerization by irradiation with ultraviolet rays, and examples thereof include photoradical polymerization initiators. Examples of the photoradical polymerization initiator include: 2,2-dimethoxy-1,2-diphenylethane-1-one and other benzoin ketals; 1-hydroxycyclohexylphenyl ketone and the like α -Hydroxy ketone; 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butane-1-one and other α-amino ketones; 1-[4-(phenylsulfide (Yl)phenyl]-1,2-octanedione-2-(benzyl)oxime and other oxime esters; bis(2,4,6-trimethylbenzyl)phenylphosphine oxide and other phosphine oxides ; 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer and other 2,4,5-triarylimidazole dimer; benzophenone, N,N,N',N'- Benzophenone compounds such as tetramethyl-4,4'-diaminobenzophenone; Quinone compounds such as 2-ethylanthraquinone; Benzoin ethers such as benzoin methyl ether; Benzoin compounds such as benzoin; Benzyldimethyl Benzyl compounds such as ketals; acridine compounds such as 9-phenylacridine; N-phenylglycine, coumarin, etc. These can be used alone or in combination with an appropriate sensitizer.

相對於(甲基)丙烯酸共聚物100質量份,光聚合起始劑含量可為0.1質量份~10質量份、或0.5質量份~5質量份。The content of the photopolymerization initiator may be 0.1 parts by mass to 10 parts by mass, or 0.5 parts by mass to 5 parts by mass relative to 100 parts by mass of the (meth)acrylic copolymer.

(交聯劑) 交聯劑只要是具有2個以上能夠與具有反應性官能基的(甲基)丙烯酸共聚物的反應性官能基(環氧基、羥基等)反應的官能基的化合物,則沒有特別限制。作為藉由交聯劑與具有反應性官能基的(甲基)丙烯酸共聚物的反應而形成的鍵,例如可以舉出酯鍵、醚鍵、醯胺鍵、醯亞胺鍵、胺基甲酸酯鍵、脲鍵等。(Crosslinking agent) The crosslinking agent is not particularly limited as long as it is a compound having two or more functional groups capable of reacting with the reactive functional group (epoxy group, hydroxyl group, etc.) of the (meth)acrylic copolymer having a reactive functional group. As the bond formed by the reaction of the crosslinking agent and the (meth)acrylic copolymer having a reactive functional group, for example, an ester bond, an ether bond, an amide bond, an imine bond, and urethane bond can be cited. Ester bond, urea bond, etc.

作為交聯劑,例如可舉出在一分子中具有2個以上的異氰酸酯基的化合物。使用此種化合物時,由於與所述(甲基)丙烯酸共聚物所具有的反應性官能基容易反應,因此有容易控制黏著性和拉絲的傾向。As a crosslinking agent, the compound which has 2 or more isocyanate groups in one molecule is mentioned, for example. When such a compound is used, since it easily reacts with the reactive functional group possessed by the (meth)acrylic copolymer, it tends to be easy to control adhesion and stringiness.

作為一分子中具有2個以上異氰酸酯基的化合物,例如可列舉出2,4-甲伸苯基二異氰酸酯、2,6-甲伸苯基二異氰酸酯、1,3-伸二甲苯基二異氰酸酯、1,4-伸二甲苯基二異氰酸酯、二苯基甲烷-4,4'-二異氰酸酯、二苯基甲烷2,4'-二異氰酸酯、3-甲基二苯基甲烷二異氰酸酯、六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、二環己基甲烷-4,4'-二異氰酸酯、二環己基甲烷-2,4'-二異氰酸酯、離胺酸異氰酸酯等異氰酸酯化合物等。As the compound having two or more isocyanate groups in one molecule, for example, 2,4-phenylene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylylene diisocyanate, 1 ,4-xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane 2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate Isocyanate compounds such as isocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, lysine isocyanate, etc.

作為一分子中具有2個以上異氰酸酯基的化合物的具體例,可舉出多官能異氰酸酯(日本聚胺基甲酸酯工業股份有限公司製,商品名「科羅耐特(Coronate)L」)。As a specific example of a compound having two or more isocyanate groups in one molecule, a polyfunctional isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate L") can be mentioned.

交聯劑可以是所述異氰酸酯化合物與一分子中具有2個以上羥基的多元醇的反應產物(含有異氰酸基的寡聚物)。作為一分子中具有2個以上羥基的多元醇,例如可列舉乙二醇、丙二醇、丁二醇、1,6-己二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、1,11-十一烷二醇、1,12-十二烷二醇、甘油、季戊四醇、二季戊四醇、1,4-環己二醇、1,3-環己二醇等。The crosslinking agent may be a reaction product (isocyanate group-containing oligomer) of the isocyanate compound and a polyol having two or more hydroxyl groups in one molecule. Examples of polyols having two or more hydroxyl groups in one molecule include ethylene glycol, propylene glycol, butylene glycol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, glycerin, pentaerythritol, dipentaerythritol, 1,4-cyclohexanediol, 1,3-cyclohexane Glycol and so on.

其中,交聯劑可以是一分子中具有2個以上異氰酸酯基的多官能異氰酸酯與一分子中具有3個以上羥基的多元醇的反應產物(含異氰酸基的寡聚物)。藉由使用此種含異氰酸酯基的寡聚物作為交聯劑,光硬化性黏著劑層20有形成更緻密的交聯結構的傾向。Wherein, the crosslinking agent may be a reaction product (isocyanate group-containing oligomer) of a polyfunctional isocyanate having two or more isocyanate groups in one molecule and a polyol having three or more hydroxyl groups in one molecule. By using such an isocyanate group-containing oligomer as a crosslinking agent, the photocurable adhesive layer 20 tends to form a denser crosslinked structure.

交聯劑的含量例如相對於(甲基)丙烯酸共聚物總質量,可為3質量%~50質量%。The content of the crosslinking agent may be 3% by mass to 50% by mass relative to the total mass of the (meth)acrylic copolymer, for example.

<切割-黏晶一體型膜及其製造方法> 圖1是表示切割-黏晶一體型膜的一個實施方式的示意剖面圖。切割-黏晶一體型膜1依次積層有基材層10、包含光硬化性黏著劑的光硬化性黏著劑層20、及接著劑層30。<Cutting-bonding integrated film and its manufacturing method> Fig. 1 is a schematic cross-sectional view showing an embodiment of a dicing-bonding integrated film. In the dicing-bonding integrated film 1, a substrate layer 10, a photocurable adhesive layer 20 containing a photocurable adhesive, and an adhesive layer 30 are sequentially laminated.

(基材層) 基材層10只要可使用已知的聚合物片或膜,並且包含黏晶步驟中可以擴展的材料,則沒有特別限制。作為此種材料,例如可以列舉:結晶性聚丙烯、非晶性聚丙烯、高密度聚乙烯、中密度聚乙烯、低密度聚乙烯、超低密度聚乙烯、低密度直鏈聚乙烯、聚丁烯、聚甲基戊烯等聚烯烴;乙烯-乙酸乙烯酯共聚物;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(無規、交替)共聚物;乙烯-丙烯共聚物;乙烯-丁烯共聚物;乙烯-己烯共聚物;聚胺基甲酸酯;聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等聚酯;聚碳酸酯;聚醯亞胺;聚醚醚酮;聚醯亞胺;聚醚醯亞胺;聚醯胺;全芳香族聚醯胺;聚苯基硫醚;芳族聚醯胺(aramid)(紙);玻璃;玻璃布;氟樹脂;聚氯乙烯;聚偏二氯乙烯;纖維素系樹脂;矽酮樹脂等。該些材料可以是與增塑劑、二氧化矽、抗黏連材料、滑劑、抗靜電劑等混合的材料。(Substrate layer) The base material layer 10 is not particularly limited as long as it can use a known polymer sheet or film and includes a material that can be expanded in the die bonding step. Examples of such materials include: crystalline polypropylene, amorphous polypropylene, high-density polyethylene, medium-density polyethylene, low-density polyethylene, ultra-low-density polyethylene, low-density linear polyethylene, polybutylene Polyolefins such as olefin and polymethylpentene; ethylene-vinyl acetate copolymer; ionic polymer resin; ethylene-(meth)acrylic acid copolymer; ethylene-(meth)acrylate (random, alternating) copolymer ; Ethylene-propylene copolymer; ethylene-butene copolymer; ethylene-hexene copolymer; polyurethane; polyester such as polyethylene terephthalate and polyethylene naphthalate; polycarbonate Ester; Polyimine; Polyetheretherketone; Polyimine; Polyetherimine; Polyamide; Fully Aromatic Polyamide; Polyphenyl Sulfide; Aromatic Polyamide (aramid) (Paper ); glass; glass cloth; fluororesin; polyvinyl chloride; polyvinylidene chloride; cellulose resin; silicone resin, etc. These materials can be materials mixed with plasticizers, silica, anti-blocking materials, slip agents, antistatic agents, and the like.

其中,基材層10自楊氏模量、應力緩和性、熔點等特性、價格方面、使用後的廢材再利用等觀點而言,較佳為具有以選自聚乙烯、聚丙烯、聚乙烯-聚丙烯無規共聚物、及聚乙烯-聚丙烯嵌段共聚物中的至少一種材料為主成分的表面,且該表面與光硬化性黏著劑層20相接。基材層10可以是單層,亦可以是包含不同材料的2層以上的多層。自控制與後述的光硬化性黏著劑層20的密接性的觀點出發,基材層10可根據需要實施電暈放電處理、消光處理等表面粗糙化處理。Among them, the base layer 10 is preferably selected from polyethylene, polypropylene, polyethylene from the viewpoints of characteristics such as Young's modulus, stress relaxation, melting point, price, and recycling of waste materials after use. -A surface where at least one of a polypropylene random copolymer and a polyethylene-polypropylene block copolymer is the main component, and the surface is in contact with the light-curable adhesive layer 20. The base material layer 10 may be a single layer, or may be a multilayer of two or more layers containing different materials. From the viewpoint of controlling the adhesiveness with the photocurable adhesive layer 20 described later, the base layer 10 may be subjected to surface roughening treatments such as corona discharge treatment and matting treatment as necessary.

基材層10的厚度例如可以是70 μm~120 μm或80 μm~100 μm。如果基材層10的厚度為70 μm以上,則存在能夠進一步抑制擴展引起的破損的傾向。基材層10的厚度為120 μm以下時,拾取中的應力容易到達接著劑層,具有拾取性更優異的傾向。The thickness of the base layer 10 may be 70 μm to 120 μm or 80 μm to 100 μm, for example. If the thickness of the base layer 10 is 70 μm or more, there is a tendency that damage due to expansion can be further suppressed. When the thickness of the base layer 10 is 120 μm or less, the stress during pickup easily reaches the adhesive layer, and there is a tendency that the pickup property is more excellent.

(光硬化性黏著劑層) 光硬化性黏著劑層20為包含所述光硬化性黏著劑的層。光硬化性黏著劑層20形成於基材層10上。作為在基材層10上形成光硬化性黏著劑層20的方法,例如可列舉:調製光硬化性黏著劑層形成用清漆,將該清漆塗佈於基材層10,除去所述清漆的揮發成分,形成光硬化性黏著劑層20的方法;將該清漆塗佈於經脫模處理的膜上,除去所述清漆的揮發成分,形成光硬化性黏著劑層20,並將得到的光硬化性黏著劑層20轉印至基材層10的方法。(Light-curing adhesive layer) The photocurable adhesive layer 20 is a layer containing the photocurable adhesive. The photocurable adhesive layer 20 is formed on the base layer 10. As a method of forming the photocurable adhesive layer 20 on the base layer 10, for example, a varnish for forming a photocurable adhesive layer is prepared, the varnish is applied to the base layer 10, and the volatilization of the varnish is removed. Ingredients, a method of forming a light-curing adhesive layer 20; coating the varnish on a release-treated film, removing the volatile components of the varnish, forming a light-curing adhesive layer 20, and curing the obtained light The method of transferring the adhesive layer 20 to the base layer 10.

光硬化性黏著劑層形成用清漆含有:具有反應性官能基的(甲基)丙烯酸共聚物、光聚合起始劑、以及具有2個以上能夠與反應性官能基反應的官能基的交聯劑、及有機溶劑。有機溶劑可將具有反應性官能基的(甲基)丙烯酸共聚物、光聚合起始劑、以及具有2個以上能夠與反應性官能基反應的官能基的交聯劑用化,可藉由加熱而揮發。作為此種有機溶劑,例如可列舉甲苯、二甲苯等芳香族烴;四氫呋喃、1,4-二噁烷等環狀醚;甲醇、乙醇、乙二醇、丙二醇等醇;丙酮、甲基乙基酮、甲基異丁基酮、環己酮等酮;乙酸甲酯、乙酸乙酯、γ-丁內酯等酯;碳酸伸乙酯、碳酸伸丙酯等碳酸酯;乙二醇單甲醚、乙二醇二甲醚、丙二醇單甲醚、丙二醇單乙醚、丙二醇二甲醚等多元醇烷基醚;乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯等多元醇烷基醚乙酸酯;N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮等醯胺等。該些可單獨使用一種,亦可將兩種以上組合使用。以清漆總質量為基準,清漆固體成分濃度可以為10質量%~60質量%。The varnish for forming a photocurable adhesive layer contains: a (meth)acrylic copolymer having a reactive functional group, a photopolymerization initiator, and a crosslinking agent having two or more functional groups capable of reacting with the reactive functional group , And organic solvents. The organic solvent can be used as a (meth)acrylic copolymer having a reactive functional group, a photopolymerization initiator, and a crosslinking agent having two or more functional groups capable of reacting with the reactive functional group. And volatile. Examples of such organic solvents include aromatic hydrocarbons such as toluene and xylene; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; alcohols such as methanol, ethanol, ethylene glycol, and propylene glycol; acetone, methyl ethyl Ketones, methyl isobutyl ketone, cyclohexanone and other ketones; esters such as methyl acetate, ethyl acetate, γ-butyrolactone; carbonates such as ethylene carbonate and propylene carbonate; ethylene glycol monomethyl ether , Ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether and other polyhydric alcohol alkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and other polyhydric alcohol alkanes Base ether acetate; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and other amides. These can be used alone or in combination of two or more. Based on the total mass of the varnish, the solid content concentration of the varnish may be 10% by mass to 60% by mass.

光硬化性黏著劑層20的厚度例如可為1 μm~200 μm、3 μm~50 μm、或5 μm~30 μm。The thickness of the photocurable adhesive layer 20 may be, for example, 1 μm to 200 μm, 3 μm to 50 μm, or 5 μm to 30 μm.

(接著劑層) 接著劑層30是包含接著劑的層。接著劑只要是在黏晶膜的領域使用的接著劑,就沒有特別限制。以下,作為接著劑的一例,對含有環氧樹脂、環氧樹脂硬化劑、及具有環氧基的(甲基)丙烯酸共聚物的接著劑進行說明。根據包含此種接著劑的接著劑層30,晶片與基板之間、晶片與晶片之間的接著性優異,能夠賦予電極埋入性、導線埋入性等,並且在黏晶步驟中能夠在低溫下進行接著。(Adhesive layer) The adhesive layer 30 is a layer containing an adhesive. The adhesive is not particularly limited as long as it is an adhesive used in the field of crystal adhesion films. Hereinafter, as an example of the adhesive, an adhesive containing an epoxy resin, an epoxy resin curing agent, and a (meth)acrylic copolymer having an epoxy group will be described. According to the adhesive layer 30 containing such an adhesive, the adhesiveness between the wafer and the substrate and between the wafer and the wafer is excellent, and it is possible to impart electrode embedding properties, wire embedding properties, etc., and it can be used at low temperatures in the die bonding step. Next proceed.

作為環氧樹脂,例如可列舉:雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚A酚醛清漆型環氧樹脂、雙酚F酚醛清漆型環氧樹脂、含二環戊二烯骨架的環氧樹脂、二苯乙烯型環氧樹脂、含三嗪骨架的環氧樹脂、含芴骨架的環氧樹脂、三苯酚甲烷型環氧樹脂、聯苯型環氧樹脂、伸二甲苯基型環氧樹脂、聯苯芳烷基型環氧樹脂、萘型環氧樹脂、多官能苯酚類、蒽等多環芳香族類的二縮水甘油醚化合物等。該些可單獨使用一種或將兩種以上組合使用。As the epoxy resin, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, Bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, epoxy resin containing dicyclopentadiene skeleton, stilbene type epoxy resin, epoxy resin containing triazine skeleton, Fluorene skeleton epoxy resin, triphenol methane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, polyfunctional phenols , Anthracene and other polycyclic aromatic diglycidyl ether compounds. These can be used alone or in combination of two or more.

環氧樹脂硬化劑例如可以是酚醛樹脂。酚醛樹脂只要在分子內具有酚性羥基,則可無特別限制地使用。作為酚醛樹脂,例如可列舉:使苯酚、甲酚、間苯二酚(resorcin)、鄰苯二酚、雙酚A、雙酚F、苯基苯酚、胺基苯酚等酚類及/或α-萘酚、β-萘酚、二羥基萘等萘酚類與甲醛等具有醛基的化合物於酸性觸媒下縮合或共縮合而獲得的酚醛清漆型酚醛樹脂、由烯丙基化雙酚A、烯丙基化雙酚F、烯丙基化萘二醇、苯酚酚醛清漆、苯酚等酚類及/或萘酚類與二甲氧基對二甲苯或雙(甲氧基甲基)聯苯所合成的苯酚芳烷基樹脂、萘酚芳烷基樹脂等。該些可單獨使用一種或將兩種以上組合使用。The epoxy resin hardener may be a phenol resin, for example. The phenol resin can be used without particular limitation as long as it has a phenolic hydroxyl group in the molecule. Examples of phenol resins include phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, and/or α- Naphthol, β-naphthol, dihydroxynaphthalene, and other naphthols, and compounds with aldehyde groups such as formaldehyde, are condensed or co-condensed in an acidic catalyst. Novolac-type phenolic resins are obtained by condensation of allylated bisphenol A, Allylated bisphenol F, allylated naphthalenediol, phenol novolac, phenol and other phenols and/or naphthols and dimethoxypara-xylene or bis(methoxymethyl)biphenyl Synthetic phenol aralkyl resin, naphthol aralkyl resin, etc. These can be used alone or in combination of two or more.

具有環氧基的(甲基)丙烯酸共聚物可以是將作為原料的(甲基)丙烯酸縮水甘油酯相對於得到的共聚物調整為0.5質量%~6質量%的量的共聚物。該量為0.5質量%以上時,有容易得到高接著力的傾向,該量為6質量%以下時,有能夠抑制凝膠化的傾向。(甲基)丙烯酸縮水甘油酯的其餘部分可以是(甲基)丙烯酸甲酯等具有碳原子數1~8的烷基的(甲基)丙烯酸烷基酯以及苯乙烯、丙烯腈等的混合物。(甲基)丙烯酸烷基酯可包含(甲基)丙烯酸乙酯及/或(甲基)丙烯酸丁酯。各成分的混合比率可考慮得到的具有環氧基的(甲基)丙烯酸共聚物的Tg(玻璃轉移溫度)來調整。如果Tg為-10℃以上,則B階段狀態下的接著劑層30的黏性有變好的傾向,有處理性優異的傾向。具有環氧基的(甲基)丙烯酸共聚物的Tg的上限值例如可為30℃。The (meth)acrylic copolymer having an epoxy group may be a copolymer obtained by adjusting the glycidyl (meth)acrylate as a raw material to an amount of 0.5% by mass to 6% by mass relative to the obtained copolymer. When the amount is 0.5% by mass or more, high adhesive strength tends to be easily obtained, and when the amount is 6% by mass or less, there is a tendency that gelation can be suppressed. The remainder of the glycidyl (meth)acrylate may be a mixture of alkyl (meth)acrylates having an alkyl group having 1 to 8 carbon atoms, such as methyl (meth)acrylate, and styrene, acrylonitrile, and the like. The alkyl (meth)acrylate may include ethyl (meth)acrylate and/or butyl (meth)acrylate. The mixing ratio of each component can be adjusted in consideration of the Tg (glass transition temperature) of the obtained epoxy-containing (meth)acrylic copolymer. If the Tg is -10°C or higher, the adhesive layer 30 in the B-stage state tends to have better viscosity and tends to be excellent in handleability. The upper limit of the Tg of the (meth)acrylic copolymer having an epoxy group may be 30°C, for example.

具有環氧基的(甲基)丙烯酸共聚物的重量平均分子量可為10萬以上,亦可為30萬~300萬或50萬~200萬。如果重量平均分子量為300萬以下,則有能夠控制半導體晶片與支撐基板之間的填充性降低的傾向。重量平均分子量是利用凝膠滲透層析法(GPC)並使用根據標準聚苯乙烯的標準曲線而得的聚苯乙烯換算值。The weight average molecular weight of the (meth)acrylic copolymer having an epoxy group may be 100,000 or more, and may also be 300,000 to 3 million or 500,000 to 2 million. If the weight average molecular weight is 3 million or less, it tends to be able to control the decrease in fillability between the semiconductor wafer and the supporting substrate. The weight average molecular weight is a polystyrene conversion value obtained by gel permeation chromatography (GPC) using a standard curve based on standard polystyrene.

接著劑可根據需要進一步含有三級胺、咪唑類、四級銨鹽等硬化促進劑。作為硬化促進劑,例如可列舉:2-甲基咪唑、2-乙基-4-甲基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-苯基咪唑鎓偏苯三酸酯。該些可單獨使用一種或將兩種以上組合使用。The adhesive may further contain hardening accelerators such as tertiary amines, imidazoles, and quaternary ammonium salts as needed. Examples of hardening accelerators include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-phenyl Imidazolium trimellitate. These can be used alone or in combination of two or more.

接著劑亦可視需要進一步含有無機填料。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、硼酸鋁晶須、氮化硼、結晶質二氧化矽、非晶質二氧化矽等。該些可單獨使用一種或將兩種以上組合使用。The adhesive may further contain inorganic fillers as needed. 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, etc. These can be used alone or in combination of two or more.

接著劑層30形成於光硬化性黏著劑層20上。作為在光硬化性黏著劑層20上形成接著劑層30的方法,例如可舉出如下方法,即,調製接著劑層形成用清漆、並將該清漆塗佈在經脫模處理的膜上,形成接著劑層30,將得到的接著劑層30轉印到光硬化性黏著劑層20上。接著劑層形成用清漆含有環氧樹脂、環氧樹脂硬化劑及具有環氧基的(甲基)丙烯酸共聚物和有機溶劑。有機溶劑可與光硬化性黏著劑層形成用清漆中所使用的有機溶劑中所例示的有機溶劑相同。The adhesive layer 30 is formed on the photocurable adhesive layer 20. As a method of forming the adhesive layer 30 on the photocurable adhesive layer 20, for example, a method of preparing a varnish for forming an adhesive layer and applying the varnish on a film that has undergone a mold release treatment may be mentioned. The adhesive layer 30 is formed, and the obtained adhesive layer 30 is transferred onto the photocurable adhesive layer 20. The varnish for forming an adhesive layer contains an epoxy resin, an epoxy resin curing agent, a (meth)acrylic copolymer having an epoxy group, and an organic solvent. The organic solvent may be the same as the organic solvent exemplified in the organic solvent used in the varnish for forming a photocurable adhesive layer.

接著劑層30的厚度例如可以是1 μm~300 μm、5 μm~150 μm、或10 μm~100 μm。The thickness of the adhesive layer 30 may be, for example, 1 μm to 300 μm, 5 μm to 150 μm, or 10 μm to 100 μm.

[拉絲的影響因素] 拉絲可因接著劑層與光硬化性黏著劑層的硬化物的界面處的相互作用而產生。因此,作為拉絲現象的影響因素之一,列舉了交聯劑的種類及含量。例如,如果減少交聯劑的含量,有拉絲痕跡的痕跡數增加、拉絲痕跡的痕跡寬度亦變大的傾向。因此,藉由調整交聯劑的種類及含量,可控制拉絲痕跡數及痕跡寬度。另外,作為光硬化性黏著劑的組成以外的拉絲現象的影響因素,舉出塗佈條件。可藉由改變塗佈速度、塗佈溫度、風量等塗佈條件來控制拉絲痕跡數及痕跡寬度。進而,作為拉絲現象的影響因素,可以列舉:切割-黏晶一體型膜的製作時的貼合接著劑層與光硬化性黏著劑層時的條件、接著劑層及光硬化性黏著劑層的表面物性(表面粗糙度、表面自由能等)、具有反應性官能基的(甲基)丙烯酸共聚物的分子量、極性及玻璃轉移點。[Influencing factors of wire drawing] The wire drawing can be produced by the interaction between the adhesive layer and the hardened object of the light-curable adhesive layer. Therefore, as one of the influencing factors of the wire drawing phenomenon, the type and content of the crosslinking agent are listed. For example, if the content of the crosslinking agent is reduced, the number of wire drawing traces will increase and the width of the wire drawing traces will also increase. Therefore, by adjusting the type and content of the crosslinking agent, the number of wire drawing traces and the width of traces can be controlled. In addition, as an influence factor of the wire drawing phenomenon other than the composition of the photocurable adhesive, coating conditions are mentioned. The number of drawing traces and trace width can be controlled by changing coating conditions such as coating speed, coating temperature, and air volume. Furthermore, as the influencing factor of the wire drawing phenomenon, there can be mentioned: the conditions for bonding the adhesive layer and the photocurable adhesive layer during the production of the dicing-bonding integrated film, and the conditions of the adhesive layer and the photocurable adhesive layer Surface physical properties (surface roughness, surface free energy, etc.), molecular weight, polarity, and glass transition point of (meth)acrylic copolymers with reactive functional groups.

<第一步驟> 在本步驟中,首先,準備依次積層有基材層、包含作為評價對象的光硬化性黏著劑的光硬化性黏著劑層、以及接著劑層而得的評價用切割-黏晶一體型膜。<First step> In this step, first, a dicing-bonding integrated film for evaluation in which a substrate layer, a photocurable adhesive layer containing a photocurable adhesive as an evaluation target, and an adhesive layer are sequentially laminated is prepared.

在評價用切割-黏晶一體型膜中,基材層、光硬化性黏著劑層及接著劑層的種類等沒有特別限制,可使用任意選擇的切割-黏晶一體型膜。包含作為評價對象的光硬化性黏著劑的光硬化性黏著劑的厚度例如可為10 μm。接著劑層的厚度例如可以是10 μm。In the dicing-bonding integrated film for evaluation, the types of the substrate layer, the photocurable adhesive layer, and the adhesive layer are not particularly limited, and any selected dicing-bonding integrated film can be used. The thickness of the photocurable adhesive containing the photocurable adhesive as the evaluation target may be, for example, 10 μm. The thickness of the adhesive layer may be 10 μm, for example.

接著,在下述照射條件下對光硬化性黏著劑層照射紫外線,使光硬化性黏著劑硬化,形成光硬化性黏著劑層的硬化物(包含光硬化性黏著劑的硬化物的層)。紫外線的光源可根據使用的光聚合起始劑的種類適當選擇最合適的光源。紫外線的光源沒有特別限定,但是可以是選自由低壓水銀燈、遠紫外線燈、準分子紫外線燈、高壓水銀燈及金屬鹵化物燈(metal halide lamp)所組成的群組中的一種。其中,紫外線的光源較佳為中心波長為365 nm的高壓水銀燈。另外,在紫外線的照射中,為了減少光源所產生的熱的影響,亦可併用冷鏡等。Next, the photocurable adhesive layer was irradiated with ultraviolet rays under the following irradiation conditions to cure the photocurable adhesive to form a cured product of the photocurable adhesive layer (layer containing a cured product of the photocurable adhesive). The light source of ultraviolet rays can be appropriately selected according to the kind of photopolymerization initiator used. The light source of ultraviolet light is not particularly limited, but may be one selected from the group consisting of a low-pressure mercury lamp, a far ultraviolet lamp, an excimer ultraviolet lamp, a high-pressure mercury lamp, and a metal halide lamp. Among them, the ultraviolet light source is preferably a high-pressure mercury lamp with a center wavelength of 365 nm. In addition, in order to reduce the influence of heat generated by the light source in the irradiation of ultraviolet rays, a cold mirror or the like may be used in combination.

(照射條件) 照射強度:70 mW/cm2 累計光量:150 mJ/cm2 (Irradiation conditions) Irradiation intensity: 70 mW/cm 2 Cumulative light quantity: 150 mJ/cm 2

紫外線照射條件中的照射溫度可為60℃以下或40℃以下。The irradiation temperature in the ultraviolet irradiation conditions may be 60°C or lower or 40°C or lower.

最後,測定在下述剝離條件下剝離接著劑層與光硬化性黏著劑層的硬化物時的剝離力(低角剝離強度)。剝離接著劑層與光硬化性黏著劑層的硬化物時,較佳為藉由使用可調整剝離角度的剝離強度測定裝置,在接著劑層上貼附黏著帶、支撐帶等並拉伸該些帶來進行。Finally, the peeling force (low angle peel strength) when peeling the cured product of the adhesive layer and the photocurable adhesive layer under the following peeling conditions was measured. When peeling the cured product of the adhesive layer and the photocurable adhesive layer, it is preferable to attach an adhesive tape, a support tape, etc. on the adhesive layer by using a peel strength measuring device that can adjust the peeling angle, and stretch the Bring in.

(剝離條件) 溫度:25±5℃ 濕度:55±10% 剝離角度:30° 剝離速度:600 mm/分鐘(Peeling conditions) Temperature: 25±5℃ Humidity: 55±10% Peel angle: 30° Peeling speed: 600 mm/min

再者,剝離角度越低,越有能夠排除剝離力下的基材層的影響的傾向,但是不足15°時難以測定。因此,30°適合作為低角剝離強度的試驗條件。Furthermore, the lower the peeling angle, the more likely the influence of the base layer under the peeling force can be excluded, but it is difficult to measure when it is less than 15°. Therefore, 30° is suitable as a test condition for low-angle peel strength.

<第二步驟> 在本步驟中,首先,準備依次積層有基材層、包含作為評價對象的光硬化性黏著劑的光硬化性黏著劑層、以及接著劑層而得的評價用切割-黏晶一體型膜。第二步驟的評價用切割-黏晶一體型膜可與第一步驟的評價用切割-黏晶一體型膜相同,但使用未進行第一步驟的剝離力的測定的膜。<The second step> In this step, first, a dicing-bonding integrated film for evaluation in which a substrate layer, a photocurable adhesive layer containing a photocurable adhesive as an evaluation target, and an adhesive layer are sequentially laminated is prepared. The dicing-bonding integrated film for evaluation in the second step may be the same as the dicing-bonding integrated film for evaluation in the first step, but a film that has not been subjected to the measurement of the peeling force in the first step is used.

接著,在下述加熱冷卻條件下處理評價用切割-黏晶一體型膜的光硬化性黏著劑層。未在加熱冷卻條件下處理光硬化性黏著劑層時,光硬化性黏著劑層與接著劑層的密接性可能不充分,剝離接著劑層與光硬化性黏著劑層的硬化物時,有難以觀察到拉絲痕跡的傾向。下述加熱冷卻條件設想為半導體裝置的晶圓層壓步驟,具有更容易觀察拉絲痕跡的傾向。加熱冷卻條件下的加熱處理較佳為使用加熱器等自基材層側進行。再者,基材層較佳為使用在加熱處理(65℃、15分鐘)中不會發生褶皺、鬆弛等變形的基材層。在加熱處理中,為了使評價用切割-黏晶一體型膜不彎曲,較佳為一邊用耐加熱的布等進行抑制一邊進行加熱。此時的表面壓力可以是0.1 g/cm2 左右。如果表面壓力過高,則光硬化性黏著劑層與接著劑層會過度密接,有可能過剩地形成拉絲痕跡。為了防止光硬化性黏著劑層的硬化,較佳為一邊遮光一邊進行。Next, the photocurable adhesive layer of the dicing-bonding integrated film for evaluation was processed under the following heating and cooling conditions. If the photocurable adhesive layer is not processed under heating and cooling conditions, the adhesion between the photocurable adhesive layer and the adhesive layer may be insufficient, and it may be difficult to peel off the cured product of the adhesive layer and the photocurable adhesive layer. A tendency to draw traces is observed. The following heating and cooling conditions are assumed to be a wafer lamination step of a semiconductor device, which tends to be easier to observe the traces of wire drawing. The heat treatment under heating and cooling conditions is preferably performed from the side of the base material layer using a heater or the like. In addition, it is preferable to use a base material layer that does not undergo deformation such as wrinkles or slack during heat treatment (65° C., 15 minutes). In the heat treatment, in order to prevent the dicing-bonding integrated film for evaluation from bending, it is preferable to heat it while suppressing it with a heat-resistant cloth or the like. The surface pressure at this time may be about 0.1 g/cm 2 . If the surface pressure is too high, the light-curing adhesive layer and the adhesive layer will be in excessive close contact, and there is a possibility of excessive drawing marks. In order to prevent the hardening of the photocurable adhesive layer, it is preferably performed while shielding light.

(加熱冷卻條件) 加熱處理:65℃、15分鐘 冷卻處理:空冷至25±5℃(Heating and cooling conditions) Heat treatment: 65°C, 15 minutes Cooling treatment: air cooling to 25±5℃

接著,對光硬化性黏著劑層以與第一步驟同樣的照射條件照射紫外線,形成光硬化性黏著劑層的硬化物,在與第一步驟同樣的剝離條件下拉伸接著劑層,使接著劑層與光硬化性黏著劑層的硬化物剝離。將具備接著劑層被剝離後的光硬化性黏著劑層的硬化物的基材層作為測量樣品回收。此時,以不污染接著劑層被剝離後的光硬化性黏著劑層的硬化物的方式進行回收。另外,較佳為將具備接著劑層被剝離後的光硬化性黏著劑層的硬化物的基材層切成5 mm×5 mm的尺寸來作為測量樣品。Next, the photo-curable adhesive layer is irradiated with ultraviolet rays under the same irradiation conditions as in the first step to form a cured product of the photo-curable adhesive layer, and the adhesive layer is stretched under the same peeling conditions as in the first step. The cured product of the agent layer and the photocurable adhesive layer is peeled off. The base material layer provided with the cured product of the photocurable adhesive layer after the adhesive layer was peeled off was collected as a measurement sample. At this time, recovery is performed so as not to contaminate the cured product of the photocurable adhesive layer after the adhesive layer is peeled off. In addition, it is preferable to cut the base material layer including the cured product of the photocurable adhesive layer after the adhesive layer is peeled into a size of 5 mm×5 mm as a measurement sample.

最後,利用掃描型探針顯微鏡觀察接著劑層被剝離後的光硬化性黏著劑層的硬化物的表面,測量該表面上的拉絲痕跡的痕跡數和痕跡寬度。自避免靜電影響的觀點出發,測量樣品向掃描型探針顯微鏡上的固定較佳為使用掃描型電子顯微鏡觀察等中使用的通常的碳雙面膠帶。另外,自避免靜電影響的觀點出發,利用掃描型探針顯微鏡的觀察較佳為在固定半天(12小時)以上的狀態下靜置除電後進行,或者使用除靜電器等適當地除去靜電後進行。Finally, the surface of the cured product of the photocurable adhesive layer after the adhesive layer was peeled was observed with a scanning probe microscope, and the number and width of the wire drawing traces on the surface were measured. From the viewpoint of avoiding the influence of static electricity, it is preferable to fix the measurement sample to the scanning probe microscope by using a normal carbon double-sided tape used in scanning electron microscope observation. In addition, from the viewpoint of avoiding the influence of static electricity, observation with a scanning probe microscope is preferably carried out after static electricity has been statically removed for more than half a day (12 hours), or after static electricity has been properly removed using a static electricity eliminator, etc. .

較佳為在掃描型探針顯微鏡的探針上設置有最適於測量接著劑層被剝離後的光硬化性黏著劑層的硬化物的表面的彈簧常數低的懸臂。另外,利用掃描型探針顯微鏡的觀察較佳為在動態力模式(Dynamic Force Mode,DFM)下進行。Preferably, a cantilever with a low spring constant is provided on the probe of the scanning probe microscope, which is most suitable for measuring the surface of the hardened object of the photocurable adhesive layer after the adhesive layer is peeled off. In addition, the observation with a scanning probe microscope is preferably performed in a dynamic force mode (Dynamic Force Mode, DFM).

關於拉絲痕跡,在光硬化性黏著劑層的硬化物的表面以痕跡(突起)的形式被觀測到,可取得光硬化性黏著劑層的硬化物的表面的相位圖像的資料,將所述相位圖像中硬度明顯與周圍不同的部位作為拉絲痕跡。拉絲痕跡的痕跡數是在相位圖像中硬度明顯與周圍不同的部位的數量。With regard to wire drawing traces, traces (protrusions) are observed on the surface of the cured product of the photocurable adhesive layer, and the phase image data of the surface of the cured product of the photocurable adhesive layer can be obtained. In the phase image, the parts whose hardness is obviously different from the surroundings are regarded as drawing traces. The number of traces of wire drawing is the number of parts whose hardness is obviously different from the surroundings in the phase image.

拉絲痕跡的痕跡寬度可如以下方式求出。首先,使用掃描型探針顯微鏡,取得在相位圖像中包含硬度明顯與周圍不同的部位的光硬化性黏著劑層的硬化物的表面的形狀圖像分佈及相位圖像分佈。圖2的(a)及圖2的(b)是表示光硬化性黏著劑層的硬化物的表面的形狀圖像分佈及相位圖像分佈的一個例子的圖,圖2的(a)是形狀圖像分佈,圖2的(b)是相位圖像分佈。在圖2的(a)的形狀圖像分佈中,拉絲痕跡觀測到呈隆起的部分為向上凸出的曲線的形式,以最淡的顏色(在黑白圖像的情況下,例如白色)來表示。另一方面,在相位圖像分佈中,相位差小於周圍意味著比周圍硬。在圖2的(b)的相位圖像分佈中,拉絲痕跡由於光硬化黏著劑層被延伸到極限,因此以與周圍相比,與周圍的相位差為50%以下的部位的形式被觀測到,用最濃的顏色(在黑白圖像的情況下,例如黑色)表示。如此,不僅從形狀圖像分佈還從相位圖像分佈觀察拉絲痕跡。接著,根據所取得的圖2的(a)的形狀圖像分佈,使用市售的圖像處理軟體(掃描探針顯微鏡附屬的圖像處理軟體等),對於作為測定對象的全部拉絲痕跡,分別輸出各拉絲痕跡的痕跡寬度最大的剖面線的剖面分佈。圖3的(a)及圖3的(b)是表示光硬化性黏著劑層的硬化物的表面的剖面分佈的一個例子的圖,圖3的(a)是形狀圖像分佈,圖3的(b)是圖3的(a)中的拉絲痕跡X的iii-iii線的剖面分佈。圖3的(b)是觀測到的拉絲痕跡的兩端的高度實質上沒有差異(例如1 nm以下)時的剖面分佈。在此種剖面分佈中,拉絲痕跡X的兩端(極小值)彼此的寬度Wx可設為拉絲痕跡X的痕跡寬度。另一方面,圖4的(a)及圖4的(b)是表示光硬化性黏著劑層的硬化物的表面的剖面分佈的一個例子的圖,圖4的(a)是形狀圖像分佈,圖4的(b)是圖4的(a)中的拉絲痕跡Y的iv-iv線的剖面分佈。圖4的(b)是觀測到的拉絲痕跡的兩端的高度存在差異(例如超過1 nm)時的剖面分佈。在此種情況下,可將自拉絲痕跡Y的頂點起高度近的一端(極小值)設為基準高度Hy,將該基準高度Hy處的寬度Wy設為拉絲痕跡Y的痕跡寬度。The trace width of the drawing trace can be obtained as follows. First, a scanning probe microscope is used to acquire the shape image distribution and phase image distribution of the surface of the hardened object including the photocurable adhesive layer whose hardness is significantly different from the surrounding area in the phase image. 2(a) and 2(b) are diagrams showing an example of the shape image distribution and the phase image distribution on the surface of the cured product of the photocurable adhesive layer, and FIG. 2(a) is the shape Image distribution, Figure 2(b) is the phase image distribution. In the shape image distribution of Figure 2(a), the part where the drawing traces are observed to be raised is in the form of an upwardly convex curve, expressed in the lightest color (in the case of a black and white image, for example, white) . On the other hand, in the phase image distribution, a phase difference smaller than the surrounding means harder than the surrounding. In the phase image distribution of Fig. 2(b), the wire drawing traces are observed as parts with a phase difference of 50% or less from the surroundings because the photo-curable adhesive layer is extended to the limit. , Expressed with the strongest color (in the case of black and white images, such as black). In this way, not only the shape image distribution but also the phase image distribution can observe the drawing traces. Next, based on the acquired shape image distribution of Figure 2(a), using commercially available image processing software (image processing software attached to the scanning probe microscope, etc.), all the wire drawing traces that are the measurement objects are separately The cross-sectional distribution of the hatch line with the largest trace width of each drawing trace is output. Figure 3 (a) and Figure 3 (b) are diagrams showing an example of the cross-sectional distribution of the surface of the cured product of the photocurable adhesive layer, Figure 3 (a) is the shape image distribution, and Figure 3 (B) is the cross-sectional distribution of the line iii-iii of the drawing trace X in FIG. 3(a). Fig. 3(b) is the cross-sectional distribution when there is substantially no difference (for example, 1 nm or less) in the height of the two ends of the wire drawing trace observed. In such a cross-sectional distribution, the width Wx between the two ends (minimum value) of the drawing trace X can be set as the trace width of the drawing trace X. On the other hand, FIGS. 4(a) and 4(b) are diagrams showing an example of the cross-sectional distribution of the surface of the cured product of the photocurable adhesive layer, and FIG. 4(a) is the shape image distribution , Figure 4(b) is the cross-sectional distribution of the iv-iv line of the drawing trace Y in Figure 4(a). Fig. 4(b) is the cross-sectional distribution when there is a difference (for example, more than 1 nm) between the heights of the two ends of the wire drawing traces. In this case, the end (minimum value) of the closest height from the apex of the wire drawing trace Y may be set as the reference height Hy, and the width Wy at the reference height Hy may be set as the trace width of the drawing trace Y.

<第三步驟> 在本步驟中,基於剝離力以及拉絲痕跡的痕跡數、及痕跡寬度,判定光硬化性黏著劑是否良好。作為評價基準的剝離力以及拉絲痕跡的痕跡數、及痕跡寬度的基準可根據半導體晶圓的厚度等適宜設定。<The third step> In this step, it is determined whether the photocurable adhesive is good or not based on the peeling force, the number of traces of the wire drawing, and the width of the traces. The peeling force, the number of wire drawing marks, and the mark width as evaluation criteria can be appropriately set according to the thickness of the semiconductor wafer.

第三步驟可以是根據剝離力以及拉絲痕跡的痕跡數、及痕跡寬度是否滿足下述條件(a)及下述條件(b)來判定光硬化性黏著劑是否良好的步驟。關於具備包含滿足下述條件(a)及下述條件(b)的光硬化性黏著劑的光硬化性黏著劑層的切割-黏晶一體型膜,可較佳地用於厚度比較薄(例如35 μm以下)的半導體晶圓所應用的切割製程(例如隱形切割等)。The third step may be a step of judging whether the photocurable adhesive is good or not based on whether the peeling force, the number of traces of wire drawing, and the width of the trace satisfy the following condition (a) and the following condition (b). Regarding a dicing-bonding integrated film with a photocurable adhesive layer containing a photocurable adhesive that satisfies the following conditions (a) and (b), it can be preferably used for a thinner thickness (for example The cutting process (such as stealth cutting, etc.) applied to semiconductor wafers below 35 μm.

條件(a):剝離力為0.70 N/25 mm以下。 條件(b):在剝離接著劑層後的光硬化性黏著劑層的硬化物的表面存在拉絲痕跡的痕跡數為15以上的25 μm×25 μm的區域(有時稱為「特定區域」),區域內的拉絲痕跡的痕跡寬度的中位數為120 nm~200 nm。Condition (a): The peel force is 0.70 N/25 mm or less. Condition (b): There is a 25 μm×25 μm area (sometimes referred to as "specific area") with 15 or more traces on the surface of the cured product of the photocurable adhesive layer after the adhesive layer is peeled off. , The median of the trace width of the drawing traces in the area is 120 nm to 200 nm.

將滿足條件(a)的光硬化性黏著劑適用於切割-黏晶一體型膜時,有拾取的成功率進一步提高的傾向。條件(a)中的剝離力可為0.65 N/25 mm以下或0.63 N/25 mm以下。條件(a)中的剝離力的下限值沒有特別限制,但可為0.10 N/25 mm以上。When a photocurable adhesive that satisfies the condition (a) is applied to a dicing-bonding integrated film, the picking success rate tends to be further improved. The peel force in condition (a) may be 0.65 N/25 mm or less or 0.63 N/25 mm or less. The lower limit of the peel force in the condition (a) is not particularly limited, but may be 0.10 N/25 mm or more.

將滿足條件(b)的光硬化性黏著劑適用於切割-黏晶一體型膜時,存在拾取的剝離時間變得更短的傾向。When a photocurable adhesive that satisfies the condition (b) is applied to a dicing-bonding integrated film, the peeling time of pick-up tends to be shorter.

藉由在接著劑層被剝離後的光硬化性黏著劑層的硬化物的表面存在特定區域,應力傳播性變得良好,剝離速度有提高的傾向。存在於特定區域內的拉絲痕跡的痕跡數可以是15以上或20以上,亦可以是70以下、60以下或50以下。關於剝離速度,特定區域的存在與存在於該特定區域的拉絲痕跡的痕跡寬度雙方都有貢獻。在特定區域,拉絲痕跡的痕跡數為15以上時,應力傳播性高、有加快剝離速度的傾向。在特定區域,拉絲痕跡的痕跡數為70以下時,有能夠抑制剝離力過度增大的傾向。Since a specific area exists on the surface of the cured product of the photocurable adhesive layer after the adhesive layer is peeled off, the stress propagation property becomes better, and the peeling speed tends to increase. The number of wire drawing traces existing in a specific area may be 15 or more or 20 or more, or it may be 70 or less, 60 or less or 50 or less. Regarding the peeling speed, both the existence of a specific area and the width of the trace of the drawing trace existing in the specific area contribute. In a specific area, when the number of wire drawing traces is 15 or more, the stress propagation is high and the peeling speed tends to be increased. In a specific area, when the number of traces of wire drawing is 70 or less, there is a tendency that excessive increase in peeling force can be suppressed.

於在接著劑層被剝離後的光硬化性黏著劑層的硬化物的表面存在拉絲痕跡的痕跡數為15以上的特定區域的情況下,計算該些特定區域中存在的拉絲痕跡的痕跡寬度的中位數。此處,中位數是指將有限個資料按從小到大的順序排列時位於中央的值,在資料為偶數個的情況下,是指接近中央的值的平均值。例如,在拉絲痕跡的痕跡數為15的情況下,按照拉絲痕跡的痕跡寬度從小到大的順序排列時的第8個拉絲痕跡的痕跡寬度為中位數,在拉絲痕跡的痕跡數為16的情況下,按照拉絲痕跡的痕跡寬度從小到大的順序排列時的第8個拉絲痕跡的痕跡寬度與第9個拉絲痕跡的痕跡寬度的平均值為中位數。存在於特定區域的拉絲痕跡的痕跡寬度的中位數可為130 nm以上或150 nm以上,亦可為190 nm以下或180 nm以下。特定區域存在的拉絲痕跡的痕跡寬度的中位數為120 nm以上時,拉絲的斷裂衝擊容易傳播,剝離速度有提高的傾向。特定區域存在的拉絲痕跡的痕跡寬度的中位數為200 nm以下時,容易引起拉絲的斷裂,剝離速度有提高的傾向。In the case where there are specific areas where the number of wire drawing marks is 15 or more on the surface of the cured product of the photocurable adhesive layer after the adhesive layer is peeled off, calculate the width of the wire drawing marks existing in these specific areas median. Here, the median refers to the value located in the center when a limited number of data are arranged in ascending order, and when the data is an even number, it refers to the average value of the values close to the center. For example, when the number of wire drawing traces is 15, the 8th wire drawing trace width is the median when the wire drawing traces are arranged in ascending order, and the number of wire drawing traces is 16. In this case, the average value of the trace width of the eighth drawing trace and the trace width of the ninth drawing trace when the trace widths of the drawing traces are arranged in ascending order is the median. The median of the trace width of the wire drawing trace existing in a specific area may be 130 nm or more or 150 nm or more, and may also be 190 nm or less or 180 nm or less. When the median width of the wire drawing traces in a specific area is 120 nm or more, the breaking impact of the wire drawing tends to propagate, and the peeling speed tends to increase. When the median width of the wire drawing traces in a specific area is 200 nm or less, the wire drawing tends to break and the peeling speed tends to increase.

[切割-黏晶一體型膜的製造方法] 一個實施方式的切割-黏晶一體型膜的製造方法包括:在基材層上形成包含藉由所述光硬化性黏著劑的評價方法判定為良好的光硬化性黏著劑的光硬化性黏著劑層的步驟;以及在光硬化性黏著劑層上形成接著劑層的步驟。基材層以及接著劑層可與所述光硬化性黏著劑的評價方法中例示者相同。光硬化性黏著劑層的形成方法以及接著劑層的形成方法亦可與所述光硬化性黏著劑的評價方法中例示的方法相同。[Manufacturing method of cutting-bonding integrated film] The manufacturing method of the dicing-bonding integrated film of one embodiment includes forming a photocurable adhesive including a photocurable adhesive judged to be good by the evaluation method of the photocurable adhesive on a substrate layer And forming an adhesive layer on the photocurable adhesive layer. The substrate layer and the adhesive layer may be the same as those exemplified in the evaluation method of the photocurable adhesive. The method of forming the photocurable adhesive layer and the method of forming the adhesive layer may be the same as the method exemplified in the evaluation method of the photocurable adhesive.

[切割-黏晶一體型膜] 一個實施方式的切割-黏晶一體型膜依次具備基材層、包含藉由所述光硬化性黏著劑的評價方法被判定為良好的光硬化性黏著劑的光硬化性黏著劑層、接著劑層。基材層以及接著劑層可與所述光硬化性黏著劑的評價方法中所例示者相同。[Cutting-bonding integrated film] The dicing-bonding integrated film of one embodiment sequentially includes a base layer, a photocurable adhesive layer including a photocurable adhesive judged to be good by the photocurable adhesive evaluation method, and an adhesive Floor. The base layer and the adhesive layer may be the same as those exemplified in the evaluation method of the photocurable adhesive.

[半導體裝置(半導體封裝)的製造方法] 圖5的(a)~圖5的(e)及圖6的(f)~圖6的(i)是用於說明半導體裝置的製造方法的一個實施方式的示意剖面圖。本實施方式的半導體裝置的製造方法包括:將藉由所述製造方法得到的切割-黏晶一體型膜1的接著劑層30貼付於半導體晶圓W2的步驟(晶圓層壓步驟);將半導體晶圓W2、接著劑層30、及光硬化性黏著劑層20單片化的步驟(切割步驟);對光硬化性黏著劑層20照射紫外線的步驟(紫外線照射步驟);自基材層10拾取附著有接著劑層30a的半導體元件(帶接著劑層的半導體元件50)的步驟(拾取步驟)、經由接著劑層30a將帶接著劑層的半導體元件50接著在半導體元件搭載用支撐基板60上的步驟(半導體元件接著步驟)。[Method of Manufacturing Semiconductor Device (Semiconductor Package)] FIGS. 5( a) to 5 (e) and FIGS. 6 (f) to 6 (i) are schematic cross-sectional views for explaining an embodiment of a method of manufacturing a semiconductor device. The manufacturing method of the semiconductor device of this embodiment includes: attaching the adhesive layer 30 of the dicing-bonding integrated film 1 obtained by the manufacturing method to the semiconductor wafer W2 (wafer lamination step); The step of singulating the semiconductor wafer W2, the adhesive layer 30, and the photocurable adhesive layer 20 (dicing step); the step of irradiating the photocurable adhesive layer 20 with ultraviolet rays (ultraviolet irradiation step); from the base material layer 10. The step of picking up the semiconductor element (semiconductor element 50 with an adhesive layer) to which the adhesive layer 30a is attached (pickup step), and attaching the semiconductor element 50 with the adhesive layer via the adhesive layer 30a to the semiconductor element mounting support substrate Step on 60 (semiconductor device next step).

切割步驟中的切割沒有特別限制,例如可以舉出刀片切割(blade dicing)、雷射光切割、隱形切割等。在半導體晶圓W2的厚度為35 μm以下的情況下,切割可以應用隱形切割。以下,對作為切割主要使用隱形切割的形態進行詳細說明。The cutting in the cutting step is not particularly limited, and examples thereof include blade dicing, laser cutting, and stealth cutting. In the case where the thickness of the semiconductor wafer W2 is 35 μm or less, stealth dicing can be applied to the dicing. Hereinafter, a form in which stealth cutting is mainly used as cutting will be described in detail.

<改質層形成步驟> 在切割應用了隱形切割的情況下,半導體裝置的製造方法可在晶圓層壓步驟之前具備改質層形成步驟。<Formation steps of modified layer> In the case where stealth dicing is applied to the dicing, the manufacturing method of the semiconductor device may include a reforming layer forming step before the wafer lamination step.

首先,準備厚度H1的半導體晶圓W1。形成改質層的半導體晶圓W1的厚度H1可超過35 μm。接著,在半導體晶圓W1的一個主面上貼附保護膜2(參照圖5的(a))。貼附有保護膜2的面較佳為半導體晶圓W1的電路面。保護膜2可以是在半導體晶圓的背面研削(背面研磨)中使用的背面研磨帶。接著,對半導體晶圓W1內部照射雷射光而形成改質層4(參照圖5的(b)),對半導體晶圓W1的與貼附有保護膜2的面相反的一側(背面側)進行背面研磨(背面研削)及拋光(研磨),藉此製作具有改質層4的半導體晶圓W2(參照圖5的(c))。得到的半導體晶圓W2的厚度H2可為35 μm以下。First, a semiconductor wafer W1 with a thickness H1 is prepared. The thickness H1 of the semiconductor wafer W1 forming the modified layer may exceed 35 μm. Next, the protective film 2 is attached to one main surface of the semiconductor wafer W1 (see FIG. 5(a)). The surface on which the protective film 2 is attached is preferably the circuit surface of the semiconductor wafer W1. The protective film 2 may be a back grinding tape used for back grinding (back grinding) of a semiconductor wafer. Next, laser light is irradiated to the inside of the semiconductor wafer W1 to form the modified layer 4 (see FIG. 5(b)), on the side (rear side) of the semiconductor wafer W1 opposite to the surface on which the protective film 2 is attached By performing back grinding (back grinding) and polishing (grinding), a semiconductor wafer W2 having the modified layer 4 is produced (see FIG. 5(c)). The thickness H2 of the obtained semiconductor wafer W2 may be 35 μm or less.

<晶圓層壓步驟> 接著,將切割-黏晶一體型膜1的接著劑層30配置在規定的裝置。接著,在半導體晶圓W2的主面Ws,經由接著劑層30貼附切割-黏晶一體型膜1(參照圖5的(d)),剝離半導體晶圓W2的保護膜2(參照圖5的(e))。<Wafer lamination steps> Next, the adhesive layer 30 of the integrated dicing-bonding film 1 is arranged in a predetermined device. Next, on the main surface Ws of the semiconductor wafer W2, the dicing-bonding integrated film 1 is attached via the adhesive layer 30 (see FIG. 5(d)), and the protective film 2 of the semiconductor wafer W2 is peeled off (see FIG. 5 (E)).

<切割步驟> 接著,藉由切割至少將半導體晶圓W2及接著劑層30單片化(參照圖6的(f))。在切割應用了隱形切割的情況下,可藉由進行冷擴展以及熱收縮來進行單片化。<Cutting steps> Next, at least the semiconductor wafer W2 and the adhesive layer 30 are singulated by dicing (refer to FIG. 6(f)). When invisible cutting is used for cutting, it can be singulated by cold expansion and heat shrinkage.

<紫外線照射步驟> 接著,藉由對光硬化性黏著劑層20照射紫外線,使光硬化性黏著劑層20中的光硬化性黏著劑硬化,形成光硬化性黏著劑層的硬化物(包含光硬化性黏著劑的硬化物的層)(參照圖6的(g))。因此,可降低光硬化性黏著劑層20與接著劑層30之間的黏著力。在紫外線照射中,較佳為使用波長200 nm~400 nm的紫外線。紫外線照射條件較佳為調整成照度:30 mW/cm2 ~240 mW/cm2 且照射量為200 mJ/cm2 ~500 mJ/cm2<Ultraviolet irradiation step> Next, by irradiating the photocurable adhesive layer 20 with ultraviolet rays, the photocurable adhesive in the photocurable adhesive layer 20 is cured to form a cured product of the photocurable adhesive layer (including light The layer of the cured product of the curable adhesive) (see Fig. 6(g)). Therefore, the adhesive force between the photocurable adhesive layer 20 and the adhesive layer 30 can be reduced. In the ultraviolet irradiation, it is preferable to use ultraviolet rays having a wavelength of 200 nm to 400 nm. The ultraviolet irradiation conditions are preferably adjusted to an illuminance of 30 mW/cm 2 to 240 mW/cm 2 and an irradiation amount of 200 mJ/cm 2 to 500 mJ/cm 2 .

<拾取步驟> 接著,使基材層10擴展,藉此使藉由切斷而獲得的帶接著劑層的半導體元件50彼此分開,並且利用抽吸夾頭44抽吸自基材層10側由頂針42頂起的帶接著劑層的半導體元件50,並自光硬化性黏著劑層的硬化物20ac拾取(參照圖6的(h))。再者,帶接著劑層的半導體元件50具有半導體元件Wa和接著劑層30a。半導體元件Wa是半導體晶圓W2藉由切割而被分割而得的元件,接著劑層30a是接著劑層30藉由切割而被分割而得者。光硬化性黏著劑層的硬化物20ac是光硬化性黏著劑層的硬化物藉由切割而被分割而得者。光硬化性黏著劑層的硬化物20ac在拾取帶接著劑層的半導體元件50時可殘留在基材層10上。在拾取步驟中,不一定需要擴張,但藉由擴張,能夠進一步提高拾取性。<Pick up steps> Next, the base layer 10 is expanded, thereby separating the semiconductor elements 50 with the adhesive layer obtained by cutting from each other, and is sucked from the base layer 10 side by the ejector pin 42 by the suction chuck 44 The semiconductor element 50 with an adhesive layer is picked up from the cured product 20ac of the photocurable adhesive layer (refer to FIG. 6(h)). Furthermore, the semiconductor element 50 with an adhesive layer has a semiconductor element Wa and an adhesive layer 30a. The semiconductor element Wa is an element obtained by dividing the semiconductor wafer W2 by dicing, and the adhesive layer 30a is an element obtained by dividing the adhesive layer 30 by dicing. The cured product 20ac of the photocurable adhesive layer is obtained by dividing the cured product of the photocurable adhesive layer by cutting. The cured product 20ac of the photocurable adhesive layer may remain on the base layer 10 when the semiconductor element 50 with the adhesive layer is picked up. In the picking step, expansion is not necessarily required, but the expansion can further improve the picking performance.

利用頂針42的頂起量可適當設定。進而,自對於極薄晶圓亦確保充分的拾取性的觀點出發,例如亦可進行2級或3級的拾取。另外,亦可藉由使用抽吸夾頭44的方法以外的方法來進行帶接著劑層的半導體元件50的拾取。The lifting amount of the thimble 42 can be appropriately set. Furthermore, from the viewpoint of ensuring sufficient pick-up properties for ultra-thin wafers, for example, 2-level or 3-level pick-up is also possible. In addition, the semiconductor element 50 with the adhesive layer may be picked up by a method other than the method using the suction chuck 44.

<半導體元件接著步驟> 在拾取帶接著劑層的半導體元件50後,將帶接著劑層的半導體元件50利用熱壓接,經由接著劑層30a而與半導體元件搭載用支撐基板60接著(參照圖6的(i))。可將多個帶接著劑層的半導體元件50接著在半導體元件搭載用支撐基板60上。<Semiconductor device next steps> After picking up the semiconductor element 50 with the adhesive layer, the semiconductor element 50 with the adhesive layer is bonded by thermocompression, and is bonded to the semiconductor element mounting support substrate 60 via the adhesive layer 30a (see FIG. 6(i)) . A plurality of semiconductor elements 50 with adhesive layers can be attached to the support substrate 60 for mounting semiconductor elements.

圖7是示意性示出半導體裝置的一個實施方式的剖面圖。圖7所示的半導體裝置100可藉由如下製造方法來製造,所述製造方法更包括:上述步驟;藉由打線接合線70將半導體元件Wa與半導體元件搭載用支撐基板60電連接的步驟;使用樹脂密封材80將半導體元件Wa樹脂密封在半導體元件搭載用支撐基板60的表面60a上的步驟。在半導體元件搭載用支撐基板60的與表面60a相反的一側的面上,可形成焊球90來用於與外部基板(母板)電連接。 [實施例]FIG. 7 is a cross-sectional view schematically showing an embodiment of a semiconductor device. The semiconductor device 100 shown in FIG. 7 can be manufactured by the following manufacturing method, the manufacturing method further comprising: the above-mentioned steps; the step of electrically connecting the semiconductor element Wa and the semiconductor element mounting support substrate 60 through the wire bonding wire 70; A step of resin-sealing the semiconductor element Wa on the surface 60a of the semiconductor element mounting support substrate 60 using the resin sealing material 80. On the surface of the semiconductor element mounting support substrate 60 opposite to the surface 60 a, solder balls 90 may be formed for electrical connection with an external substrate (mother board). [Example]

以下,藉由實施例更具體地說明本發明,但本發明並不限定於該些實施例。再者,除非另有記載,化合物使用市售試劑。Hereinafter, the present invention will be explained in more detail through examples, but the present invention is not limited to these examples. In addition, unless otherwise stated, commercially available reagents are used for the compound.

[切割-黏晶一體型膜的準備]((甲基)丙烯酸共聚物溶液A~E的製備) 在具備三一馬達(Three-One Motor)、攪拌翼以及氮氣導入管的容量2000 mL的高壓釜中,以表1所示的比例(單位:質量份)加入丙烯酸2-乙基己酯(2EHA)、丙烯酸2-羥基乙酯(HEA)、以及甲基丙烯酸(MAA),進而加入127質量份的乙酸乙酯及0.04質量份的偶氮雙異丁腈。將其攪拌至均勻,以流量500 ml/min實施60分鐘起泡,對系統中的溶存氧進行脫氣。接著,用1小時升溫至78℃,在維持78℃~83℃的狀態下聚合6小時。然後,將反應溶液轉移到具備三一馬達、攪拌翼以及氮氣導入管的容量2000 mL的加壓釜中,在120℃、0.28 MPa條件下加熱4.5小時後,冷卻至室溫(25℃,以下相同)。接著,進一步加入98質量份的乙酸乙酯進行稀釋。向其中添加作為聚合抑制劑的對苯二酚-單甲醚0.05質量份及作為胺基甲酸酯化觸媒的二月桂酸二辛基錫0.02質量份,並加入作為具有能夠鏈聚合的官能基的化合物的2-甲基丙烯醯氧基乙基異氰酸酯(昭和電工股份有限公司製,商品名「卡萊茲(Karenz)MOI」)10質量份,在70℃下反應6小時,冷卻至室溫。然後,以使不揮發成分(固體成分)含量為35質量%的方式加入乙酸乙酯,從而得到具有羥基作為反應性官能基的(甲基)丙烯酸共聚物溶液A~E。[Preparation of cutting-bonding integrated film] (Preparation of (meth)acrylic acid copolymer solutions A~E) In an autoclave with a capacity of 2000 mL equipped with a Three-One Motor, stirring wings, and nitrogen introduction pipe, add 2-ethylhexyl acrylate (2EHA) at the ratio shown in Table 1 (unit: parts by mass) ), 2-hydroxyethyl acrylate (HEA), and methacrylic acid (MAA), and 127 parts by mass of ethyl acetate and 0.04 parts by mass of azobisisobutyronitrile were added. Stir it until it is uniform, and foam it for 60 minutes at a flow rate of 500 ml/min to degas the dissolved oxygen in the system. Then, the temperature was raised to 78°C over 1 hour, and polymerization was carried out for 6 hours while maintaining 78°C to 83°C. Then, the reaction solution was transferred to a 2000 mL autoclave equipped with a Trinity motor, a stirring blade, and a nitrogen introduction tube, heated at 120°C and 0.28 MPa for 4.5 hours, and then cooled to room temperature (25°C, below the same). Then, 98 parts by mass of ethyl acetate was further added for dilution. To this, 0.05 parts by mass of hydroquinone monomethyl ether as a polymerization inhibitor and 0.02 parts by mass of dioctyltin dilaurate as a carbamate catalyst were added, and added as a function capable of chain polymerization 10 parts by mass of 2-methacryloxyethyl isocyanate (manufactured by Showa Denko Co., Ltd., trade name "Karenz MOI") of the compound of the base, reacted at 70°C for 6 hours, and cooled to the room temperature. Then, ethyl acetate was added so that the non-volatile content (solid content) content might be 35% by mass to obtain (meth)acrylic copolymer solutions A to E having a hydroxyl group as a reactive functional group.

按照JIS K0070測定(甲基)丙烯酸共聚物溶液A~E中的(甲基)丙烯酸共聚物的酸值及羥基值。將結果示於表1。另外,將得到的丙烯酸樹脂在60℃下真空乾燥一夜,利用艾里蒙塔(Elementar)公司製全自動元素分析裝置瓦瑞奧(vario)EL對得到的固體成分實施元素分析,自氮含量算出導入的2-甲基丙烯醯氧基乙基異氰酸酯的含量。將結果示於表1。進而,作為GPC裝置使用東曹(Tosoh)股份有限公司製SD-8022/DP-8020/RI-8020、作為管柱使用日立化成股份有限公司製的蓋爾派克(Gelpack) GL-A150-S/GL-A160-S、及作為洗脫液使用四氫呋喃,測定聚苯乙烯換算的重量平均分子量(Mw)。將結果示於表1。The acid value and hydroxyl value of the (meth)acrylic copolymer in the (meth)acrylic copolymer solutions A to E were measured in accordance with JIS K0070. The results are shown in Table 1. In addition, the obtained acrylic resin was vacuum-dried at 60°C overnight, and elemental analysis was performed on the obtained solid content using a full-automatic elemental analyzer made by Elementar Corporation, Vario EL, and the nitrogen content was calculated The content of 2-methacryloxyethyl isocyanate introduced. The results are shown in Table 1. Furthermore, SD-8022/DP-8020/RI-8020 manufactured by Tosoh Co., Ltd. was used as the GPC device, and Gelpack GL-A150-S/ manufactured by Hitachi Chemical Co., Ltd. was used as the column. GL-A160-S and tetrahydrofuran were used as the eluent to measure the weight average molecular weight (Mw) in terms of polystyrene. The results are shown in Table 1.

表1 (甲基)丙烯酸共聚物溶液 A B C D F (甲基)丙烯酸 單體 2EHA 80 78 82 80 75 HEA 18 18 18 20 25 MAA 2 4 0 0 0 具有聚合性官能基的單體 卡萊茲(Karenz)MOI 10 10 10 10 10 酸值(mgKOH/g) 13.0 26.1 0 0 0 羥基值(mgKOH/g) 46.2 46.2 46.2 46.2 46.2 MOI含量(mmol/g) 0.59 0.59 0.59 0.59 0.59 重量平均分子量(Mw) 40萬 30萬 50萬 70萬 30萬 Table 1 (Meth) acrylic copolymer solution A B C D F (Meth) acrylic monomer 2EHA 80 78 82 80 75 HEA 18 18 18 20 25 MAA 2 4 0 0 0 Monomers with polymerizable functional groups Karenz MOI 10 10 10 10 10 Acid value (mgKOH/g) 13.0 26.1 0 0 0 Hydroxyl value (mgKOH/g) 46.2 46.2 46.2 46.2 46.2 MOI content (mmol/g) 0.59 0.59 0.59 0.59 0.59 Weight average molecular weight (Mw) 400000 300000 500000 700 thousand 300000

<製造例1:切割-黏晶一體型膜A的製作>(切割膜的製備) 將以固體成分計為100質量份的作為具有反應性官能基的(甲基)丙烯酸共聚物的所述製備的(甲基)丙烯酸共聚物溶液A、0.5質量份的作為光聚合起始劑的1-羥基環己基苯基酮(汽巴精化(Ciba Specialty Chemicals)股份有限公司製、豔佳固(IRGACURE)184)、以及2質量份的作為交聯劑的多官能異氰酸酯(日本聚胺基甲酸酯工業股份有限公司製、商品名「科羅耐特(Coronate)L」、固體成分75%)混合。相對於該混合物,以使固體成分的總含量達到25質量%的方式加入乙酸乙酯,均勻攪拌10分鐘,得到光硬化性黏著劑層形成用清漆。將所得到光硬化性黏著劑層形成用清漆以乾燥後的光硬化性黏著劑層的厚度為10 μm的方式一邊調整間隙一邊塗佈在單面經脫模處理的寬350 mm、長400 mm、厚38 μm的聚對苯二甲酸乙二酯(PET)膜上,在80℃~100℃下將光硬化性黏著劑層形成用清漆加熱乾燥3分鐘。然後,貼合單面實施了電暈放電處理的聚烯烴製膜(基材層,厚度:90 μm),在40℃、72小時的條件下進行養護,進行交聯處理,藉此得到具備基材層和光硬化性黏著劑層的切割膜。再者,交聯處理使用傅立葉轉換紅外光譜儀(Fourier transform infrared spectrometer,FT-IR)光譜,一邊確認養護的進展一邊進行。<Manufacturing Example 1: Preparation of Die-Bonding Integrated Film A> (Preparation of Dicing Film) The (meth)acrylic copolymer solution A prepared as described above as a (meth)acrylic copolymer having a reactive functional group as a solid content of 100 parts by mass, and 0.5 parts by mass as a photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals Co., Ltd., IRGACURE 184), and 2 parts by mass of polyfunctional isocyanate (Japan polyamino Produced by Formate Industry Co., Ltd., brand name "Coronate L", solid content 75%). With respect to this mixture, ethyl acetate was added so that the total content of solids might reach 25% by mass, and the mixture was uniformly stirred for 10 minutes to obtain a varnish for forming a light-curable adhesive layer. The obtained varnish for forming a photocurable adhesive layer was coated on a single side with a width of 350 mm and a length of 400 mm, which was subjected to mold release treatment, so that the thickness of the photocurable adhesive layer after drying was 10 μm while adjusting the gap. 、On a 38 μm thick polyethylene terephthalate (PET) film, heat and dry the varnish for forming the light-curable adhesive layer at 80°C-100°C for 3 minutes. Then, a polyolefin film (base material layer, thickness: 90 μm) that had been corona-discharged on one side was laminated, cured at 40°C for 72 hours, and crosslinked to obtain a base material. Cutting film of material layer and light-curing adhesive layer. Furthermore, the cross-linking process uses Fourier transform infrared spectrometer (FT-IR) spectroscopy, which is performed while checking the progress of the maintenance.

(黏晶膜的製作) 在55質量份的作為環氧樹脂的YDCN-703(東都化成股份有限公司製、商品名、甲酚酚醛清漆型環氧樹脂、環氧當量210、分子量1200、軟化點80℃),45質量份的作為酚醛樹脂的米萊斯(Milex)XLC-LL(三井化學股份有限公司製、商品名、羥基當量175、吸水率1.8%,350℃下的加熱質量減少率4%)、1.7質量份的作為矽烷偶合劑的NUCA-189(日本尤尼卡(Nippon Unicar)股份有限公司製,商品名,γ-巰基丙基三甲氧基矽烷)及3.2質量份的NUCA-1160(日本尤尼卡(Nippon Unicar)股份有限公司製,商品名,γ-脲基丙基三乙氧基矽烷)、以及32質量份的作為填料的艾羅技(AEROSIL)972(二氧化矽表面被二甲基二氯矽烷包覆,在400℃的反應器中水解,被甲基等有機基團表面修飾的二氧化矽填料、日本艾羅技(AEROSIL)股份有限公司製、商品名、平均粒徑0.016 μm)中加入環己酮並攪拌混合,進而使用珠磨機混煉90分鐘。相對於得到的混合物,添加280質量份的作為丙烯酸橡膠的HTR-860P-3(長瀨化成(Nagase ChemteX)股份有限公司製、商品名、重量平均分子量80萬、含有丙烯酸縮水甘油酯或甲基丙烯酸縮水甘油酯3質量%的丙烯酸橡膠)及0.5質量份的作為硬化促進劑的固唑(Curezol)2PZ-CN(四國化成工業股份有限公司製、商品名,1-氰基乙基-2-苯基咪唑),攪拌混合,並真空脫氣,藉此得到接著劑層形成用清漆。將得到的接著劑層形成用清漆以成為設定的厚度的方式塗佈在經脫模處理的聚對苯二甲酸乙二酯(PET)膜上,在140℃下加熱乾燥5分鐘,形成厚度10 μm的B階段狀態的接著劑層,製作具備接著劑層的黏晶膜。(Making of mucous film) In 55 parts by mass of YDCN-703 as an epoxy resin (manufactured by Dongdu Chemical Co., Ltd., trade name, cresol novolac type epoxy resin, epoxy equivalent 210, molecular weight 1200, softening point 80°C), 45 parts by mass Phenolic resin of Milex XLC-LL (manufactured by Mitsui Chemicals Co., Ltd., brand name, hydroxyl equivalent 175, water absorption rate 1.8%, heating mass reduction rate at 350°C 4%), 1.7 parts by mass As a silane coupling agent, NUCA-189 (manufactured by Nippon Unicar Co., Ltd., trade name, γ-mercaptopropyl trimethoxysilane) and 3.2 parts by mass of NUCA-1160 (Nippon Unicar) Unicar Co., Ltd., trade name, γ-ureidopropyl triethoxysilane), and 32 parts by mass of AEROSIL 972 as a filler (silica surface is coated with dimethyldichlorosilane Coated, hydrolyzed in a reactor at 400°C, and added cyclohexane to a silica filler surface-modified with organic groups such as methyl, manufactured by AEROSIL Co., Ltd., trade name, average particle size 0.016 μm The ketone was stirred and mixed, and further kneaded for 90 minutes using a bead mill. To the obtained mixture, 280 parts by mass of HTR-860P-3 (manufactured by Nagase ChemteX Co., Ltd., brand name, weight average molecular weight 800,000, containing glycidyl acrylate or methyl Glycidyl acrylate 3% by mass acrylic rubber) and 0.5 parts by mass of Curezol 2PZ-CN (manufactured by Shikoku Chemical Industry Co., Ltd., trade name, 1-cyanoethyl-2) as a hardening accelerator -Phenylimidazole), stirred and mixed, and vacuum degassed, thereby obtaining a varnish for forming an adhesive layer. The obtained varnish for forming an adhesive layer was coated on a release-treated polyethylene terephthalate (PET) film so as to have a predetermined thickness, and heated and dried at 140°C for 5 minutes to form a thickness of 10 The adhesive layer in the B-stage state of μm is used to prepare a mucous film with the adhesive layer.

(切割-黏晶一體型膜的製作) 將所述製作的黏晶膜切割成容易連同PET膜一起處理的尺寸。對切割後的黏晶膜的接著劑層,在即將貼附之前剝去PET膜貼合切割膜的光硬化性黏著劑層。貼合是在潔淨室(溫度23℃、濕度50%的無塵室內)使用層壓機、在不加熱輥(即溫度23℃)下進行。其後,自保持接著劑層與光硬化性黏著劑層的密接性恆定的觀點出發,藉由在4℃的冰箱中保管1天,得到切割-黏晶一體型膜A。(Production of cutting-bonding integrated film) The fabricated mucosal film is cut into a size that is easy to handle together with the PET film. For the adhesive layer of the die-cut film, peel off the PET film and attach the photo-curable adhesive layer of the dicing film immediately before attaching. Laminating is performed in a clean room (a clean room with a temperature of 23°C and a humidity of 50%) using a laminator without heating the roller (ie, a temperature of 23°C). Thereafter, from the viewpoint of keeping the adhesiveness between the adhesive layer and the photocurable adhesive layer constant, the dicing-bonding integrated film A was obtained by storing it in a refrigerator at 4°C for one day.

<製造例2:切割-黏晶一體型膜B的製作> 除了將交聯劑的含量自8質量份變更為10質量份以外,與製造例1同樣地操作,得到切割-黏晶一體型膜B。<Manufacturing example 2: Production of dicing-bonding integrated film B> Except that the content of the crosslinking agent was changed from 8 parts by mass to 10 parts by mass, the same procedure as in Production Example 1 was carried out to obtain a dicing-bonding integrated film B.

<製造例3:切割-黏晶一體型膜C的製作> 除了將(甲基)丙烯酸共聚物溶液自A變更為B,將交聯劑的含量自8質量份變更為6質量份以外,與製造例1同樣地操作,得到切割-黏晶一體型膜C。<Manufacturing example 3: Production of dicing-bonding integrated film C> Except that the (meth)acrylic copolymer solution was changed from A to B, and the content of the crosslinking agent was changed from 8 parts by mass to 6 parts by mass, the same procedure as in Production Example 1 was carried out to obtain a dicing-bonding integrated film C .

<製造例4:切割-黏晶一體型膜D的製作> 除了將光硬化性黏著劑層形成用清漆的塗佈速度變更為製造例1的塗佈速度的0.8倍以外,與製造例1同樣地操作,得到切割-黏晶一體型膜D。<Manufacturing example 4: Production of dicing-bonding integrated film D> Except that the coating speed of the varnish for forming a photocurable adhesive layer was changed to 0.8 times the coating speed of Production Example 1, the same procedure as in Production Example 1 was carried out to obtain a dicing-bonding integrated film D.

<製造例5:切割-黏晶一體型膜E的製作> 除了將光硬化性黏著劑層形成用清漆的塗佈速度變更為製造例1的塗佈速度的1.2倍以外,與製造例1同樣地操作,得到切割-黏晶一體型膜E。<Manufacturing example 5: Production of dicing-bonding integrated film E> Except that the coating speed of the varnish for forming a photocurable adhesive layer was changed to 1.2 times the coating speed of Production Example 1, the same procedure as in Production Example 1 was carried out to obtain a dicing-bonding integrated film E.

<製造例6:切割-黏晶一體型膜F的製作> 除了將(甲基)丙烯酸共聚物溶液自A變更為C,將交聯劑的含量自8質量份變更為6質量份以外,與製造例1同樣地操作,得到切割-黏晶一體型膜F。<Manufacturing example 6: Production of dicing-bonding integrated film F> Except that the (meth)acrylic copolymer solution was changed from A to C, and the content of the crosslinking agent was changed from 8 parts by mass to 6 parts by mass, the same procedure as in Production Example 1 was carried out to obtain a dicing-bonding integrated film F .

<製造例7:切割-黏晶一體型膜G的製作> 除了將(甲基)丙烯酸共聚物溶液自A變更為D,將交聯劑的含量自8質量份變更為6質量份以外,與製造例1同樣地操作,得到切割-黏晶一體型膜G。<Manufacturing example 7: Production of dicing-bonding integrated film G> Except that the (meth)acrylic copolymer solution was changed from A to D, and the content of the crosslinking agent was changed from 8 parts by mass to 6 parts by mass, the same procedure as in Production Example 1 was carried out to obtain a dicing-bonding integrated film G .

<製造例8:切割-黏晶一體型膜H的製作> 除了將交聯劑的含量自8質量份變更為6質量份以外,與製造例1同樣地操作,得到切割-黏晶一體型膜H。<Manufacturing Example 8: Production of Die-Bonding Integrated Film H> Except that the content of the crosslinking agent was changed from 8 parts by mass to 6 parts by mass, the same procedure as in Production Example 1 was performed to obtain a dicing-bonding integrated film H.

<製造例9:切割-黏晶一體型膜I的製作> 除了自(甲基)丙烯酸共聚物溶液A變更為(甲基)丙烯酸共聚物溶液E以外,與製造例1同樣地操作,得到切割-黏晶一體型膜I。<Manufacturing Example 9: Production of Die-Bonding Integrated Film I> Except having changed from (meth)acrylic copolymer solution A to (meth)acrylic copolymer solution E, it carried out similarly to manufacture example 1, and obtained the dicing-bonding integrated film I.

<製造例10:切割-黏晶一體型膜J的製作> 除了將光硬化性黏著劑層形成用清漆的塗佈速度變更為製造例1的塗佈速度的1.5倍以外,與製造例1同樣地操作,得到切割-黏晶一體型膜J。<Production Example 10: Production of Die-bonding Integrated Film J> Except that the coating speed of the varnish for forming a photocurable adhesive layer was changed to 1.5 times the coating speed of Manufacturing Example 1, the same procedure as in Manufacturing Example 1 was carried out to obtain a dicing-bonding integrated film J.

<製造例11:切割-黏晶一體型膜K的製作> 除了將光硬化性黏著劑層形成用清漆的塗佈速度變更為製造例1的塗佈速度的0.6倍以外,與製造例1同樣地操作,得到切割-黏晶一體型膜K。<Production Example 11: Production of Die-Bonding Integrated Film K> Except that the coating speed of the varnish for forming a photocurable adhesive layer was changed to 0.6 times the coating speed of Manufacturing Example 1, the same procedure as in Manufacturing Example 1 was carried out to obtain a dicing-bonding integrated film K.

<製造例12:切割-黏晶一體型膜L的製作> 在切割-黏晶一體型膜的製作中,在潔淨室(溫度23℃、濕度50%的無塵室內)剝離切割膜的PET膜,將使光硬化性黏著劑層暴露於空氣中放置1天以上後的層貼附在黏晶膜的接著劑層上,除此以外與製造例1相同同樣地操作,得到切割-黏晶一體型膜L。<Production Example 12: Production of Die-bonding Integrated Film L> In the production of the dicing-bonding integrated film, the PET film of the dicing film is peeled off in a clean room (a clean room with a temperature of 23°C and a humidity of 50%), and the light-curing adhesive layer is exposed to the air for 1 day The above-mentioned layers were attached to the adhesive layer of the die-bonding film, and except for that, the same operations as in Production Example 1 were carried out to obtain a dicing-die-bonding integrated film L.

<製造例13:切割-黏晶一體型膜M的製作> 除了在切割-黏晶一體型膜的製作中,一邊將層壓機的輥加熱至50℃,一邊貼附黏晶膜的接著劑層與切割膜的光硬化性黏著劑層以外,與製造例1同樣地,得到切割-黏晶一體型膜M。<Manufacturing example 13: Production of dicing-bonding integrated film M> In addition to the production of the dicing-bonding integrated film, the adhesive layer of the die-bonding film and the photo-curing adhesive layer of the dicing film are attached while heating the roll of the laminator to 50°C, and the production example 1 In the same manner, a dicing-bonding integrated film M is obtained.

[剝離力的測定]<測定樣品的製作> 將切割-黏晶一體型膜A~切割-黏晶一體型膜M分別切成寬30 mm、長200 mm,剝離黏晶膜的接著劑層側的PET膜,使用輥將支撐膜(王子塔庫(OJI TAC)股份有限公司製、EC帶)貼附在接著劑層側,切成寬25 mm、長170 mm。接著,自切出的帶黏著膜的切割-黏晶一體型膜的基材層(聚烯烴製膜)側,使用紫外線照射裝置(GS湯淺(YUASA)股份有限公司製、UV SYSTEM、中心波長365 nm的紫外線),在照射溫度40℃以下、照射強度70 mW/cm2 以及累計光量150 mJ/cm2 下照射,形成光硬化性黏著劑層的硬化物,藉此獲得測定樣品。[Measurement of peeling force] <Preparation of measurement sample> Cut the dicing-bonding integrated film A to the dicing-bonding integrated film M into a width of 30 mm and a length of 200 mm, and peel off the adhesive layer side of the adhesive film Use a roller to attach a support film (manufactured by OJI TAC Co., Ltd., EC tape) to the adhesive layer side, and cut it into a width of 25 mm and a length of 170 mm. Next, from the base layer (polyolefin film) side of the cut-out die-bonding integrated film with adhesive film, an ultraviolet irradiation device (manufactured by GS Yuasa Co., Ltd., UV SYSTEM, center wavelength 365 nm ultraviolet rays), irradiated at an irradiation temperature of 40°C or lower, an irradiation intensity of 70 mW/cm 2 and a cumulative light amount of 150 mJ/cm 2 to form a cured product of the photocurable adhesive layer, thereby obtaining a measurement sample.

<剝離力的測定> 針對如所述般製作的測定樣品,使用角度自由型的黏著-覆膜剝離解析裝置VPA-2S(協和界面科學股份有限公司製),以溫度25±5℃、濕度55±10%、剝離角度30°、以及剝離速度600 mm/分鐘拉伸支撐膜,測定剝離接著劑層與光硬化性黏著劑層的硬化物時的剝離力(低角(30°)剝離強度)。進行3次同樣的測定,將其平均值作為低角剝離強度。將結果示於表2、表3、及表4。另外,條件(a)(剝離力為0.70 N/25 mm以下)的滿足性亦示於表2、表3、及表4。<Measurement of peel strength> For the measurement sample prepared as described above, the angle-free adhesion-film peeling analysis device VPA-2S (manufactured by Kyowa Interface Science Co., Ltd.) was used at a temperature of 25±5°C, a humidity of 55±10%, and a peeling angle The support film was stretched at 30° and a peeling speed of 600 mm/min, and the peel strength (low angle (30°) peel strength) when peeling the cured product of the adhesive layer and the photocurable adhesive layer was measured. The same measurement was performed three times, and the average value was taken as the low-angle peel strength. The results are shown in Table 2, Table 3, and Table 4. In addition, the satisfaction of the condition (a) (the peel force is 0.70 N/25 mm or less) is also shown in Table 2, Table 3, and Table 4.

[拉絲痕跡的痕跡數及痕跡寬度測量]<測定樣品的製作> 切割-黏晶一體型膜與上述剝離力的測定中使用的膜相同,且使用未進行上述剝離力的測定的膜。將切割-黏晶一體型膜A~M分別切成寬30 mm、長50 mm以上。接著,將加熱器與切割-黏晶一體型膜的基材層(聚烯烴製膜)接觸,將光硬化性黏著劑層在65℃加熱15分鐘,然後空冷至25±5℃。空冷後,剝下黏晶膜的接著劑層側的PET膜,貼合支撐膜(王子塔庫(OJI TAC)股份有限公司製,EC帶),整齊切成寬度為25 mm。接著,自加熱冷卻後的帶支撐膜的切割-黏晶一體型膜的基材層(聚烯烴製膜)側,使用紫外線照射裝置(GS湯淺(YUASA)股份有限公司製、UV SYSTEM、中心波長365 nm的紫外線),在照射溫度40℃以下、照射強度70 mW/cm2 以及累計光量150 mJ/cm2 下照射,形成光硬化性黏著劑層的硬化物。接著,使用角度自由型的黏著-覆膜剝離解析裝置VPA-2S(協和界面科學股份有限公司製),以溫度25±5℃、濕度55±10%、剝離角度30°、以及剝離速度600 mm/分鐘拉伸支撐膜,剝離接著劑層與光硬化性黏著劑層的硬化物,將具備接著劑層被剝離後的光硬化性黏著劑層的硬化物的基材層回收,藉由切成5 mm×5 mm的尺寸,獲得測量樣品。[Measurement of the number of traces of the wire drawing and the width of the trace] <Preparation of a measurement sample> The dicing-bonding integrated film is the same as the film used in the above-mentioned peeling force measurement, and a film that has not been subjected to the above-mentioned peeling force measurement is used. Cut the cutting-bonding integrated film A~M into width 30 mm and length 50 mm or more. Next, the heater is brought into contact with the base layer (polyolefin film) of the dicing-bonding integrated film, and the photocurable adhesive layer is heated at 65°C for 15 minutes, and then air-cooled to 25±5°C. After air cooling, peel off the PET film on the adhesive layer side of the mucosal film, attach the support film (manufactured by OJI TAC Co., Ltd., EC tape), and cut neatly into a width of 25 mm. Next, on the base layer (polyolefin film) side of the dicing-bonding integrated film with support film after heating and cooling, the ultraviolet irradiation device (manufactured by GS Yuasa Co., Ltd., UV SYSTEM, center wavelength 365 nm ultraviolet rays), irradiate at an irradiation temperature of 40°C or lower, an irradiation intensity of 70 mW/cm 2 and a cumulative light quantity of 150 mJ/cm 2 to form a cured product of the photocurable adhesive layer. Next, use the angle-free adhesive-film peeling analysis device VPA-2S (manufactured by Kyowa Interface Science Co., Ltd.) at a temperature of 25±5°C, a humidity of 55±10%, a peeling angle of 30°, and a peeling speed of 600 mm The support film is stretched per minute, the cured product of the adhesive layer and the photocurable adhesive layer is peeled off, and the substrate layer with the cured product of the photocurable adhesive layer after the adhesive layer is peeled off is recovered and cut into With a size of 5 mm×5 mm, a measurement sample is obtained.

<拉絲痕跡的痕跡數及痕跡寬度的測量> 將上述製作的測量樣品固定在板狀的台上。測量樣品的固定使用了碳雙面膠帶。使用掃描型探針顯微鏡(日本精工電子納米科技(SII NanoTechnology))股份有限公司製,商品名「SPA400」),觀察接著劑層被剝離後的光硬化性黏著劑層的硬化物的表面,使用圖像解析軟體(附屬於「SPA400」)進行解析。在掃描型探針顯微鏡的探針上設置彈簧常數低的懸臂(奧林巴斯(Olympus)股份有限公司製,商品名「OMCL-AC240TS」)來進行。在光硬化性黏著劑層的硬化物的觀察中,以動態力模式(DFM)進行觀察,同時取得相位圖像的資料,將該相位圖像中硬度明顯與周圍不同的部位作為拉絲痕跡。在測量樣品的觀察中,確認了在作為觀察對象的表面是否存在拉絲痕跡的痕跡數為15以上的25 μm×25 μm的區域(特定區域)。於在接著劑層被剝離後的光硬化性黏著劑層的硬化物的表面存在拉絲痕跡的痕跡數為15以上的特定區域的情況下,計算出特定區域存在的拉絲痕跡的痕跡寬度的中位數。拉絲痕跡的痕跡寬度如下求出。首先,使用掃描型探針顯微鏡,取得包含相位圖像中硬度明顯與周圍不同的部位的光硬化性黏著劑層的硬化物表面的形狀圖像分佈及相位圖像分佈。接著,根據取得的形狀圖像分佈,使用市售的圖像處理軟體(掃描型探針顯微鏡附屬的圖像處理軟體等),對於成為測定對象的全部拉絲痕跡,分別輸出各拉絲痕跡的痕跡寬度最大的剖面線的剖面分佈,根據上述基準求出拉絲痕跡的痕跡寬度。再者,在形狀圖像分佈中,拉絲痕跡以最淡的顏色(在黑白圖像的情況下,例如白色)表示,但在相位圖像中硬度明顯與周圍不同的部位的個數與在形狀圖像分佈中以最淡的顏色表示的部位的個數相同。將結果示於表2、表3、及表4中。另外,對於條件(b)(接著劑層被剝離後的光硬化性黏著劑層的硬化物的表面存在拉絲痕跡的痕跡數為15以上的25 μm×25 μm的區域,區域內的拉絲痕跡的痕跡寬度的中位數為120 nm~200 nm)的滿足性,亦示於表2、表3、及表4。<Measurement of the number of traces of wire drawing and the width of traces> The measurement sample prepared above is fixed on a plate-shaped table. Carbon double-sided tape was used to fix the measurement sample. Use a scanning probe microscope (manufactured by SII NanoTechnology Co., Ltd., trade name "SPA400") to observe the surface of the cured product of the photocurable adhesive layer after the adhesive layer is peeled off, and use Image analysis software (attached to "SPA400") for analysis. A cantilever with a low spring constant (manufactured by Olympus Co., Ltd., trade name "OMCL-AC240TS") is installed on the probe of the scanning probe microscope. In the observation of the cured product of the photocurable adhesive layer, the observation is performed in the dynamic force mode (DFM), and the data of the phase image is obtained at the same time, and the parts in the phase image whose hardness is obviously different from the surroundings are regarded as the drawing traces. In the observation of the measurement sample, it was confirmed whether there was a 25 μm×25 μm area (specific area) with 15 or more traces of wire drawing on the surface of the observation target. In the case of a specific area where the number of wire drawing marks is 15 or more on the surface of the cured product of the photocurable adhesive layer after the adhesive layer is peeled off, calculate the median of the width of the wire drawing marks in the specific area number. The trace width of the drawing trace is obtained as follows. First, a scanning probe microscope is used to obtain the shape image distribution and the phase image distribution of the hardened object surface of the photocurable adhesive layer including parts whose hardness is significantly different from the surroundings in the phase image. Next, according to the acquired shape image distribution, using commercially available image processing software (image processing software attached to the scanning probe microscope, etc.), for all the wire drawing traces to be measured, the trace width of each wire drawing trace is outputted. The cross-sectional distribution of the largest hatch line is used to obtain the trace width of the drawing trace based on the above-mentioned reference. Furthermore, in the shape image distribution, the drawing traces are expressed in the lightest color (in the case of a black-and-white image, for example, white), but in the phase image, the number of parts whose hardness is obviously different from that of the surroundings and the shape The number of parts represented by the lightest color in the image distribution is the same. The results are shown in Table 2, Table 3, and Table 4. In addition, for condition (b) (the number of traces of drawing traces on the surface of the cured product of the photocurable adhesive layer after the adhesive layer is peeled off is 15 or more, the number of traces in the region of 25 μm×25 μm The median of the trace width is 120 nm ~ 200 nm). The satisfaction is also shown in Table 2, Table 3, and Table 4.

[切割步驟中的拾取性的評價] 對於得到的製造例1~13的切割-黏晶一體型膜A~M,評價切割步驟的規定條件下的拾取的成功率及拾取所花費的剝離時間。[Evaluation of Pickup in Cutting Step] For the obtained dicing-die-bonding integrated films A to M of Manufacturing Examples 1 to 13, the success rate of picking up under the predetermined conditions of the cutting step and the peeling time taken for picking up were evaluated.

<評價樣品的製作>(改質層形成) 在半導體晶圓(矽晶圓(厚度750 μm、外徑12英吋))的一面貼附背面研磨帶(back grind tape),得到帶背面研磨帶的半導體晶圓。對半導體晶圓的與貼附有背面研磨帶的一側相反一側的面照射雷射光,在半導體晶圓內部形成改質層。雷射光的照射條件如下。<Preparation of evaluation samples> (Formation of modified layer) A back grind tape is attached to one side of a semiconductor wafer (silicon wafer (thickness 750 μm, outer diameter 12 inches)) to obtain a semiconductor wafer with back grind tape. Laser light is irradiated to the surface of the semiconductor wafer on the side opposite to the side where the back grinding tape is attached to form a modified layer inside the semiconductor wafer. The irradiation conditions of the laser light are as follows.

雷射振動器型式:半導體雷射光激發Q開關固體雷射 波長:1342 nm 振動形式:脈衝 頻率:90 kHz 輸出:1.7W 半導體晶圓載置台的移動速度:700 mm/秒Laser vibrator type: semiconductor laser light excites Q-switch solid laser Wavelength: 1342 nm Vibration form: pulse Frequency: 90 kHz Output: 1.7W Movement speed of semiconductor wafer mounting table: 700 mm/sec

接著,對半導體晶圓的與貼附有背面研磨帶的一側相反的一側的面進行背面研磨和拋光,藉此得到厚度為30 μm的半導體晶圓。Next, back grinding and polishing were performed on the surface of the semiconductor wafer on the side opposite to the side where the back grinding tape was attached, thereby obtaining a semiconductor wafer with a thickness of 30 μm.

(晶圓層壓) 在半導體晶圓的與貼附有背面研磨帶的一側相反一側的面上,剝下切割-黏晶一體型膜的PET膜,貼附接著劑層。(Wafer lamination) On the surface of the semiconductor wafer opposite to the side where the back polishing tape is attached, the PET film of the dicing-bonding integrated film is peeled off, and the adhesive layer is attached.

(切割) 接著,將帶具有改質層的切割-黏晶一體型膜的半導體晶圓固定在擴展裝置上。接著,在下述條件下擴展切割膜,將半導體晶圓、接著劑層、及光硬化性黏著劑層單片化。(Cutting) Next, the semiconductor wafer with the integrated dicing-bonding film with the modified layer is fixed on the expansion device. Next, the dicing film was expanded under the following conditions, and the semiconductor wafer, the adhesive layer, and the photocurable adhesive layer were singulated.

裝置:迪士科(Disco)股份有限公司製,商品名「DDS 2300 全自動晶粒分離器(Fully Automatic Die Separator)」 冷擴展條件: 溫度:-15℃、高度:9 mm、冷卻時間:90秒、速度:300 mm/秒、待機時間:0秒 熱收縮條件: 溫度:220℃、高度:7 mm、保持時間:15秒、速度:30 mm/秒、加熱速度:7℃/秒Device: manufactured by Disco Co., Ltd., trade name "DDS 2300 Fully Automatic Die Separator" Cold expansion conditions: Temperature: -15°C, height: 9 mm, cooling time: 90 seconds, speed: 300 mm/sec, standby time: 0 seconds Heat shrinkage conditions: Temperature: 220°C, height: 7 mm, holding time: 15 seconds, speed: 30 mm/sec, heating speed: 7°C/sec

(紫外線照射) 對經單片化的半導體晶圓的光硬化性黏著劑層以照射強度70 mW/cm2 和累計光量150 mJ/cm2 照射中心波長365 nm的紫外線,形成光硬化性黏著劑層的硬化物,藉此獲得後述的拾取性的評價樣品。(Ultraviolet radiation) The photocurable adhesive layer of the singulated semiconductor wafer is irradiated with ultraviolet rays with a central wavelength of 365 nm at an intensity of 70 mW/cm 2 and a cumulative light amount of 150 mJ/cm 2 to form a photocurable adhesive. The cured product of the layer was used to obtain the evaluation sample of the pick-up described later.

<拾取性的評價> 使用固晶機DB-830P(法斯福德科技(FASFORD TECHNOLOGY)股份有限公司製(原日立高新技術(Hitachi High-technologies)股份有限公司製)),用9根銷進行了拾取試驗。拾取用夾頭使用橡膠吸嘴(RUBBER TIP)13-087E-33(微機械公司(micromechanics)製,商品名,尺寸:10×10 mm)。上頂銷使用噴射針(EJECTOR NEEDLE)SEN2-83-05(微機械公司製,商品名,直徑:0.7 mm,前端形狀:直徑350 μm的半圓)。上頂銷從銷中心等間隔地配置了9根。<Evaluation of pickup ability> Using a die bonder DB-830P (manufactured by FASFORD TECHNOLOGY Co., Ltd. (formerly manufactured by Hitachi High-technologies Co., Ltd.)), a pick-up test was carried out with 9 pins. The pick-up chuck uses a rubber nozzle (RUBBER TIP) 13-087E-33 (manufactured by Micromechanics, trade name, size: 10×10 mm). The ejector needle (EJECTOR NEEDLE) SEN2-83-05 (manufactured by Micromachine, trade name, diameter: 0.7 mm, tip shape: semicircle with a diameter of 350 μm) is used for the top pin. Nine top pins are arranged at equal intervals from the center of the pin.

<拾取的成功率> 在上述拾取試驗中,將拾取成功率為95%~100%的評價為「A」,不到95%的評價為「B」。將結果示於表2、表3、及表4。<Success rate of picking> In the above-mentioned picking test, the picking success rate of 95% to 100% is evaluated as "A", and the picking success rate is less than 95% as "B". The results are shown in Table 2, Table 3, and Table 4.

<拾取的剝離時間> 使用高速相機MEMRECM GX-1Plus(NAC圖像技術(NAC Image Technology)股份有限公司製,商品名),拍攝上述拾取試驗,將夾頭與晶片接觸後到接著劑層與光硬化性黏著劑層完全剝離為止的時間作為剝離時間進行評價。拾取以1 mm/秒的速度上頂到300 μm來進行。訊框速率為1000訊框/秒。剝離時間在60m秒以下的評價為「A」,超過60m秒小於90m秒的評價為「B」,超過90m秒的評價為「C」。將結果示於表2、表3、及表4。<Peeling time of pickup> A high-speed camera MEMRECM GX-1Plus (manufactured by NAC Image Technology Co., Ltd., trade name) was used to photograph the above-mentioned pickup test. After the chuck was in contact with the wafer, the adhesive layer and the light-curing adhesive layer were completely The time until peeling was evaluated as peeling time. The pick-up is carried out at a speed of 1 mm/sec up to 300 μm. The frame rate is 1000 frames per second. A peeling time of 60 msec or less was evaluated as "A", a peeling time exceeding 60 msec and less than 90 msec was evaluated as "B", and a peeling time exceeding 90 msec was evaluated as "C". The results are shown in Table 2, Table 3, and Table 4.

表2   製造例 1 製造例 2 製造例 3 製造例 4 製造例 5 切割-黏晶一體型膜 A B C D E (甲基)丙烯酸共聚物溶液 種類 A A B A A 固體成分含量 100 100 100 100 100 光聚合起始劑 1 1 1 1 1 交聯劑 固體成分含量 8 10 6 8 8 塗佈速度比(製造例1為基準) 1 1 1 0.8 1.2 貼合溫度(℃) 23 23 23 23 23 有無光硬化性樹脂層的空氣暴露 剝離力(低角剝離強度) (N/25 mm) 0.55 0.61 0.61 0.60 0.60 條件(a)的滿足性 滿足 滿足 滿足 滿足 滿足 拉絲痕跡 有無特定區域 特定區域內的拉絲痕跡的痕跡數 55 54 54 38 20 拉絲痕跡的痕跡寬度的中位數(nm) 172 192 122 168 147 條件(b)的滿足性 滿足 滿足 滿足 滿足 滿足 拾取性的評價 成功率 A A A A A 剝離時間 A A A A A Table 2 Manufacturing example 1 Manufacturing example 2 Manufacturing example 3 Manufacturing example 4 Manufacturing example 5 Cutting-bonding integrated film A B C D E (Meth) acrylic copolymer solution species A A B A A Solid content 100 100 100 100 100 Photopolymerization initiator 1 1 1 1 1 Crosslinking agent Solid content 8 10 6 8 8 Coating speed ratio (based on manufacturing example 1) 1 1 1 0.8 1.2 Fitting temperature (℃) twenty three twenty three twenty three twenty three twenty three Whether the light-curable resin layer is exposed to air no no no no no Peel strength (low angle peel strength) (N/25 mm) 0.55 0.61 0.61 0.60 0.60 Satisfaction of condition (a) Satisfy Satisfy Satisfy Satisfy Satisfy Drawing traces Is there a specific area Have Have Have Have Have Number of traces of wire drawing in a specific area 55 54 54 38 20 The median of the trace width of the drawing trace (nm) 172 192 122 168 147 Satisfaction of condition (b) Satisfy Satisfy Satisfy Satisfy Satisfy Pick-up evaluation Success rate A A A A A Peeling time A A A A A

表3   製造例 6 製造例 7 製造例 8 製造例 9 製造例 10 切割-黏晶一體型膜 F G H I J (甲基)丙烯酸共聚物溶液 種類 C D A E A 固體成分含量 100 100 100 100 100 光聚合起始劑 1 1 1 1 1 交聯劑 固體成分含量 6 6 6 8 8 塗佈速度比(製造例1為基準) 1 1 1 1 1.5 貼合溫度(℃) 23 23 23 23 23 有無光硬化性樹脂層的空氣暴露 剝離力(低角剝離強度) (N/25 mm) 0.55 0.91 0.75 0.69 0.70 條件(a)的滿足性 滿足 不滿足 不滿足 滿足 滿足 拉絲痕跡 有無特定區域 特定區域內的拉絲痕跡的痕跡數 55 54 54 38 20 拉絲痕跡的痕跡寬度的中位數(nm) 104 122 16 232 250 條件(b)的滿足性 不滿足 滿足 不滿足 不滿足 不滿足 拾取性的評價 成功率 B B A B B 剝離時間 B B C C B table 3 Manufacturing example 6 Manufacturing example 7 Manufacturing example 8 Manufacturing example 9 Manufacturing example 10 Cutting-bonding integrated film F G H I J (Meth) acrylic copolymer solution species C D A E A Solid content 100 100 100 100 100 Photopolymerization initiator 1 1 1 1 1 Crosslinking agent Solid content 6 6 6 8 8 Coating speed ratio (based on manufacturing example 1) 1 1 1 1 1.5 Fitting temperature (℃) twenty three twenty three twenty three twenty three twenty three Whether the light-curable resin layer is exposed to air no no no no no Peel strength (low angle peel strength) (N/25 mm) 0.55 0.91 0.75 0.69 0.70 Satisfaction of condition (a) Satisfy Not satisfied Not satisfied Satisfy Satisfy Drawing traces Is there a specific area Have Have Have Have Have Number of traces of wire drawing in a specific area 55 54 54 38 20 The median of the trace width of the drawing trace (nm) 104 122 16 232 250 Satisfaction of condition (b) Not satisfied Satisfy Not satisfied Not satisfied Not satisfied Pick-up evaluation Success rate B B A B B Peeling time B B C C B

表4   製造例 11 製造例 12 製造例 13 切割-黏晶一體型膜 K L M (甲基)丙烯酸共聚物溶液 種類 A A B 固體成分含量 100 100 100 光聚合起始劑 1 1 1 交聯劑 固體成分含量 8 8 8 塗佈速度比(製造例1為基準) 0.6 1 1 貼合溫度(℃) 23 23 50 有無光硬化性樹脂層的空氣暴露 剝離力(低角剝離強度)(N/25 mm) 0.56 0.50 0.90 條件(a)的滿足性 滿足 滿足 不滿足 拉絲痕跡 有無特定區域 特定區域內的拉絲痕跡的痕跡數 19 15 56 拉絲痕跡的痕跡寬度的中位數(nm) 60 100 210 條件(b)的滿足性 不滿足 不滿足 不滿足 拾取性的評價 成功率 A B B 剝離時間 B C C Table 4 Manufacturing example 11 Manufacturing example 12 Manufacturing example 13 Cutting-bonding integrated film K L M (Meth) acrylic copolymer solution species A A B Solid content 100 100 100 Photopolymerization initiator 1 1 1 Crosslinking agent Solid content 8 8 8 Coating speed ratio (based on manufacturing example 1) 0.6 1 1 Fitting temperature (℃) twenty three twenty three 50 Whether the light-curable resin layer is exposed to air no Have no Peel strength (low angle peel strength) (N/25 mm) 0.56 0.50 0.90 Satisfaction of condition (a) Satisfy Satisfy Not satisfied Drawing traces Is there a specific area Have Have Have Number of traces of wire drawing in a specific area 19 15 56 The median of the trace width of the drawing trace (nm) 60 100 210 Satisfaction of condition (b) Not satisfied Not satisfied Not satisfied Pick-up evaluation Success rate A B B Peeling time B C C

如表2、表3以及表4所示,製造例1~5的切割-黏晶一體型膜A~E的剝離力為0.70 N/25 mm以下,且在接著劑層被剝離後的光硬化性黏著劑層的硬化物的表面存在拉絲痕跡的痕跡數為15以上的25 μm×25 μm的區域,區域內的拉絲痕跡的痕跡寬度的中位數為120 nm~200 nm,滿足條件(a)及條件(b)兩者。判明所述製造例1~5的切割-黏晶一體型膜A~E在拾取性的評價方面優異。與此相對,判明不滿足條件(a)或條件(b)的任一方、或不滿足條件(a)和條件(b)雙方的製造例6~13的切割-黏晶一體型膜F~M在拾取性的評價中不充分。As shown in Table 2, Table 3, and Table 4, the dicing-bonding integrated films A to E of Production Examples 1 to 5 have a peeling force of 0.70 N/25 mm or less, and light curing after the adhesive layer is peeled off The surface of the cured product of the adhesive layer has a 25 μm×25 μm area where the number of wire drawing traces is 15 or more, and the median width of the wire drawing traces in the area is 120 nm to 200 nm, which satisfies the condition (a ) And condition (b). It turned out that the dicing-bonding integrated films A to E of the above-mentioned production examples 1 to 5 are excellent in the evaluation of pick-up properties. On the other hand, it was found that either of condition (a) or condition (b) was not satisfied, or both conditions (a) and (b) were not satisfied, the dicing-bonding integrated films F to M of Manufacturing Examples 6 to 13 It is insufficient in the evaluation of pick-up properties.

1:切割-黏晶一體型膜 2:保護膜 4:改質層 10:基材層 20:光硬化性黏著劑層 20ac:光硬化性黏著劑層的硬化物 30、30a:接著劑層 42:頂針 44:抽吸夾頭 50:帶接著劑層的半導體元件 60:半導體元件搭載用支撐基板 60a:表面 70:打線接合線 80:樹脂密封材 90:焊球 100:半導體裝置 W1、W2:半導體晶圓 Wa:半導體元件 Ws:主面 Wx:拉絲痕跡X的兩端(極小值)彼此的寬度 Wy:基準高度處的寬度 H1、H2:厚度 Hy:基準高度 X、Y:拉絲痕跡 iii-iii、iv-iv:線1: Cutting-bonding integrated film 2: Protective film 4: modified layer 10: Substrate layer 20: Light-curing adhesive layer 20ac: Cured product of light-curing adhesive layer 30, 30a: Adhesive layer 42: thimble 44: Suction Chuck 50: Semiconductor components with adhesive layer 60: Support substrate for mounting semiconductor elements 60a: surface 70: Bonding wire 80: Resin sealing material 90: Solder ball 100: Semiconductor device W1, W2: semiconductor wafer Wa: Semiconductor components Ws: main side Wx: The width of the two ends (minimum) of the drawing trace X Wy: the width at the base height H1, H2: thickness Hy: base height X, Y: wire drawing trace iii-iii, iv-iv: line

圖1是表示切割-黏晶一體型膜的一個實施方式的示意剖面圖。 圖2的(a)及圖2的(b)是表示光硬化性黏著劑層的硬化物的表面的形狀圖像分佈及相位圖像分佈的一個例子的圖,圖2的(a)是形狀圖像分佈,圖2的(b)是相位圖像分佈。 圖3的(a)及圖3的(b)是表示光硬化性黏著劑層的硬化物的表面的剖面分佈的一例的圖,圖3的(a)是形狀圖像分佈,圖3的(b)是圖3的(a)中拉絲痕跡X的iii-iii線的剖面分佈。 圖4的(a)及圖4的(b)是表示光硬化性黏著劑層的硬化物的表面的剖面分佈的一例的圖,圖4的(a)是形狀圖像分佈,圖4的(b)是圖4的(a)中拉絲痕跡Y的iv-iv線的剖面分佈。 圖5的(a)~圖5的(e)是用於說明半導體裝置的製造方法的一個實施方式的示意剖面圖,圖5的(a)、圖5的(b)、圖5的(c)、圖5的(d)及圖5的(e)是表示各步驟的示意剖面圖。 圖6的(f)~圖6的(i)是用於說明半導體裝置的製造方法的一個實施方式的示意剖面圖,圖6的(f)、圖6的(g)、圖6的(h)、及圖6的(i)是表示各步驟的示意剖面圖。 圖7是表示半導體裝置的一個實施方式的示意剖面圖。Fig. 1 is a schematic cross-sectional view showing an embodiment of a dicing-bonding integrated film. 2(a) and 2(b) are diagrams showing an example of the shape image distribution and the phase image distribution on the surface of the cured product of the photocurable adhesive layer, and FIG. 2(a) is the shape Image distribution, Figure 2(b) is the phase image distribution. Figures 3(a) and 3(b) are diagrams showing an example of the cross-sectional distribution of the surface of the cured product of the photocurable adhesive layer, Figure 3(a) is the shape image distribution, and Figure 3(() b) is the cross-sectional distribution of the line iii-iii of the drawing trace X in Fig. 3(a). 4(a) and 4(b) are diagrams showing an example of the cross-sectional distribution of the surface of the cured product of the photocurable adhesive layer. FIG. 4(a) is the shape image distribution, and FIG. 4( b) is the cross-sectional distribution of the iv-iv line of the drawing trace Y in Fig. 4(a). 5(a) to 5(e) are schematic cross-sectional views for explaining an embodiment of a method of manufacturing a semiconductor device, and FIG. 5(a), FIG. 5(b), and FIG. 5(c) ), Fig. 5(d) and Fig. 5(e) are schematic cross-sectional views showing each step. 6(f) to 6(i) are schematic cross-sectional views for explaining an embodiment of the method of manufacturing a semiconductor device, and FIG. 6(f), FIG. 6(g), and FIG. 6(h) ), and Fig. 6(i) are schematic cross-sectional views showing each step. FIG. 7 is a schematic cross-sectional view showing an embodiment of a semiconductor device.

Claims (10)

一種光硬化性黏著劑的評價方法,是切割-黏晶一體型膜所使用的光硬化性黏著劑的評價方法,包括: 第一步驟,準備切割-黏晶一體型膜,所述切割-黏晶一體型膜依次積層有基材層、包含光硬化性黏著劑的光硬化性黏著劑層、以及接著劑層,在下述照射條件下對所述光硬化性黏著劑層照射紫外線,形成所述光硬化性黏著劑層的硬化物,並測定在下述剝離條件下剝離所述接著劑層和所述光硬化性黏著劑層的硬化物時的剝離力; 第二步驟,準備切割-黏晶一體型膜,所述切割-黏晶一體型膜依次積層有基材層、包含光硬化性黏著劑的光硬化性黏著劑層、以及接著劑層,在下述加熱冷卻條件下對所述光硬化性黏著劑層進行處理,並在下述照射條件下對所述光硬化性黏著劑層照射紫外線,形成所述光硬化性黏著劑層的硬化物,在下述剝離條件下剝離所述接著劑層與所述光硬化性黏著劑層的硬化物,利用掃描型探針顯微鏡觀察剝離所述接著劑層後的所述光硬化性黏著劑層的硬化物的表面,並測量所述表面的拉絲痕跡的痕跡數及痕跡寬度;以及 第三步驟,基於所述剝離力及所述拉絲痕跡的痕跡數及痕跡寬度,判定所述光硬化性黏著劑是否良好, (照射條件) 照射強度:70 mW/cm2 累計光量:150 mJ/cm2 (剝離條件) 溫度:25±5℃ 濕度:55±10% 剝離角度:30° 剝離速度:600 mm/分鐘 (加熱冷卻條件) 加熱處理:65℃、15分鐘 冷卻處理:空冷靜置30分鐘,直至25±5℃。An evaluation method of a photocurable adhesive is an evaluation method of a photocurable adhesive used in a cutting-bonding integrated film, which includes: The first step is to prepare a cutting-bonding integrated film, and the cutting-bonding integrated film is prepared. The crystal-integrated film is sequentially laminated with a substrate layer, a photocurable adhesive layer containing a photocurable adhesive, and an adhesive layer. The photocurable adhesive layer is irradiated with ultraviolet rays under the following irradiation conditions to form the The cured product of the light-curable adhesive layer, and the peeling force when the adhesive layer and the cured product of the light-curable adhesive layer are peeled off under the following peeling conditions are measured; the second step is to prepare for cutting-bonding one A body-shaped film in which a substrate layer, a photocurable adhesive layer containing a photocurable adhesive, and an adhesive layer are sequentially laminated on the dicing-bonding integrated film, and the photocurable film is heated and cooled under the following heating and cooling conditions. The adhesive layer is processed, and the photo-curable adhesive layer is irradiated with ultraviolet rays under the following irradiation conditions to form a cured product of the photo-curable adhesive layer, and the adhesive layer and the adhesive layer are peeled off under the following peeling conditions The hardened product of the light-curable adhesive layer is observed using a scanning probe microscope to observe the surface of the hardened product of the light-curable adhesive layer after the adhesive layer is peeled off, and the traces of wire drawing on the surface are measured And the third step, based on the peeling force and the number of traces and the width of the traces of the wire drawing, determine whether the photocurable adhesive is good, (irradiation conditions) irradiation intensity: 70 mW/cm 2 Cumulative light quantity: 150 mJ/cm 2 (Peeling conditions) Temperature: 25±5°C Humidity: 55±10% Peeling angle: 30° Peeling speed: 600 mm/min (heating and cooling conditions) Heat treatment: 65°C, 15 minutes cooling Treatment: Let it cool for 30 minutes until it is 25±5℃. 如請求項1所述的光硬化性黏著劑的評價方法,其中所述第三步驟是根據所述剝離力及所述拉絲痕跡的痕跡數及痕跡寬度是否滿足下述條件(a)及下述條件(b)來判定所述光硬化性黏著劑是否良好的步驟, 條件(a):所述剝離力為0.70 N/25 mm以下, 條件(b):在剝離所述接著劑層後的所述光硬化性黏著劑層的硬化物的表面存在拉絲痕跡的痕跡數為15以上的25 μm×25 μm的區域,所述區域內的所述拉絲痕跡的痕跡寬度的中位數為120 nm~200 nm。The method for evaluating a photocurable adhesive according to claim 1, wherein the third step is based on whether the peeling force and the number of traces of the drawing trace and the trace width satisfy the following condition (a) and the following Condition (b) to determine whether the photocurable adhesive is good, Condition (a): The peeling force is 0.70 N/25 mm or less, Condition (b): A region of 25 μm×25 μm where the number of traces of drawing marks is 15 or more on the surface of the cured product of the photocurable adhesive layer after the adhesive layer is peeled off. The median of the trace width of the wire drawing trace is 120 nm to 200 nm. 如請求項1或請求項2所述的光硬化性黏著劑的評價方法,其中所述光硬化性黏著劑含有:具有反應性官能基的(甲基)丙烯酸系共聚物、光聚合起始劑、及交聯劑,所述交聯劑具有2個以上能夠與所述反應性官能基反應的官能基。The method for evaluating a photocurable adhesive according to claim 1 or 2, wherein the photocurable adhesive contains: a (meth)acrylic copolymer having a reactive functional group and a photopolymerization initiator , And a crosslinking agent, the crosslinking agent having two or more functional groups that can react with the reactive functional group. 如請求項3所述的光硬化性黏著劑的評價方法,其中所述(甲基)丙烯酸系共聚物含有(甲基)丙烯酸作為單體單元。The method for evaluating a photocurable adhesive according to claim 3, wherein the (meth)acrylic copolymer contains (meth)acrylic acid as a monomer unit. 如請求項1至請求項4中任一項所述的光硬化性黏著劑的評價方法,其中所述接著劑層含有:環氧樹脂、環氧樹脂硬化劑、及具有環氧基的(甲基)丙烯酸系共聚物。The method for evaluating a photocurable adhesive according to any one of claims 1 to 4, wherein the adhesive layer contains an epoxy resin, an epoxy resin curing agent, and (former) having an epoxy group Base) acrylic copolymer. 一種切割-黏晶一體型膜的製造方法,包括: 在基材層上形成光硬化性黏著劑層的步驟,所述光硬化性黏著劑層包括藉由如請求項1至請求項5中任一項所述的光硬化性黏著劑的評價方法而判定為良好的光硬化性黏著劑;以及 在所述光硬化性黏著劑層上形成接著劑層的步驟。A manufacturing method of cutting-bonding integrated film includes: A step of forming a photocurable adhesive layer on a substrate layer, the photocurable adhesive layer including the method for evaluating the photocurable adhesive according to any one of claims 1 to 5 Judged as a good light-curing adhesive; and The step of forming an adhesive layer on the photocurable adhesive layer. 一種半導體裝置的製造方法,包括: 將藉由如請求項6所述的切割-黏晶一體型膜的製造方法而獲得的切割-黏晶一體型膜的所述接著劑層貼附於半導體晶圓的步驟; 藉由切割將所述半導體晶圓、所述接著劑層及所述光硬化性黏著劑層單片化的步驟; 對所述光硬化性黏著劑層照射紫外線,形成所述光硬化性黏著劑層的硬化物的步驟; 自所述光硬化性黏著劑層的硬化物拾取附著有所述接著劑層的半導體元件的步驟;以及 經由所述接著劑層將所述半導體元件接著在半導體元件搭載用的支撐基板的步驟。A method for manufacturing a semiconductor device includes: The step of attaching the adhesive layer of the dicing-bonding integrated film obtained by the method of manufacturing the dicing-bonding integrated film according to claim 6 to a semiconductor wafer; A step of singulating the semiconductor wafer, the adhesive layer, and the photocurable adhesive layer by dicing; The step of irradiating the photo-curable adhesive layer with ultraviolet rays to form a cured product of the photo-curable adhesive layer; A step of picking up the semiconductor element to which the adhesive layer is attached from the cured product of the photocurable adhesive layer; and The step of attaching the semiconductor element to a supporting substrate for mounting a semiconductor element via the adhesive layer. 如請求項7所述的半導體裝置的製造方法,其中所述半導體晶圓的厚度為35 μm以下。The method of manufacturing a semiconductor device according to claim 7, wherein the thickness of the semiconductor wafer is 35 μm or less. 如請求項7或請求項8所述的半導體裝置的製造方法,其中所述切割應用隱形切割。The method for manufacturing a semiconductor device according to claim 7 or 8, wherein the cutting applies stealth cutting. 一種切割-黏晶一體型膜,依次包括基材層、光硬化性黏著劑層、及接著劑層,所述光硬化性黏著劑層包含藉由如請求項1至請求項5中任一項所述的光硬化性黏著劑的評價方法而判定為良好的光硬化性黏著劑。A dicing-bonding integrated film, comprising a substrate layer, a light-curing adhesive layer, and an adhesive layer in sequence. The light-curing adhesive layer includes any one of claims 1 to 5 The evaluation method of the photocurable adhesive described above was judged to be a good photocurable adhesive.
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