TWI816004B - Evaluation method of photocurable adhesive, dicing-die bonding integrated film and manufacturing method thereof, and semiconductor device manufacturing method - Google Patents

Evaluation method of photocurable adhesive, dicing-die bonding integrated film and manufacturing method thereof, and semiconductor device manufacturing method Download PDF

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TWI816004B
TWI816004B TW108147291A TW108147291A TWI816004B TW I816004 B TWI816004 B TW I816004B TW 108147291 A TW108147291 A TW 108147291A TW 108147291 A TW108147291 A TW 108147291A TW I816004 B TWI816004 B TW I816004B
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adhesive layer
photocurable adhesive
photocurable
meth
cutting
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TW108147291A
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TW202035604A (en
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彼谷美千子
尾崎義信
大久保恵介
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日商力森諾科股份有限公司
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N19/00—Investigating materials by mechanical methods
    • G01N19/04—Measuring adhesive force between materials, e.g. of sealing tape, of coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives 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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    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly 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
    • H01L21/52—Mounting semiconductor bodies in containers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L21/683—Apparatus 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
    • H01L21/6835—Apparatus 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
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
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    • H01—ELECTRIC ELEMENTS
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture 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
    • H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
    • H01L21/78—Manufacture 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus 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
    • H01L2221/683—Apparatus 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
    • H01L2221/68304—Apparatus 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
    • H01L2221/68327—Apparatus 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L2221/67—Apparatus 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
    • H01L2221/683—Apparatus 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
    • H01L2221/68304—Apparatus 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
    • H01L2221/68381—Details of chemical or physical process used for separating the auxiliary support from a device or wafer
    • H—ELECTRICITY
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    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition 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
    • H01L2224/32221—Disposition 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
    • H01L2224/32225—Disposition 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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    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—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
    • H01L2224/48221—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
    • H01L2224/48225—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
    • H01L2224/48227—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 connecting the wire to a bond pad of the item
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    • H01L2924/1531—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface
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  • Adhesive Tapes (AREA)
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Abstract

本發明揭示了一種切割-黏晶一體型膜所使用的光硬化性黏著劑的評價方法。另外，揭示了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，揭示了使用此種切割-黏晶一體型膜的半導體裝置的製造方法。The present invention discloses a method for evaluating photocurable adhesive used in cutting-crystallization integrated films. In addition, a cutting-crystallization integrated film based on this evaluation method of a photocurable adhesive and a manufacturing method thereof are disclosed. Furthermore, a method of manufacturing a semiconductor device using such a dicing-bonding integrated film is disclosed.

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, cutting-die 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 cutting-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 wafers to a lead frame, a packaging substrate, or the like. In the manufacture of such semiconductor wafers, a dicing-die integrated film that is a combination of a dicing film and a die-adhesive film having a photohardening film for fixing the semiconductor wafer during the dicing step is mainly used. A photocurable adhesive layer of a flexible adhesive, the die-adhesive film having an adhesive layer for bonding a semiconductor chip to a lead frame, a packaging 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。 In recent years, as an example of a method of manufacturing a semiconductor wafer by singulating a thin semiconductor wafer, it has been proposed to form a modified layer by irradiating the inside of the semiconductor wafer with laser light on the planned cutting line without completely cutting the semiconductor wafer. , so-called stealth dicing in which the semiconductor wafer is cut by expanding the dicing film (for example, Patent Document 1). From the viewpoint of preventing damage in the subsequent pickup step, semiconductor wafers singulated by stealth dicing are required to peel off the die attach film and the dicing film with smaller force. However, if small force is used to peel off, the peeling time will become longer and the productivity will be adversely affected. tendency. Therefore, in the dicing-die integrated film used in the manufacture of thin semiconductor wafers, there is a demand for a photocurable adhesive that can constitute a photocurable adhesive layer by improving the success rate of pickup and shortening the peeling time of pickup. Selection becomes important.

[現有技術文獻] [Prior art documents]

專利文獻1：日本專利特開2003-338467號公報 Patent Document 1: Japanese Patent Application Publication No. 2003-338467

專利文獻2：日本專利特開2004-017639號公報 Patent Document 2: Japanese Patent Application Publication No. 2004-017639

專利文獻3：日本專利特開2006-089521號公報 Patent Document 3: Japanese Patent Application Publication No. 2006-089521

專利文獻4：日本專利特開2006-266798號公報 Patent Document 4: Japanese Patent Application Publication No. 2006-266798

專利文獻5：日本專利特開2014-055250號公報 Patent document 5: Japanese Patent Application Publication No. 2014-055250

專利文獻6：日本專利特開2014-181258號公報 Patent Document 6: Japanese Patent Application Publication No. 2014-181258

專利文獻7：日本專利特開2015-028146號公報 Patent Document 7: Japanese Patent Application Publication 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 manufacturing 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 will have excellent pick-up properties. In many cases, it can only be determined during actual use. Just known.

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 used for a cutting-die 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。 Factors that influence the peelability of the adherend and the adhesive include the adhesive force of the adhesive (the overall properties of the adhesive), the interaction at the interface between the adherend and the adhesive (the surface properties of the adhesive), etc. . Generally speaking, it is known that the overall characteristics Properties contribute more to peelability than surface properties, and there is a tendency to control peelability by adjusting overall properties. However, it is considered that the influence of surface characteristics cannot be ignored regarding the pick-up properties of thin semiconductor wafers. For example, the deformation form of the adhesive between the adherend and the adhesive. For example, when the adherend and the adhesive are peeled off, the adhesive changes depending on the situation. Drawn wire, which deforms as much as a thread or a wall without breaking between the adherend and the bonded object, also has a great influence on the peelability. In conventional industrial fields, the occurrence of stringing was considered to be a defective phenomenon of adhesives, and the peelability was improved by reducing or suppressing the occurrence of stringing (for example, refer to the above-mentioned Patent Documents 2 to 7, etc.). Under such circumstances, the present inventors conducted diligent research and found that when a specific stringing phenomenon is observed when the adherend and the adhesive are peeled off, compared with the case where the stringing phenomenon is not observed, due to The present invention was completed by propagation of the breaking impact of wire drawing, faster peeling progress, and increased peeling speed.

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， One aspect of the present invention provides a method for evaluating photocurable adhesives used for cutting-die bonding integrated films. The evaluation method of the photocurable adhesive includes: in the first step, preparing a cutting-crystallization integrated film in which a base material layer, a photocurable adhesive layer containing a photocurable adhesive, and an adhesive layer are laminated in this order. The photocurable adhesive layer is irradiated with ultraviolet rays under the following irradiation conditions to form a cured product of the photocurable adhesive layer, and the peeling force when the adhesive layer and the cured product of the photocurable adhesive layer are peeled off under the following peeling conditions is measured; In the second step, prepare a cutting-crystal integrated film in which a base material layer, a photocurable adhesive layer containing a photocurable adhesive, and an adhesive layer are laminated in sequence, and the photocurable adhesive is adhered under the following heating and cooling conditions. The agent layer is processed, and the photocurable adhesive layer is irradiated with ultraviolet rays under the following irradiation conditions to form To form a cured product of the photocurable adhesive layer, peel off the adhesive layer and the cured product of the photocurable adhesive layer under the following peeling conditions, and observe the photocurable adhesive after the adhesive layer is peeled off using a scanning probe microscope. The surface of the hardened object of the layer is measured to measure the number and width of the drawing marks on the surface; and the third step is to determine whether the light-hardening adhesive is good based on the peeling force and the number and width of the drawing marks.

(照射條件) (irradiation conditions)

照射強度：70mW/cm2 Irradiation intensity: 70mW/cm 2

累計光量：150mJ/cm2 Cumulative light intensity: 150mJ/cm 2

(剝離條件) (stripping conditions)

溫度：25±5℃ Temperature: 25±5℃

濕度：55±10% Humidity: 55±10%

剝離角度：30° Peeling angle: 30°

剝離速度：600mm/分鐘 Peeling speed: 600mm/min

(加熱冷卻條件) (Heating and cooling conditions)

加熱處理：65℃、15分鐘 Heat treatment: 65℃, 15 minutes

冷卻處理：空冷靜置30分鐘，直至25±5℃。 Cooling treatment: Leave in air for 30 minutes until 25±5℃.

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。 This evaluation method of a photocurable adhesive is useful for predicting in advance whether a photocurable adhesive expected to be used as a photocurable adhesive layer of a dicing-die bonding integrated film has excellent pick-up 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。 The third step may be a step of determining whether the photocurable adhesive is good or not based on whether the peeling force, the number of drawing traces, and the trace width satisfy the following conditions (a) and (b).

條件(a)：剝離力為0.70N/25mm以下。 Condition (a): Peeling force is 0.70N/25mm or less.

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25μm×25μm的區域，區域內的拉絲痕跡的痕跡寬度的中位數為120nm~200nm。 Condition (b): There is a 25 μm × 25 μm area with a number of 15 or more wire drawing marks on the surface of the cured product of the photocurable adhesive layer after peeling off the adhesive layer, and the median of the mark widths of the wire drawing marks in the area The number is 120nm~200nm.

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 acid copolymer having a reactive functional group, a photopolymerization initiator, and a cross-linking agent having two or more functional groups capable of reacting with the reactive functional group. The (meth)acrylic acid copolymer may further contain (meth)acrylic acid 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 acid 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 for manufacturing a cutting-die integrated film, which includes the step of forming a photo-curing adhesive layer on a base material layer, the photo-curing adhesive layer comprising: The photocurable adhesive is judged to be good according to the photocurable adhesive evaluation method; 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 for manufacturing a semiconductor device, which includes the steps of attaching an adhesive layer of the dicing-die integrated film obtained by the manufacturing method to a semiconductor wafer; Steps for singulating semiconductor wafers, adhesive layers, and photocurable adhesive layers; steps for irradiating the photocurable adhesive layer with ultraviolet rays to form a cured product of the photocurable adhesive layer; self-photocurable adhesive The step of picking up the semiconductor element to which the adhesive layer is attached using the cured material of the layer; and the step of bonding the semiconductor element to the supporting substrate for mounting the semiconductor element via the adhesive layer. steps.

半導體晶圓的厚度可以在35μm以下。切割可以應用隱形切割。 The thickness of semiconductor wafers can be below 35μm. Invisible cuts can be applied to cuts.

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 and die-bonding integrated film, which is provided with a base material layer and photocurable properties of 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 used for a cutting-die bonding integrated film is provided. In addition, according to the present invention, there is provided a cutting and die-bonding integrated film based on the evaluation method of such a photocurable adhesive and a manufacturing method thereof. Furthermore, according to the present invention, a method of manufacturing a semiconductor device using such a dicing-die integrated film is provided.

1:切割-黏晶一體型膜 1: Cutting-crystallization integrated film

2:保護膜 2: Protective film

4:改質層 4: Modified layer

10:基材層 10:Substrate layer

20:光硬化性黏著劑層 20: Light hardening adhesive layer

20ac:光硬化性黏著劑層的硬化物 20ac: Hardened product of photocurable adhesive layer

30、30a:接著劑層 30, 30a: Adhesive layer

42:頂針 42: thimble

44:抽吸夾頭 44:Suction chuck

50:帶接著劑層的半導體元件 50: Semiconductor components with adhesive layer

60:半導體元件搭載用支撐基板 60:Support substrate for mounting semiconductor components

60a:表面 60a: Surface

70:打線接合線 70: Wire bonding wire

80:樹脂密封材 80: Resin sealing material

90:焊球 90: Solder ball

100:半導體裝置 100:Semiconductor device

W1、W2:半導體晶圓 W1, W2: semiconductor wafer

Wa:半導體元件 Wa: semiconductor element

Ws:主面 Ws: Main side

Wx:拉絲痕跡X的兩端(極小值)彼此的寬度 Wx: The width of the two ends (minimum value) of the drawing trace X from each other

Wy:基準高度處的寬度 Wy: Width at base height

H1、H2:厚度 H1, H2: Thickness

Hy:基準高度 Hy: base height

X、Y:拉絲痕跡 X, Y: drawing traces

iii-iii、iv-iv:線 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。 FIG. 1 is a schematic cross-sectional view showing one embodiment of the cutting-die bonding integrated film.

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。 2(a) and 2(b) are diagrams showing an example of the shape image distribution and the phase image distribution of the surface of the cured product of the photocurable adhesive layer, and FIG. 2(a) is the shape Image distribution, (b) in Figure 2 is the phase image distribution.

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。 3(a) and 3(b) are diagrams showing an example of the cross-sectional distribution on the surface of the cured product of the photocurable adhesive layer. FIG. 3(a) is the shape image distribution, and FIG. 3((a) is the shape image distribution. b) is the cross-sectional distribution of the iii-iii line of the drawing mark X in Figure 3(a).

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。 Figure 4 (a) and Figure 4 (b) show the curing of the photocurable adhesive layer. An example of cross-sectional distribution on the surface of an object is shown. Figure 4 (a) is the shape image distribution, and Figure 4 (b) is the cross-sectional distribution along the iv-iv line of the drawing trace Y in Figure 4 (a).

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。 5(a) to 5(e) are schematic cross-sectional views for explaining one embodiment of a manufacturing method of a semiconductor device, and FIG. 5(a), FIG. 5(b), and FIG. 5(c) ), Figure 5(d) and Figure 5(e) are schematic cross-sectional views showing each step.

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。 6(f) to 6(i) are schematic cross-sectional views for explaining one embodiment of a manufacturing method of a semiconductor device, and FIG. 6(f), FIG. 6(g), and FIG. 6(h) ), and (i) of FIG. 6 are schematic cross-sectional views showing each step.

圖7是表示半導體裝置的一個實施方式的示意剖面圖。 FIG. 7 is a schematic cross-sectional view showing one embodiment of the semiconductor device.

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, embodiments of the present invention will be described with reference to the drawings as appropriate. However, the present invention is not limited to the following embodiments. In the following embodiments, the above-described constituent elements (including steps, etc.) are not essential unless otherwise specified. The sizes of the constituent elements in each drawing are conceptual, and the relative size relationship between the constituent elements is not limited to what is shown in each drawing.

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 their ranges in this specification, and does not limit the present invention. In this specification, the numerical range represented by "~" means the range including the numerical values written before and after "~" as the minimum value and the maximum value respectively. Within the numerical ranges described in stages in this specification, the upper limit or lower limit described in one numerical range may also be replaced by the upper limit or lower limit of the numerical range described in another stage. 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 its corresponding methacrylate. The same applies to other similar expressions such as (meth)acrylyl 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 and becomes silky. Large deformation. "String mark" refers to the partial shrinkage of the adhesive due to rupture of the adhesive after the occurrence of drawing, partial shrinkage after large deformation, or partial shrinkage of the adhesive after being irreversibly stretched or peeled off from the adherend after large deformation. The surface was observed in the form of traces (protrusions).

[光硬化性黏著劑的評價方法] [Evaluation method for photocurable adhesives]

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。 The evaluation method of the photocurable adhesive used in the cutting-die bonding integrated film according to one embodiment includes: a first step of preparing a base material layer and a photocurable adhesive layer including a photocurable adhesive layer laminated in sequence; As well as the cutting and die-bonding integrated film of the adhesive layer, the photocurable adhesive layer is irradiated with ultraviolet rays under specific irradiation conditions to form a hardened product of the photocurable adhesive layer, and the peeling of the adhesive under specific peeling conditions is measured. The peeling force when the layer and the photo-curing adhesive layer are cured; the second step is to prepare the cutting and die-bonding of the base material layer, the photo-curing adhesive layer containing the photo-curing adhesive layer, and the adhesive layer in order. In an integrated film, the photocurable adhesive layer is processed under specific heating and cooling conditions, and the photocurable adhesive layer is irradiated with ultraviolet rays under specific irradiation conditions to form a hardened product of the photocurable adhesive layer. The hardened product of the adhesive layer and the photo-curing adhesive layer is peeled off under specific peeling conditions, and the photo-curing adhesive after the adhesive layer is peeled is observed using a scanning probe microscope. The surface of the hardened object of the layer is measured, and the number and width of the drawing marks on the surface are measured; and the third step is to determine whether the light-curing adhesive is good based on the peeling force and the number and width of the drawing marks.

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。 Hereinafter, the photocurable adhesive to be evaluated, the dicing and die-bonding integrated film including the photocurable adhesive layer including the photocurable adhesive, and the manufacturing method thereof are first described, and then the influencing factors of the stringing phenomenon are examined. , and finally explain each step.

<光硬化性黏著劑> <Light-hardening adhesive>

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。 In the evaluation method of the photocurable adhesive of this embodiment, the photocurable adhesive hardened by irradiation of ultraviolet rays can be evaluated. Hereinafter, as an example of the photocurable adhesive to be evaluated, a (meth)acrylic acid copolymer containing a reactive functional group, a photopolymerization initiator, and a photocurable adhesive having two or more reactive functional groups are described. The photocurable adhesive with functional group cross-linking agent will be described.

(具有反應性官能基的(甲基)丙烯酸共聚物) ((Meth)acrylic acid copolymer with reactive functional groups)

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。 A (meth)acrylic acid copolymer having a reactive functional group can be produced, for example, by combining one or two or more (meth)acrylate monomers (a1) or (meth)acrylic acid, and a copolymer 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, for example, selected from the group consisting of (meth)acrylic acid linear or branched alkyl ester, alicyclic (meth)acrylate, aromatic (meth)acrylate, (meth)acrylate, Alkoxyalkyl acrylate, alkoxy (poly)alkylene glycol (meth)propylene At least one of the group consisting of acid ester, (meth)acrylic acid alkoxyalkoxyalkyl ester, and (meth)acrylic acid dialkylaminoalkyl ester.

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 (meth)acrylic acid linear or branched alkyl esters include: (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid n-propyl ester, (meth)acrylic acid n-butyl ester Ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-(meth)ethylhexyl 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。 Examples of the alicyclic (meth)acrylate include: (meth)acrylic acid cyclohexyl, (meth)acrylic acid isobornyl, and (meth)acrylic acid dicyclopentyl.

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。 Examples of aromatic (meth)acrylates include phenoxyethyl (meth)acrylate and the like.

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 (meth)acrylic acid alkoxyalkyl esters include: (meth)acrylic acid ethoxyethyl ester, (meth)acrylic acid butoxyethyl ester, 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。 Examples of the alkoxy (poly)alkylene glycol (meth)acrylate include methoxy diethylene glycol (meth)acrylate, ethoxy diethylene glycol (meth)acrylate, methyl Oxytriethylene glycol (meth)acrylate, butoxytriethylene glycol (meth)acrylate, and 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 ester and (meth)acrylic acid 2-ethoxyethoxyethoxy 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: (meth)acrylic acid N,N-dimethylaminoethyl ester and (meth)acrylic acid N,N-diethylamine base 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 the 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。 Examples of the polymerizable compound (a2) having a hydroxyl group as a reactive functional group include: (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxybutyl, (meth)acrylic acid 2 -Hydroxyalkyl (meth)acrylate, etc. such as hydroxypropyl ester.

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。 Examples of the polymerizable compound (a2) having an epoxy group as a reactive functional group include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and the like. Oxygen-based (meth)acrylate, 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 acid copolymer may contain (meth)acrylic acid as a monomer unit. 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 vinyltoluene.

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 acid copolymer having reactive functional groups may further have functional groups 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 a polymerizable double bond may be a (meth)acrylyl group, but is not limited thereto. A (meth)acrylic acid copolymer having a chain-polymerizable functional group can be obtained by reacting a (meth)acrylic acid copolymer having a reactive functional group One or two or more compounds (b) of a functional group capable of reacting with a functional group and a functional group capable of chain polymerization are reacted to introduce a functional group capable of chain polymerization into the side chain of the (meth)acrylic acid 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。 Examples of the functional group that reacts with the reactive functional group (epoxy group, hydroxyl group, etc.) include an isocyanate group.

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」)。 Specific examples of the compound (b) having an isocyanate group include 2-methacryloyloxyethyl isocyanate (for example, manufactured by Showa Denko Co., Ltd., trade name "Karenz MOI").

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0.3mmol/g~1.5mmol/g。 Relative to the (meth)acrylic acid copolymer with reactive functional groups, the content of compound (b) may be 0.3mmol/g~1.5mmol/g.

具有反應性官能基的(甲基)丙烯酸共聚物的酸值例如可為0mgKOH/g~150mgKOH/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0mgKOH/g~150mgKOH/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 acid copolymer having reactive functional groups can be, for example, 0 mgKOH/g to 150 mgKOH/g. The hydroxyl value of the (meth)acrylic acid copolymer having reactive functional groups can be, for example, 0 mgKOH/g to 150 mgKOH/g. The acid value and hydroxyl value are measured according to 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 acid copolymer with reactive functional groups can be 100,000 to 1,000,000, 200,000 to 800,000, or 300,000 to 700,000. The weight average molecular weight is a polystyrene-converted value obtained by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene.

(光聚合起始劑) (Photopolymerization initiator)

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。 As a photopolymerization initiator, as long as it starts polymerization by irradiation with ultraviolet rays The photopolymerization initiator is not particularly limited, and examples thereof include photoradical polymerization initiators. Examples of the photoradical polymerization initiator include benzoin ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one; -Hydroxyketone; 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one and other α-aminoketones; 1-[4-(phenylthio) 1,2-Octanedione-2-(benzoyl)oxime and other oxime esters; bis(2,4,6-trimethylbenzoyl)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-phenyl acridine; N-phenylglycine, coumarin, etc. These may 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 to 10 parts by mass, or 0.5 to 5 parts by mass relative to 100 parts by mass of the (meth)acrylic acid copolymer.

(交聯劑) (cross-linking agent)

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。 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 groups (epoxy group, hydroxyl group, etc.) of the (meth)acrylic copolymer having a reactive functional group. Examples of the bond formed by the reaction between the crosslinking agent and the (meth)acrylic copolymer having a reactive functional group include an ester bond, an ether bond, an amide bond, an imine bond, and a carbamate bond. 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。 Examples of the crosslinking agent include compounds having two or more isocyanate groups in one molecule. When using this compound, due to its interaction with the (meth)acrylic acid The reactive functional groups of the copolymer are easy to react, so the copolymer tends to easily 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。 Examples of compounds having two or more isocyanate groups in one molecule include 2,4-methylphenylene diisocyanate, 2,6-methylphenylene diisocyanate, 1,3-methylphenylene diisocyanate, 1 , 4-Diphenyldiisocyanate, 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, lysate 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」)。 Specific examples of compounds having two or more isocyanate groups in one molecule include polyfunctional isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate L").

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 cross-linking agent may be a reaction product of the isocyanate compound and a polyol having two or more hydroxyl groups in one molecule (isocyanate group-containing oligomer). Examples of the polyhydric alcohol having two or more hydroxyl groups in one molecule include ethylene glycol, propylene glycol, butylene glycol, 1,6-hexanediol, 1,8-octanediol, and 1,9-nonanediol. 1,10-Decanediol, 1,11-Undecanediol, 1,12-Dodecanediol, glycerin, pentaerythritol, dipentaerythritol, 1,4-cyclohexanediol, 1,3-cyclohexane Diols etc.

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。 The cross-linking agent may be a reaction product (isocyanate group-containing oligomer) of a multifunctional 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 cross-linking agent, the photo-curable adhesive layer 20 can form a denser cross-linked structure. tendency.

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 cross-linking agent may be, for example, 3% to 50% by mass relative to the total mass of the (meth)acrylic acid copolymer.

<切割-黏晶一體型膜及其製造方法> <Cutting-crystal bonding integrated film and its manufacturing method>

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。 FIG. 1 is a schematic cross-sectional view showing one embodiment of the cutting-die bonding integrated film. The dicing-die bonding integrated film 1 has a base material layer 10, a photocurable adhesive layer 20 containing a photocurable adhesive, and an adhesive layer 30 laminated in this order.

(基材層) (Substrate layer)

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。 The base material layer 10 is not particularly limited as long as a known polymer sheet or film can be used and it contains 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 ethylene and polymethylpentene; ethylene-vinyl acetate copolymer; ionomer resin; ethylene-(meth)acrylic acid copolymer; ethylene-(meth)acrylate (random, alternating) copolymer ; Ethylene-propylene copolymer; Ethylene-butylene copolymer; Ethylene-hexene copolymer; Polyurethane; Polyethylene terephthalate, polyethylene naphthalate and other polyesters; Polycarbonate Ester; polyimide; polyetheretherketone; polyetherimide; 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 may be materials mixed with plasticizers, silica, anti-adhesive materials, lubricants, antistatic agents, etc.

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 material layer 10 has properties such as Young's modulus, stress relaxation, melting point, etc. In terms of price, recycling of waste materials after use, etc., it is preferable to have one selected from the group consisting of polyethylene, polypropylene, polyethylene-polypropylene random copolymers, and polyethylene-polypropylene block copolymers. The surface of at least one material as the main component is in contact with the photohardening adhesive layer 20 . The base material layer 10 may be a single layer or a multilayer including two or more layers of different materials. From the viewpoint of controlling the adhesion with the photocurable adhesive layer 20 described below, the base material layer 10 may be subjected to surface roughening treatment such as corona discharge treatment and matting treatment as necessary.

基材層10的厚度例如可以是70μm~120μm或80μm~100μm。如果基材層10的厚度為70μm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120μm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 material layer 10 may be, for example, 70 μm to 120 μm or 80 μm to 100 μm. If the thickness of the base material layer 10 is 70 μm or more, damage due to propagation tends to be further suppressed. When the thickness of the base material layer 10 is 120 μm or less, the stress during pickup easily reaches the adhesive layer, and the pickup property tends to be more excellent.

(光硬化性黏著劑層) (Photo-hardening adhesive layer)

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。 The photocurable adhesive layer 20 is a layer containing the photocurable adhesive. The photocurable adhesive layer 20 is formed on the base material layer 10 . As a method of forming the photocurable adhesive layer 20 on the base material layer 10, for example, preparing a varnish for forming a photocurable adhesive layer, applying the varnish to the base material layer 10, and removing volatilization of the varnish Components, a method of forming a photohardening adhesive layer 20; coating the varnish on a release-treated film, removing volatile components of the varnish to form a photohardening adhesive layer 20, and photohardening the resulting A method of transferring the adhesive layer 20 to the base material 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溶解，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. Organic solvents can The (meth)acrylic copolymer having a reactive functional group, the photopolymerization initiator, and the cross-linking agent having two or more functional groups capable of reacting with the reactive functional group are dissolved and volatilized by heating. 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, methylethyl Ketones such as ketone, methyl isobutyl ketone, and cyclohexanone; esters such as methyl acetate, ethyl acetate, and γ-butyrolactone; carbonates such as ethyl carbonate and propyl carbonate; ethylene glycol monomethyl ether , ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether and other polyol alkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and other polyol alkyl ethers base ether acetate; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and other amides, etc. These may be used individually by 1 type, and may be used in combination of 2 or more types. Based on the total mass of the varnish, the solid content concentration of the varnish can be 10 mass% to 60 mass%.

光硬化性黏著劑層20的厚度例如可為1μm~200μm、3μm~50μm、或5μm~30μm。 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) (adhesive layer)

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。 The adhesive layer 30 is a layer containing an adhesive. The adhesive is not particularly limited as long as it is used in the field of crystal adhesion films. Hereinafter, an adhesive containing an epoxy resin, an epoxy resin hardener, and a (meth)acrylic copolymer having an epoxy group will be described as an example of the adhesive. The adhesive layer 30 containing such an adhesive has excellent adhesion between wafers and substrates and between wafers, can provide electrode embedding properties, wire embedding properties, etc., and can be used at low temperatures in the die bonding step. Continue below.

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。 Examples of the epoxy resin include 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 novolak type epoxy resin, bisphenol F novolak type epoxy resin, dicyclopentadiene skeleton-containing epoxy resin, stilbene-type epoxy resin, triazine skeleton-containing epoxy resin, Fluorene skeleton epoxy resin, trisphenolmethane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, multifunctional phenols , anthracene and other polycyclic aromatic diglycidyl ether compounds. These can be used individually by 1 type or in combination of 2 or more types.

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醛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, for example, a phenolic resin. The phenolic resin can be used without particular restrictions as long as it has a phenolic hydroxyl group in the molecule. Examples of the phenolic resin include phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, and/or α- Novolac-type phenolic resin obtained by condensation or co-condensation of naphthols, β-naphthol, dihydroxynaphthalene and other naphthols with compounds with aldehyde groups such as formaldehyde under an aldehyde catalyst, and is composed of allylized bisphenol A , allylated bisphenol F, allylated naphthalenediol, phenol novolac, phenols such as phenol and/or naphthols and dimethoxy-p-xylene or bis(methoxymethyl)biphenyl Synthesized phenol aralkyl resin, naphthol aralkyl resin, etc. These can be used individually by 1 type or in combination of 2 or more types.

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 in which glycidyl (meth)acrylate as a raw material is adjusted to an amount of 0.5 mass % to 6 mass % with respect to the obtained copolymer. When this amount is 0.5% by mass or more, it is easy to obtain high When the amount is 6% by mass or less, gelation tends to be suppressed. The remainder of the glycidyl (meth)acrylate may be a mixture of an alkyl (meth)acrylate having an alkyl group with 1 to 8 carbon atoms, such as methyl (meth)acrylate, 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 taking into consideration the Tg (glass transition temperature) of the obtained (meth)acrylic copolymer having an epoxy group. If Tg is -10° C. or higher, the viscosity of the adhesive layer 30 in the B-stage state tends to become better, and the handleability tends to be excellent. The upper limit of Tg of the (meth)acrylic copolymer having an epoxy group may be, for example, 30°C.

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 more than 100,000, or may be 300,000 to 3 million, or 500,000 to 2 million. If the weight average molecular weight is 3 million or less, the ability to control the filling ability between the semiconductor wafer and the supporting substrate tends to decrease. The weight average molecular weight is a polystyrene-converted value obtained by gel permeation chromatography (GPC) using a calibration curve of 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 the hardening accelerator include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-phenyl. Imidazolium trimellitate. These can be used individually by 1 type or in combination of 2 or more types.

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 if necessary. Examples of the inorganic filler include: aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whiskers, Boron nitride, crystalline silicon dioxide, amorphous silicon dioxide, etc. These can be used individually by 1 type or in combination of 2 or more types.

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 to the release-treated film is exemplified. The adhesive layer 30 is formed, and the obtained adhesive layer 30 is transferred to the photocurable adhesive layer 20 . The varnish for forming an adhesive layer contains an epoxy resin, an epoxy resin hardener, a (meth)acrylic copolymer having an epoxy group, and an organic solvent. The organic solvent may be the same as the organic solvent exemplified as the organic solvent used in the varnish for forming the photocurable adhesive layer.

接著劑層30的厚度例如可以是1μm~300μm、5μm~150μm、或10μm~100μm。 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] [Factors affecting wire drawing]

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。 Stringing may occur due to the interaction at the interface between the adhesive layer and the hardened material of the photocurable adhesive layer. Therefore, as one of the influencing factors of wire drawing phenomenon, the type and content of cross-linking agent are listed. For example, if the content of the cross-linking agent is reduced, the number of drawing marks tends to increase and the width of the drawing marks also tends to become larger. Therefore, by adjusting the type and content of the cross-linking agent, the number and width of drawing marks can be controlled. In addition, coating conditions are cited as factors affecting the stringing phenomenon other than the composition of the photocurable adhesive. The number and width of drawing traces can be controlled by changing coating conditions such as coating speed, coating temperature, and air volume. Furthermore, factors that influence the stringing phenomenon include: the bonding adhesive layer and photocuring during the production of the cutting-bonding integrated film. conditions when forming the adhesive layer, the surface physical properties (surface roughness, surface free energy, etc.) of the adhesive layer and the photocurable adhesive layer, the molecular weight, polarity and Glass transfer point.

<第一步驟> <First step>

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。 In this step, first, a dicing and die-bonding integrated film for evaluation is prepared in which a base material layer, a photocurable adhesive layer containing a photocurable adhesive to be evaluated, and an adhesive layer are laminated in this order.

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層的厚度例如可為10μm。接著劑層的厚度例如可以是10μm。 In the dicing and die bonding integrated film for evaluation, the types of the base material layer, the photocurable adhesive layer, and the adhesive layer are not particularly limited, and any selected dicing and die bonding integrated film can be used. The thickness of the photocurable adhesive layer including the photocurable adhesive to be evaluated may be, for example, 10 μm. The thickness of the adhesive layer may be, for example, 10 μm.

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365nm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 is irradiated with ultraviolet rays under the following irradiation conditions to cure the photocurable adhesive layer, thereby forming a cured product of the photocurable adhesive layer (a layer including the cured product of the photocurable adhesive). The most suitable light source for the ultraviolet light source can be appropriately selected according to the type of photopolymerization initiator used. The ultraviolet light source is not particularly limited, but may be one selected from the group consisting of a low-pressure mercury lamp, a far-UV 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 central wavelength of 365 nm. In addition, in order to reduce the influence of heat generated by the light source during ultraviolet irradiation, a cold mirror or the like may be used in combination.

(照射條件) (irradiation conditions)

照射強度：70mW/cm2 Irradiation intensity: 70mW/cm 2

累計光量：150mJ/cm2 Cumulative light intensity: 150mJ/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 off the cured product of the adhesive layer and the photocurable adhesive layer under the following peeling conditions was measured. When peeling off the hardened material of the adhesive layer and the photocurable adhesive layer, it is preferable to attach an adhesive tape, a support tape, etc. to the adhesive layer and stretch them by using a peel strength measuring device that can adjust the peeling angle. Bring on.

(剝離條件) (stripping conditions)

溫度：25±5℃ Temperature: 25±5℃

濕度：55±10% Humidity: 55±10%

剝離角度：30° Peeling angle: 30°

剝離速度：600mm/分鐘 Peeling speed: 600mm/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。 In addition, the lower the peeling angle, the more likely it is that the influence of the base material layer under the peeling force can be eliminated. However, when it is less than 15°, it is difficult to measure. Therefore, 30° is suitable as the test condition for low-angle peel strength.

<第二步驟> <Second step>

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。 In this step, first, a dicing and die-bonding integrated film for evaluation is prepared in which a base material layer, a photocurable adhesive layer containing a photocurable adhesive to be evaluated, and an adhesive layer are laminated in this order. The cutting-crystallization integrated film for evaluation in the second step may be the same as the cutting-crystallization integrated film for evaluation in the first step, but the use has not been carried out. The first step is the determination of the peel force of the film.

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0.1g/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 and die-bonding integrated film for evaluation was processed under the following heating and cooling conditions. If the photo-curing adhesive layer is not processed under heating and cooling conditions, the adhesion between the photo-curing adhesive layer and the adhesive layer may not be sufficient, and it may be difficult to peel off the cured product of the adhesive layer and the photo-curing adhesive layer. A tendency to draw marks is observed. The following heating and cooling conditions are assumed to be the wafer lamination step of a semiconductor device, and wire drawing marks tend to be more easily observed. The heat treatment under heating and cooling conditions is preferably performed from the base material layer side using a heater or the like. Furthermore, it is preferable to use a base material layer that does not undergo deformation such as wrinkles or relaxation during heat treatment (65° C., 15 minutes). During the heat treatment, in order to prevent the dicing-bonding integrated film for evaluation from bending, it is preferable to heat while restraining it with a heat-resistant cloth or the like. The surface pressure at this time can be about 0.1g/ cm2 . If the surface pressure is too high, the photocurable adhesive layer and the adhesive layer will be in excessive close contact, possibly causing excessive stringing marks. In order to prevent the photocurable adhesive layer from hardening, it is preferably performed while shielding from light.

(加熱冷卻條件) (Heating and cooling conditions)

加熱處理：65℃、15分鐘 Heat treatment: 65℃, 15 minutes

冷卻處理：空冷至25±5℃ 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5mm×5mm的尺寸來作為測量樣品。 Next, the photocurable adhesive layer is irradiated with ultraviolet rays under the same irradiation conditions as in the first step to form a cured product of the photocurable adhesive layer, and the adhesive layer is stretched under the same peeling conditions as in the first step to allow the adhesive layer to adhere The hardened material of the agent layer and the photocurable adhesive layer is peeled off. The base material layer including the cured product of the photocurable adhesive layer after the adhesive layer was peeled off was collected as a measurement sample. At this time, in order not to contaminate the adhesive layer The peeled photocurable adhesive layer is recovered as a cured product. In addition, it is preferable to cut the base material layer including the cured product of the photocurable adhesive layer after peeling off the adhesive layer 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 has been peeled off is observed with a scanning probe microscope, and the number of traces and the width of the traces on the surface are measured. From the viewpoint of avoiding the influence of static electricity, the measurement sample is preferably fixed to the scanning probe microscope using a common carbon double-sided tape used for observation with a scanning electron microscope and the like. In addition, from the viewpoint of avoiding the influence of static electricity, observation with a scanning probe microscope is preferably performed after static electricity has been removed in a fixed state for more than half a day (12 hours), or after static electricity has been appropriately removed using a static remover or the like. .

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。 It is preferable that the probe of the scanning probe microscope is provided with a cantilever with a low spring constant that is optimal for measuring the surface of the hardened product of the photocurable adhesive layer after the adhesive layer is peeled off. In addition, observation using a scanning probe microscope is preferably performed in 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。 Drawing marks are observed in the form of traces (protrusions) on the surface of the hardened material of the photocurable adhesive layer. Data on the phase image of the surface of the cured material of the photocurable adhesive layer can be obtained. In the phase image, the hardness is obviously different from the surrounding parts as drawing marks. The number of traces of drawing marks is the number of parts in the phase image where the hardness is obviously different from that of the surroundings.

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1nm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1nm)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 found as follows. First, a scanning probe microscope is used to obtain phase images containing areas whose hardness is significantly different from the surrounding areas. Shape image distribution and phase image distribution on the surface of the cured product of the photocurable adhesive layer at the location. 2(a) and 2(b) are diagrams showing an example of the shape image distribution and the phase image distribution of the surface of the cured product of the photocurable adhesive layer, and FIG. 2(a) is the shape Image distribution, (b) in Figure 2 is the phase image distribution. In the shape image distribution of Figure 2(a), the drawing traces are observed in the form of a bulging upward curve, which is 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, the phase difference being smaller than the surrounding means that it is harder than the surrounding. In the phase image distribution in Figure 2(b), the drawing trace is observed as a portion where the phase difference from the surrounding is 50% or less due to the photohardening adhesive layer being extended to the limit. , represented by the strongest color (in the case of a black and white image, for example black). In this way, drawing traces are observed not only from the shape image distribution but also from the phase image distribution. Next, based on the obtained shape image distribution in FIG. 2(a) , commercially available image processing software (image processing software attached to a scanning probe microscope, etc.) is used to measure all the wire drawing marks that are the object of measurement. Output the profile distribution of the profile line with the largest trace width for each drawing trace. 3(a) and 3(b) are diagrams showing an example of the cross-sectional distribution on the surface of the cured product of the photocurable adhesive layer. FIG. 3(a) is the shape image distribution. FIG. 3 (b) is the cross-sectional distribution of the iii-iii line of the drawing trace X in FIG. 3(a). (b) of FIG. 3 is a cross-sectional distribution when there is substantially no difference in height between the two ends of the observed wire drawing trace (for example, 1 nm or less). In such 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, FIG. 4(a) and FIG. 4(b) show the photocurable adhesive layer. Figure 4(a) is an example of the cross-sectional distribution of the surface of the hardened material. Figure 4(a) is the shape image distribution. Figure 4(b) is the iv-iv line of the drawing mark Y in Figure 4(a). Profile distribution. (b) of FIG. 4 is a cross-sectional distribution when there is a difference in height between the two ends of the observed wire drawing trace (for example, it exceeds 1 nm). In this case, the closest end (minimum value) from the vertex of the drawing trace Y can be set as the reference height Hy, and the width Wy at the reference height Hy can be set as the trace width of the drawing trace Y.

<第三步驟> <Step 3>

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。 In this step, it is determined whether the photocurable adhesive is good or not based on the peeling force and the number and width of the drawing marks. The peeling force, the number of wire drawing traces, and the trace width as evaluation criteria can be appropriately set according to the thickness of the semiconductor wafer and the like.

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35μm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 determining whether the photocurable adhesive is good or not based on whether the peeling force, the number of drawing traces, and the trace width satisfy the following conditions (a) and (b). The dicing and die-bonding integrated film having a photocurable adhesive layer including a photocurable adhesive that satisfies the following condition (a) and the following condition (b) can be preferably used for relatively thin 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0.70N/25mm以下。 Condition (a): Peeling force is 0.70N/25mm or less.

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25μm×25μm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120nm~200nm。 Condition (b): There is a 25 μm × 25 μm area (sometimes referred to as a "specific area") with a number of drawing marks of 15 or more on the surface of the cured product of the photocurable adhesive layer after peeling off the adhesive layer. The median trace width of the drawing traces is 120nm~200nm.

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0.65N/25mm以下或0.63N/25mm以下。條件(a)中的剝離力的下限值沒有特別限制，但可為0.10N/25mm以上。 When a photocurable adhesive that satisfies condition (a) is applied to a cutting-bonding integrated film, the pickup success rate tends to be further improved. The peeling force in condition (a) may be 0.65N/25mm or less or 0.63N/25mm or less. The lower limit of the peeling force in condition (a) is not particularly limited, but may be 0.10N/25mm 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 condition (b) is applied to a cutting-die integrated film, the pick-up peeling time tends to become 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 region 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 good and the peeling speed tends to increase. The number of drawing marks present in a specific area may be 15 or more or 20 or more, or may be 70 or less, 60 or less, or 50 or less. Regarding the peeling speed, both the presence of a specific region and the trace width of the drawing trace existing in the specific region contribute. In a specific area, when the number of drawing marks is 15 or more, stress propagation is high and the peeling speed tends to increase. In a specific area, when the number of drawing marks 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130nm以上或150nm以上，亦可為190nm以下或180nm以下。特定區域存在的拉絲痕跡的痕跡寬度的中位數為120nm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200nm以下時，容易引起拉絲的斷裂，剝離速度有提高的傾向。 When there are specific areas where the number of wire drawing marks is 15 or more on the surface of the hardened material of the photocurable adhesive layer after the adhesive layer has been peeled off, calculate the trace width of the wire drawing marks present 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. When there is an even number of data, the median refers to the average value of the values close to the center. For example, when the number of drawing marks is 15, the width of the eighth drawing mark is the median when the width of the drawing marks is arranged from small to large. When the number of drawing marks is 16, In this case, according to the trace width of the drawing trace, the trace width is from small to The average value of the trace width of the 8th drawing trace and the trace width of the 9th drawing trace when arranged in order of largest is the median. The median trace width of the drawing traces present in a specific area may be 130 nm or more or 150 nm or more, or may be 190 nm or less or 180 nm or less. When the median trace width of the drawing traces present in a specific area is 120 nm or more, the breaking impact of the drawing is likely to propagate, and the peeling speed tends to increase. When the median trace width of the wire drawing traces present in a specific area is 200 nm or less, wire breakage tends to occur, and the peeling speed tends to increase.

[切割-黏晶一體型膜的製造方法] [Manufacturing method of cutting-crystallization integrated film]

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。 A method for manufacturing a dicing-die integrated film according to one embodiment includes forming a photocurable adhesive containing a photocurable adhesive judged to be good by the photocurable adhesive evaluation method on a base material layer. layer; and the step of forming an adhesive layer on the photocurable adhesive layer. The base material layer and the adhesive layer may be the same as those exemplified in the evaluation method of the photocurable adhesive. The formation method of the photocurable adhesive layer and the formation method of the adhesive layer may be the same as the method illustrated in the said evaluation method of the photocurable adhesive.

[切割-黏晶一體型膜] [Cutting-crystal bonding integrated film]

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。 A dicing-die bonding integrated film according to one embodiment includes a base material layer, a photocurable adhesive layer including a photocurable adhesive judged to be good by the photocurable adhesive evaluation method, and an adhesive in this order. layer. The base material layer and the adhesive layer may be the same as those illustrated in the evaluation method of the photocurable adhesive.

[半導體裝置(半導體封裝)的製造方法] [Manufacturing method of semiconductor device (semiconductor package)]

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)。 Figure 5 (a) ~ Figure 5 (e) and Figure 6 (f) ~ Figure 6 (i) are using A schematic cross-sectional view illustrating an embodiment of a method of manufacturing a semiconductor device. The manufacturing method of the semiconductor device of this embodiment includes: a step of attaching the adhesive layer 30 of the dicing-die 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 photo-curing adhesive layer 20 into individual pieces (dicing step); the step of irradiating the photo-curing 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 with adhesive layer 50 ) to which the adhesive layer 30 a is attached (picking up step), and attaching the semiconductor element 50 with the adhesive layer to the semiconductor element mounting support substrate via the adhesive layer 30 a Step 60 (semiconductor element subsequent 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35μm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 include blade dicing, laser cutting, stealth cutting, and the like. In the case where the thickness of the semiconductor wafer W2 is 35 μm or less, stealth cutting may be applied for cutting. Hereinafter, the form in which stealth cutting is mainly used as cutting will be described in detail.

<改質層形成步驟> <Modification layer formation step>

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。 In the case where stealth dicing is used for dicing, the manufacturing method of the semiconductor device may include a modification 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35μm。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35μm以下。 First, a semiconductor wafer W1 of thickness H1 is prepared. The thickness H1 of the semiconductor wafer W1 on which the modified layer is formed may exceed 35 μm. Next, the protective film 2 is attached to one main surface of the semiconductor wafer W1 (see (a) of FIG. 5 ). 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 polishing tape used for back grinding (back polishing) of a semiconductor wafer. Next, half The inside of the conductor wafer W1 is irradiated with laser light to form the modified layer 4 (see (b) of FIG. 5 ), and the side (back side) of the semiconductor wafer W1 opposite to the side to which the protective film 2 is attached is subjected to back polishing. (back surface grinding) and polishing (polishing), thereby producing a semiconductor wafer W2 having the modified layer 4 (see (c) of FIG. 5 ). The thickness H2 of the obtained semiconductor wafer W2 may be 35 μm or less.

<晶圓層壓步驟> <Wafer lamination step>

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))。 Next, the adhesive layer 30 of the dicing-die bonding integrated film 1 is placed on a predetermined device. Next, the dicing-bonding integrated film 1 is attached to the main surface Ws of the semiconductor wafer W2 via the adhesive layer 30 (see (d) of FIG. 5 ), and the protective film 2 of the semiconductor wafer W2 is peeled off (see FIG. 5 of(e)).

<切割步驟> <Cutting steps>

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。 Next, at least the semiconductor wafer W2 and the adhesive layer 30 are separated into individual pieces by dicing (see (f) of FIG. 6 ). When invisible cutting is used for cutting, individual pieces can be carried out by cold expansion and heat shrinkage.

<紫外線照射步驟> <Ultraviolet irradiation step>

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200nm~400nm的紫外線。紫外線照射條件較佳為調整成照度：30mW/cm2~240mW/cm2且照射量為200mJ/cm2~500mJ/cm2。 Next, the photocurable adhesive layer 20 is irradiated with ultraviolet rays to harden the photocurable adhesive in the photocurable adhesive layer 20 to form a cured product of the photocurable adhesive layer (including the photocurable adhesive). layer of hardened material) (see (g) of Figure 6). Therefore, the adhesive force between the photocurable adhesive layer 20 and the adhesive layer 30 can be reduced. In ultraviolet irradiation, it is preferable to use ultraviolet rays with a wavelength of 200 nm to 400 nm. The optimal ultraviolet irradiation condition is to adjust the illumination intensity to: 30mW/cm 2 ~240mW/cm 2 and the irradiation amount to be 200mJ/cm 2 ~500mJ/cm 2 .

<拾取步驟> <Pickup steps>

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。 Next, the semiconductor elements 50 with the adhesive layer obtained by cutting are separated from each other by expanding the base material layer 10 , and are sucked from the base material layer 10 side by the suction chuck 44 and lifted up by the ejection pin 42 The semiconductor element 50 with the adhesive layer is picked up from the cured product 20ac of the photocurable adhesive layer (see (h) of FIG. 6 ). In addition, the semiconductor element with an adhesive layer 50 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 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 material layer 10 when the semiconductor element 50 with the adhesive layer is picked up. In the picking step, expansion is not necessarily required, but through expansion, the picking performance can be further improved.

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 amount of lifting by the ejector pin 42 can be appropriately set. Furthermore, from the viewpoint of ensuring sufficient pickup performance even for extremely thin wafers, for example, 2-stage or 3-stage pickup may be performed. In addition, the semiconductor element 50 with the adhesive layer can also be picked up by a method other than the method using the suction chuck 44 .

<半導體元件接著步驟> <Semiconductor element attachment steps>

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。 After picking up the semiconductor element 50 with the adhesive layer, the semiconductor element 50 with the adhesive layer is bonded by thermocompression bonding to the semiconductor element mounting support substrate 60 via the adhesive layer 30 a (see (i) of FIG. 6 ). . A plurality of semiconductor elements 50 with adhesive layers can be bonded to the semiconductor element mounting support substrate 60 .

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。 FIG. 7 is a cross-section schematically showing one embodiment of a semiconductor device. Figure. The semiconductor device 100 shown in FIG. 7 can be manufactured by the following manufacturing method, which further includes: the above 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 60 a 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 can be formed for electrical connection with an external substrate (motherboard).

[實施例] [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 using examples, but the present invention is not limited to these examples. In addition, unless otherwise stated, commercially available reagents were used for the compounds.

[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) [Preparation of cutting-crystallization integrated membrane] (Preparation of (meth)acrylic acid copolymer solutions A~E)

在具備三一馬達(Three-One Motor)、攪拌翼以及氮氣導入管的容量2000mL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500ml/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2000mL的加壓釜中，在120℃、0.28MPa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。 In an autoclave with a capacity of 2000 mL equipped with a Three-One Motor, a stirring blade, and a nitrogen inlet pipe, add 2-ethylhexyl acrylate (2EHA) in the proportion (unit: parts by mass) shown in Table 1 , 2-hydroxyethyl acrylate (HEA), and methacrylic acid (MAA), and then added 127 parts by mass of ethyl acetate and 0.04 parts by mass of azobisisobutyronitrile. Stir it until uniform, perform foaming at a flow rate of 500 ml/min for 60 minutes, and degas the dissolved oxygen in the system. Next, the temperature was raised to 78°C over 1 hour, and polymerization was performed for 6 hours while maintaining 78°C to 83°C. Then, the reaction solution was transferred to a pressurized kettle with a capacity of 2000 mL equipped with a Trinity motor, stirring blades, and nitrogen introduction tubes, heated at 120°C and 0.28MPa for 4.5 hours, and then cooled to room temperature (25°C, the same below) ). Then, further add 98 parts by mass of acetonitrile Dilute with ethyl acid. 0.05 parts by mass of hydroquinone-monomethyl ether as a polymerization inhibitor and 0.02 parts by mass of dioctyltin dilaurate as a urethanation catalyst were added thereto, and a functional group capable of chain polymerization was added. 10 parts by mass of 2-methacryloxyethyl isocyanate (manufactured by Showa Denko Co., Ltd., trade name "Karenz MOI") based compound, reacted at 70° C. for 6 hours, and cooled to room temperature Warm. Then, ethyl acetate was added so that the nonvolatile matter (solid content) content would be 35% by mass, thereby obtaining (meth)acrylic acid 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 acid copolymer in the (meth)acrylic acid 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 the obtained solid content was elementally analyzed using a fully automatic elemental analysis device vario EL manufactured by Elementar Corporation, and the nitrogen content was calculated. The content of 2-methacryloyloxyethyl 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, and the weight average molecular weight (Mw) in terms of polystyrene was measured. The results are shown in Table 1.

表1

Figure 108147291-A0305-02-0035-1
Table 1
Figure 108147291-A0305-02-0035-1

<製造例1：切割-黏晶一體型膜A的製作>(切割膜的製備) <Production Example 1: Preparation of cutting-crystallization integrated film A> (Preparation of cutting film)

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10μm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400mm、厚38μm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：90μm)，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。 The prepared (meth)acrylic acid copolymer solution A, which is a (meth)acrylic acid copolymer having a reactive functional group, is 100 parts by mass in terms of solid content, and 0.5 parts by mass is a photopolymerization initiator. 1-Hydroxycyclohexyl phenyl ketone (IRGACURE 184 manufactured by Ciba Specialty Chemicals Co., Ltd.), and 2 parts by mass of polyfunctional isocyanate (Japan Polyamine-based Made by Formate Industrial Co., Ltd., brand name "Coronate L", solid content 75%) mixed. To this mixture, ethyl acetate was added so that the total solid content reached 25% by mass, and the mixture was uniformly stirred for 10 minutes to obtain a varnish for forming a photocurable adhesive layer. The obtained varnish for forming a photo-curing adhesive layer was applied to a 350-meter-wide release-treated surface on one side while adjusting the gap so that the thickness of the dried photo-curing adhesive layer would be 10 μm. mm, 400mm long, 38μm thick polyethylene terephthalate (PET) film, heat and dry the varnish used to form the photocurable adhesive layer at 80℃~100℃ for 3 minutes. Then, a polyolefin film (base material layer, thickness: 90 μm) subjected to corona discharge treatment on one side was bonded, cured at 40°C for 72 hours, and cross-linked to obtain a base material. layer and light-hardening adhesive layer. Furthermore, the cross-linking treatment is performed while confirming the progress of curing using Fourier transform infrared spectrometer (FT-IR) spectroscopy.

(黏晶膜的製作) (Preparation of mucous membrane)

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0.016μm)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10μm的B階段狀態的接著劑層，製作具備接著劑層的黏晶膜。 In 55 parts by mass of YDCN-703 (manufactured by Toto Chemical Co., Ltd., trade name, cresol novolak type epoxy resin, epoxy equivalent 210, molecular weight 1200, softening point 80°C) as an epoxy resin, 45 parts by mass Milex XLC-LL (trade name, manufactured by Mitsui Chemicals Co., Ltd., hydroxyl equivalent: 175, water absorption: 1.8%, heating mass reduction rate at 350°C: 4%) as a phenolic resin, 1.7 parts by mass As a silane coupling agent, NUCA-189 (manufactured by Nippon Unicar Co., Ltd., trade name, γ-mercaptopropyltrimethoxysilane) and 3.2 parts by mass of NUCA-1160 (Nippon Unicar Co., Ltd.) Unicar Co., Ltd., trade name, γ-ureidopropyltriethoxysilane), and 32 parts by mass of AEROSIL 972 as a filler (the surface of the silica is coated with dimethyldichlorosilane Coated, hydrolyzed in a reactor at 400°C, and cyclohexane was added to the silica filler surface-modified by organic groups such as methyl groups (manufactured by Japan AEROSIL Co., Ltd., trade name, average particle size: 0.016 μm) ketone and stirred to mix, and then kneaded using a bead mill for 90 minutes. To the obtained mixture, 280 parts by mass of acrylic rubber was added Glue HTR-860P-3 (trade name, manufactured by Nagase ChemteX Co., Ltd., weight average molecular weight 800,000, acrylic rubber containing 3 mass % of glycidyl acrylate or glycidyl methacrylate) and 0.5 Mass parts of Curezol 2PZ-CN (manufactured by Shikoku Chemical Industry Co., Ltd., trade name, 1-cyanoethyl-2-phenylimidazole) as a hardening accelerator, stir and mix, and degas in a vacuum , thereby obtaining a varnish for forming an adhesive layer. The obtained varnish for forming an adhesive layer was applied to a release-treated polyethylene terephthalate (PET) film so as to have a set thickness, and was heated and dried at 140° C. for 5 minutes to obtain a thickness of 10 μm. The adhesive layer in the B-stage state is used to produce an adhesive film having an adhesive layer.

(切割-黏晶一體型膜的製作) (Production of cutting-crystallization integrated membrane)

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。 The produced die-bonded film is cut into a size that is easy to handle together with the PET film. For the adhesive layer of the cut die-bonding film, peel off the photo-curing adhesive layer of the PET film and attach the cut film immediately before attaching it. Lamination is performed in a clean room (a dust-free room with a temperature of 23°C and a humidity of 50%) using a laminator without heating rollers (i.e., a temperature of 23°C). Thereafter, from the viewpoint of maintaining constant adhesion between the adhesive layer and the photocurable adhesive layer, the film was stored in a refrigerator at 4° C. for 1 day, thereby obtaining a dicing-die bonding integrated film A.

<製造例2：切割-黏晶一體型膜B的製作> <Manufacturing Example 2: Production of Cutting-Crystallization Integrated Film B>

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。 Except having changed the content of the crosslinking agent from 8 parts by mass to 10 parts by mass, it was carried out similarly to Production Example 1, and the cutting-crystallization integrated film B was obtained.

<製造例3：切割-黏晶一體型膜C的製作> <Manufacturing Example 3: Production of cutting-crystallization integrated film C>

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。 Except that the (meth)acrylic acid copolymer solution was changed from A to B and the content of the cross-linking agent was changed from 8 parts by mass to 6 parts by mass, the same operation was performed as in Production Example 1 to obtain a cutting-crystallization integrated film C. .

<製造例4：切割-黏晶一體型膜D的製作> <Manufacturing Example 4: Production of cutting-crystal bonding integrated film D>

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。 Except that the coating speed of the photocurable adhesive layer forming varnish was changed to 0.8 times the coating speed of Production Example 1, the same operation was performed as in Production Example 1 to obtain a dicing-die bonding integrated film D.

<製造例5：切割-黏晶一體型膜E的製作> <Manufacturing Example 5: Production of Cutting-Crystallization Integrated Film E>

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。 Except that the coating speed of the photocurable adhesive layer-forming varnish was changed to 1.2 times the coating speed of Production Example 1, the same operation was performed as in Production Example 1 to obtain the dicing-die bonding integrated film E.

<製造例6：切割-黏晶一體型膜F的製作> <Manufacturing Example 6: Production of cutting-crystallization integrated film F>

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。 Except that the (meth)acrylic acid copolymer solution was changed from A to C and the content of the cross-linking agent was changed from 8 parts by mass to 6 parts by mass, the same operation was performed as in Production Example 1 to obtain the cutting-crystallization integrated film F. .

<製造例7：切割-黏晶一體型膜G的製作> <Manufacturing Example 7: Production of cutting-crystallization integrated film G>

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。 Except that the (meth)acrylic acid copolymer solution was changed from A to D and the content of the cross-linking agent was changed from 8 parts by mass to 6 parts by mass, the same operation was performed as in Production Example 1 to obtain the cutting-crystallization integrated film G. .

<製造例8：切割-黏晶一體型膜H的製作> <Manufacturing Example 8: Production of cutting-crystal bonding integrated film H>

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。 Except having changed the content of the crosslinking agent from 8 parts by mass to 6 parts by mass, the same operation was performed as in Production Example 1 to obtain the cutting-bonding integrated film H.

<製造例9：切割-黏晶一體型膜I的製作> <Manufacture Example 9: Production of Cutting-Crystallization Integrated Film I>

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。 Except that the (meth)acrylic acid copolymer solution A was changed to the (meth)acrylic acid copolymer solution E, the same operation was performed as in Production Example 1 to obtain the cutting-crystallization integrated film I.

<製造例10：切割-黏晶一體型膜J的製作> <Manufacturing Example 10: Production of cutting-crystal bonding integrated film J>

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。 Except that the coating speed of the photocurable adhesive layer forming varnish was changed to 1.5 times the coating speed of Production Example 1, the same operation was performed as in Production Example 1 to obtain a dicing-die bonding integrated film J.

<製造例11：切割-黏晶一體型膜K的製作> <Manufacture Example 11: Production of cutting-crystallization integrated film K>

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。 Except that the coating speed of the photocurable adhesive layer forming varnish was changed to 0.6 times the coating speed of Production Example 1, the same operation was performed as in Production Example 1 to obtain a dicing-die bonding integrated film K.

<製造例12：切割-黏晶一體型膜L的製作> <Manufacture Example 12: Production of cutting-crystallization integrated film L>

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。 In the production of the cutting-crystal integrated film, the PET film of the cutting film is peeled off in a clean room (a clean room with a temperature of 23°C and a humidity of 50%), and the photohardening adhesive layer is exposed to the air for 1 day. The above layer was attached to the adhesive layer of the die-bonding film, and the cutting-die die-bonding integrated film L was obtained in the same manner as in Production Example 1 except for this.

<製造例13：切割-黏晶一體型膜M的製作> <Manufacture Example 13: Production of cutting-crystallization integrated film M>

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。 In the production of the dicing-die bonding integrated film, the adhesive layer of the die bonding film and the photocurable adhesive layer of the dicing film are attached while heating the roller of the laminator to 50°C. 1Similarly, a cutting-crystallization integrated film M was obtained.

[剝離力的測定]<測定樣品的製作> [Measurement of Peeling Force] <Preparation of Measurement Samples>

將切割-黏晶一體型膜A~切割-黏晶一體型膜M分別切成寬30mm、長200mm，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25mm、長170mm。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365nm的紫外線)，在照射溫度40℃以下、照射強度70mW/cm2以及累計光量150mJ/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。 Cut the cutting-crystal integrated film A to the cutting-crystallizing integrated film M into a width of 30 mm and a length of 200 mm respectively. Peel off the PET film on the adhesive layer side of the crystal sticking film and use a roller to remove the supporting film (Oji Taku ( OJI TAC) Co., Ltd., EC tape) is attached to the adhesive layer side, and cut into a width of 25mm and a length of 170mm. Next, an ultraviolet irradiation device (made by GS Yuasa Co., Ltd., UV SYSTEM, center wavelength 365 nm) was used from the base material layer (polyolefin film) side of the cut-out integrated film with an adhesive film. (Ultraviolet ray), irradiate at an irradiation temperature of 40°C or lower, an irradiation intensity of 70mW/ cm2 , and a cumulative light amount of 150mJ/ cm2 to form a cured product of the photocurable adhesive layer, thereby obtaining a measurement sample.

<剝離力的測定> <Measurement of Peeling Force>

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600mm/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0.70N/25mm以下)的滿足性亦示於表2、表3、及表4。 For the measurement sample prepared as described above, the angle-free adhesive-coating peeling analysis device VPA-2S (manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the temperature at 25±5°C, the humidity at 55±10%, and the peeling angle. The support film was stretched at 30° and a peeling speed of 600 mm/min, and the peeling force (low-angle (30°) peeling strength) when peeling off 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 defined as the low-angle peel strength. The results are shown in Table 2, Table 3, and Table 4. In addition, the satisfaction of condition (a) (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> [Measurement of the number of traces and trace width of drawing marks] <Preparation of measurement samples>

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30mm、長50mm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25mm。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365nm的紫外線)，在照射溫度40℃以下、照射強度70mW/cm2以及累計光量150mJ/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600mm/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5mm×5mm的尺寸，獲得測量樣品。 The dicing-crystallization integrated film was the same as the film used in the measurement of the peeling force, and a film in which the measurement of the peeling force was not performed was used. Cut the cutting-crystal bonding integrated membranes A~M to a width of 30mm and a length of more than 50mm respectively. Next, the heater was brought into contact with the base material layer (polyolefin film) of the integrated cutting-die bonding film, the photocurable adhesive layer was heated at 65°C for 15 minutes, and then air-cooled to 25±5°C. After air cooling, the PET film on the adhesive layer side of the crystal bonding film was peeled off, a support film (EC tape manufactured by OJI TAC Co., Ltd.) was attached, and neatly cut into a width of 25 mm. Next, an ultraviolet irradiation device (manufactured by GS Yuasa Co., Ltd., UV SYSTEM, center wavelength 365nm ultraviolet light), irradiate at an irradiation temperature of 40°C or less, an irradiation intensity of 70mW/ cm2 , and a cumulative light amount of 150mJ/ cm2 to form a hardened product of the photocurable adhesive layer. Next, an angle-free adhesive-coating 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%, a peeling angle of 30°, and a peeling speed of 600mm/ Stretch the support film for 1 minute, peel off the adhesive layer and the cured material of the photo-curing adhesive layer, collect the base material layer including the cured material of the photo-curing adhesive layer after the adhesive layer is peeled off, and cut it into 5 mm pieces. ×5mm size, obtain the measurement sample.

<拉絲痕跡的痕跡數及痕跡寬度的測量> <Measurement of the number of traces and trace width of drawing traces>

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25μm×25μm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25μm×25μm的區域，區域內的拉絲痕跡的痕跡寬度的中位數為120nm~200nm)的滿足性，亦示於表2、表3、及表4。 The measurement sample prepared above was fixed on a plate-shaped stage. The measurement samples were fixed using carbon double-sided tape. A scanning probe microscope (manufactured by SII NanoTechnology Co., Ltd., trade name "SPA400") was used to observe the surface of the cured product of the photocurable adhesive layer after the adhesive layer was peeled off. Image analysis software (included with "SPA400") performs analysis. Installing a cantilever with a low spring constant on the probe of a scanning probe microscope (Olympus Corporation Co., Ltd., trade name "OMCL-AC240TS"). During the observation of the cured product of the photocurable adhesive layer, the dynamic force mode (DFM) was used to observe the phase image data, and the parts in the phase image whose hardness was obviously different from the surroundings were used as drawing traces. During the observation of the measurement sample, it was confirmed whether there was a 25 μm×25 μm area (specific area) with a number of drawing marks of 15 or more on the surface to be observed. When there is 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 has been peeled off, the median mark width of the wire drawing marks present in the specific area is calculated. Count. The trace width of the drawing trace is determined as follows. First, a scanning probe microscope is used to obtain the shape image distribution and phase image distribution of the cured surface of the photocurable adhesive layer including a portion where the hardness is significantly different from the surrounding areas in the phase image. Next, based on the obtained shape image distribution, commercially available image processing software (image processing software attached to a scanning probe microscope, etc.) is used to output the trace width of each wire drawing mark for all wire drawing marks to be measured. The cross-sectional distribution of the largest cross-section line is used to determine the trace width of the drawing trace based on the above criteria. 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 the surroundings is different from that in 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 surface of the cured product of the photocurable adhesive layer after the adhesive layer is peeled off, there is a 25 μm The satisfaction of the median is 120nm~200nm) is also shown in Table 2, Table 3, and Table 4.

[切割步驟中的拾取性的評價] [Evaluation of pick-up properties in the cutting step]

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。 Regarding the obtained dicing-bonding integrated films A to M of Production Examples 1 to 13, the success rate of pickup under the predetermined conditions of the dicing step and the peeling time taken for pickup were evaluated.

<評價樣品的製作>(改質層形成) <Preparation of evaluation samples> (Formation of modified layer)

在半導體晶圓(矽晶圓(厚度750μm、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。 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 a back grind tape. The surface of the semiconductor wafer opposite to the side to which the back polishing tape is attached is irradiated with laser light to form a modified layer inside the semiconductor wafer. The irradiation conditions of 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 Laser vibrator type: semiconductor laser light excited Q-switch solid laser

波長：1342nm Wavelength: 1342nm

振動形式：脈衝 Vibration form: pulse

頻率：90kHz Frequency: 90kHz

輸出：1.7W Output: 1.7W

半導體晶圓載置台的移動速度：700mm/秒 Moving speed of semiconductor wafer mounting table: 700mm/second

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30μm的半導體晶圓。 Next, the surface of the semiconductor wafer opposite to the side to which the back polishing tape is attached is back ground and polished, thereby obtaining a semiconductor wafer having a thickness of 30 μm.

(晶圓層壓) (wafer lamination)

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。 On the surface of the semiconductor wafer opposite to the side where the back polishing tape is attached, the PET film of the dicing-die integrated film is peeled off, and an adhesive layer is attached.

(切割) (cutting)

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。 Next, the semiconductor wafer with the dicing-bonding integrated film having the modified layer is fixed on the expansion device. Next, the dicing film is expanded under the following conditions to separate the semiconductor wafer, adhesive layer, and photocurable adhesive layer into individual pieces.

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)」 Device: Made by Disco Co., Ltd., trade name "DDS 2300 Fully Automatic Die Separator"

冷擴展條件： Cold expansion conditions:

溫度：-15℃、高度：9mm、冷卻時間：90秒、速度：300mm/秒、待機時間：0秒 Temperature: -15℃, Height: 9mm, Cooling time: 90 seconds, Speed: 300mm/second, Standby time: 0 seconds

熱收縮條件： Heat shrink conditions:

溫度：220℃、高度：7mm、保持時間：15秒、速度：30mm/秒、加熱速度：7℃/秒 Temperature: 220℃, height: 7mm, holding time: 15 seconds, speed: 30mm/second, heating speed: 7℃/second

(紫外線照射) (Ultraviolet irradiation)

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70mW/cm2和累計光量150mJ/cm2照射中心波長365nm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。 The photocurable adhesive layer of the singulated semiconductor wafer is irradiated with ultraviolet rays with a center wavelength of 365 nm at an irradiation intensity of 70 mW/cm 2 and a cumulative light amount of 150 mJ/cm 2 to form a hardened product of the photocurable adhesive layer. An evaluation sample for pick-up properties described below was obtained.

<拾取性的評價> <Evaluation of pick-up properties>

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：10×10mm)。上頂銷使用噴射針(EJECTOR NEEDLE)SEN2-83-05(微機械公司製，商品名，直徑：0.7mm，前端形狀：直徑350μm的半圓)。上頂銷從銷中心等間隔地配置了9根。 A pick-up test was conducted using a die bonding machine DB-830P (manufactured by FASFORD TECHNOLOGY Co., Ltd. (formerly manufactured by Hitachi High-technologies Co., Ltd.)) using 9 pins. Use the rubber nozzle (RUBBER TIP) 13-087E-33 (Micro Machinery Co., Ltd.) for the pick-up chuck. Made by Micromechanics, trade name, size: 10×10mm). An ejection needle (EJECTOR NEEDLE) SEN2-83-05 (manufactured by Micro Machinery Co., Ltd., trade name, diameter: 0.7 mm, tip shape: semicircle with a diameter of 350 μm) was used for the upper ejection pin. Nine upper ejector pins are arranged at equal intervals from the center of the pin.

<拾取的成功率> <Success rate of picking up>

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。 In the above pickup test, those with a pickup success rate of 95% to 100% were evaluated as "A", and those with less than 95% were evaluated as "B". The results are shown in Table 2, Table 3, and Table 4.

<拾取的剝離時間> <Pick-up peeling time>

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1mm/秒的速度上頂到300μm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。 The above-mentioned pick-up test was photographed using a high-speed camera MEMRECM GX-1Plus (trade name, manufactured by NAC Image Technology Co., Ltd.), and the chuck was brought into contact with the wafer until the adhesive layer and the photocurable adhesive layer were completely The time until peeling was evaluated as peeling time. Pick-up was performed at a speed of 1 mm/sec up to 300 μm. The frame rate is 1000 frames/second. A peeling time of less than 60 m seconds is evaluated as "A", a peeling time of more than 60 m seconds and less than 90 m seconds is evaluated as "B", and a peeling time of more than 90 m seconds is evaluated as "C". The results are shown in Table 2, Table 3, and Table 4.

Figure 108147291-A0305-02-0045-2
Figure 108147291-A0305-02-0045-2
Figure 108147291-A0305-02-0046-3
Figure 108147291-A0305-02-0046-3

Figure 108147291-A0305-02-0046-4
Figure 108147291-A0305-02-0046-4

Figure 108147291-A0305-02-0046-5
Figure 108147291-A0305-02-0046-5
Figure 108147291-A0305-02-0047-7
Figure 108147291-A0305-02-0047-7

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0.70N/25mm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25μm×25μm的區域，區域內的拉絲痕跡的痕跡寬度的中位數為120nm~200nm，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 peeling force of the dicing-die bonding integrated films A to E of Production Examples 1 to 5 is 0.70N/25mm or less, and the photocurable properties after the adhesive layer is peeled off The number of drawing marks on the surface of the hardened material of the adhesive layer is 15 or more in a 25 μm × 25 μm area, and the median width of the drawing marks in the area is 120 nm to 200 nm, satisfying conditions (a) and (b). ) both. It was found that the cutting-die integrated films A to E of Production Examples 1 to 5 are excellent in the evaluation of pick-up properties. On the other hand, it was found that the cutting-crystallization integrated films F to M of Production Examples 6 to 13 did not satisfy either condition (a) or condition (b), or did not satisfy both condition (a) and condition (b). Insufficient evaluation of pick-up properties.

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：70mW/cm2 累計光量：150mJ/cm2(剝離條件)溫度：25±5℃濕度：55±10%剝離角度：30°剝離速度：600mm/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 light-hardening adhesive used in a cutting-crystal bonding integrated film, including: a first step, preparing a cutting-crystal bonding integrated film, the cutting-crystal bonding integrated film, The crystal integrated film is sequentially laminated with a base material layer, a photocurable adhesive layer containing a photocurable adhesive, and an adhesive layer, and the photocurable adhesive layer is irradiated with ultraviolet rays under the following irradiation conditions to form the above The cured product of the photocurable adhesive layer, and measure the peeling force when peeling off the adhesive layer and the cured product of the photocurable adhesive layer under the following peeling conditions; the second step is to prepare for cutting-crystallization - A body-shaped film in which a base material layer, a photocurable adhesive layer containing a photocurable adhesive, and an adhesive layer are laminated in this order, and the photocurable adhesive layer is laminated in this order under the following heating and cooling conditions. The adhesive layer is processed, and the photocurable adhesive layer is irradiated with ultraviolet rays under the following irradiation conditions to form a hardened product of the photocurable adhesive layer, and the adhesive layer and the adhesive layer are peeled off under the following peeling conditions. Observe the surface of the hardened product of the photocurable adhesive layer after peeling off the adhesive layer using a scanning probe microscope, and measure the traces of drawing marks on the surface. Count and trace width; and the third step, based on the peeling force and the trace number and trace width of the drawing trace, determine whether the photohardening adhesive is good, (irradiation conditions) irradiation intensity: 70mW/cm 2 cumulative Light quantity: 150mJ/cm 2 (peeling conditions) Temperature: 25±5℃ Humidity: 55±10% Peeling angle: 30° Peeling speed: 600mm/min (heating and cooling conditions) Heating treatment: 65℃, 15 minutes Cooling treatment: Empty Let cool for 30 minutes until 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0.70N/25mm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25μm×25μm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120nm~200nm。 The evaluation method of photocurable adhesive as claimed in claim 1, wherein the third step is based on whether the peeling force and the number and width of the drawing traces satisfy the following conditions (a) and the following The step of determining whether the photocurable adhesive is good according to condition (b), condition (a): the peeling force is 0.70N/25mm or less, condition (b): the peeling force after peeling off the adhesive layer There is a 25 μm × 25 μm area with 15 or more wire drawing marks on the surface of the cured product of the photocurable adhesive layer, and the median trace width of the wire drawing marks in the area 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 evaluation method of a photocurable adhesive according to Claim 1 or Claim 2, wherein the photocurable adhesive contains: a (meth)acrylic copolymer having a reactive functional group, a photopolymerization initiator , and a cross-linking agent, the cross-linking agent has two or more functional groups capable of reacting 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 evaluation method of 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或請求項2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 evaluation method of a photocurable adhesive according to Claim 1 or Claim 2, wherein the adhesive layer contains: epoxy resin, epoxy resin hardener, and (meth)acrylic system having an epoxy group 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 method for manufacturing a cutting-crystal integrated film, including the step of forming a photo-hardening adhesive layer on a base material layer, the photo-hardening adhesive layer comprising: The photocurable adhesive is judged to be a good photocurable adhesive by the photocurable adhesive evaluation method described in claim 1; 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 manufacturing method of a semiconductor device, comprising: attaching the adhesive layer of the dicing-die integrated film obtained by the manufacturing method of the dicing-die integrated film according to claim 6 to a semiconductor wafer The step of dicing the semiconductor wafer, the adhesive layer and the photo-curing adhesive layer into individual pieces; irradiating the photo-curing adhesive layer with ultraviolet rays to form the light The steps of curing the cured product of the curable adhesive layer; picking up the semiconductor element to which the adhesive layer is attached from the cured product of the photo-curable adhesive layer; and bonding the semiconductor element via the adhesive layer. In the step of supporting a substrate for mounting a semiconductor element. 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35μm以下。 The method of manufacturing a semiconductor device according to claim 7, wherein the semiconductor wafer has a thickness of 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 manufacturing method of a semiconductor device according to claim 7 or claim 8, wherein the cutting uses 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 cutting-crystal bonding integrated film, sequentially including a base material layer, a photo-hardening adhesive layer, and an adhesive layer, wherein the photo-hardening adhesive layer is formed by any one of claim 1 to claim 5. The photocurable adhesive was judged to be a good photocurable adhesive according to the evaluation method of the photocurable adhesive described above.
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