TWI820178B - Terminal protection tape and method for manufacturing semiconductor device with electromagnetic wave shielding film - Google Patents

Terminal protection tape and method for manufacturing semiconductor device with electromagnetic wave shielding film Download PDF

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TWI820178B
TWI820178B TW108128166A TW108128166A TWI820178B TW I820178 B TWI820178 B TW I820178B TW 108128166 A TW108128166 A TW 108128166A TW 108128166 A TW108128166 A TW 108128166A TW I820178 B TWI820178 B TW I820178B
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mass
layer
adhesive
terminals
semiconductor device
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TW108128166A
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TW202020081A (en
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坂東沙也香
佐藤明徳
中石康喜
岡本直也
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日商琳得科股份有限公司
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    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01L21/67—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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01L21/70—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/552—Protection against radiation, e.g. light or electromagnetic waves
    • 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
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • 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
    • H01L2221/6834—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 to protect an active side of a device or wafer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H01L2224/161—Disposition
    • H01L2224/16151—Disposition the bump 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
    • H01L2224/16221—Disposition the bump 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
    • H01L2224/16225—Disposition the bump 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/93—Batch processes
    • H01L2224/95—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips
    • H01L2224/97—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips the devices being connected to a common substrate, e.g. interposer, said common substrate being separable into individual assemblies after connecting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151—Die mounting substrate
    • H01L2924/153—Connection portion
    • H01L2924/1531—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface
    • H01L2924/15311—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface being a ball array, e.g. BGA
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/19—Details of hybrid assemblies other than the semiconductor or other solid state devices to be connected
    • H01L2924/191—Disposition
    • H01L2924/19101—Disposition of discrete passive components
    • H01L2924/19105—Disposition of discrete passive components in a side-by-side arrangement on a common die mounting substrate

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Electromagnetism (AREA)
  • Toxicology (AREA)
  • Mechanical Engineering (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)

Abstract

The present invention relates to a terminal protecting tape (1) used in a step of forming an electromagnetic wave shielding film on a terminal-attached semiconductor device, the terminal protecting tape comprises a viscoelastic layer (12), in which a value of tan δ at 50°C is 0.2 or more in the dynamic viscoelasticity measurement of the viscoelastic layer (12), and a relaxation elastic modulus fluctuation value X2 determined by [log G (t) max-log G (t) min] is 0.12 or more when relaxation elastic modulus of an evaluation sample of cylindrical is measured while a constant strain of 10%(36°) is applied to the evaluation sample.

Description

端子保護用膠帶以及附電磁波屏蔽膜之半導體裝置的製造方法Terminal protection tape and method for manufacturing semiconductor device with electromagnetic wave shielding film

本發明係關於端子保護用膠帶以及使用該膠帶之附電磁波屏蔽膜之半導體裝置的製造方法。 The present invention relates to a terminal protection tape and a method of manufacturing a semiconductor device with an electromagnetic wave shielding film using the tape.

本申請基於2018年8月8日於日本申請之特願2018-149700號主張其優先權，在此援引該內容。 This application claims priority based on Special Application No. 2018-149700 filed in Japan on August 8, 2018, the content of which is incorporated herein by reference.

以往，用於MPU(微處理器；Micro Processing Unit)或閘陣列等之多接腳的LSI(Large Scale Integration；大型積體電路)封裝(package)構裝在印刷線路基板的情況，作為具備複數的電子零件之半導體裝置，係採用以下的構裝方法：在該連接墊部係使用由共晶焊料、高溫焊料、金等所構成之凸狀電極(以下在本說明書中稱為「端子」)所形成者。然後，將這些端子面對搭載晶片用基板上的相對應之端子部，並使其接觸、熔融/擴散結合。 Conventionally, when an LSI (Large Scale Integration; large integrated circuit) package with multiple pins such as an MPU (Micro Processing Unit) or a gate array is built on a printed circuit board, it is considered as having multiple The semiconductor device of the electronic component adopts the following construction method: the connection pad portion uses a protruding electrode (hereinafter referred to as "terminal" in this specification) composed of eutectic solder, high-temperature solder, gold, etc. What is formed. Then, these terminals are faced with corresponding terminal portions on the substrate for mounting the chip, and are brought into contact and melted/diffusion bonded.

隨著個人電腦的普及並且網路變得普遍，現在智慧型手機或平板終端皆連接至網路，藉由無線通訊技術將經數位化之影像、音樂、照片、文字訊息等介由網路來傳達的情境日益增加。進而，物聯網(IoT；Internet of Things)普及，為了在家電、汽車等的各種的應用領域想要更聰明地使用以感應器、無線射頻辨識(RFID；Radio frequency identifier)、微機電 系統(MEMS；Micro Electro Mechanical Systems)、無線組件等的半導體裝置而在封裝技術帶來創新的變革。 With the popularization of personal computers and the widespread use of the Internet, smart phones or tablet terminals are now connected to the Internet, and digitized images, music, photos, text messages, etc. are transmitted through the Internet through wireless communication technology. The situations conveyed are increasing day by day. Furthermore, as the Internet of Things (IoT) spreads, sensors, radio frequency identifiers (RFID), and MEMS are used more intelligently in various application fields such as home appliances and automobiles. Semiconductor devices such as MEMS (Micro Electro Mechanical Systems) and wireless components have brought innovative changes in packaging technology.

像這樣電子機器持續進化之中，對半導體裝置的要求水準逐年提高。尤其為了回應高性能化、小型化、高積體化、低消耗電力化、低成本化之需求，防熱措施、防噪音措施成為2個重要的點。 As electronic equipment continues to evolve, the level of requirements for semiconductor devices is increasing year by year. Especially in response to the needs for high performance, miniaturization, high integration, low power consumption, and low cost, heat protection measures and noise prevention measures have become two important points.

對應這種防熱措施、防噪音措施，例如專利文獻1所揭示，係採用將電子零件模組以導電材料被覆並形成屏蔽層之方法。專利文獻1中，將經單片化之電子零件模組的頂面以及側面所塗布之導電性樹脂加熱並使其硬化，並形成屏蔽層。 To cope with such heat protection and noise protection measures, for example, patent document 1 discloses a method of covering the electronic component module with a conductive material and forming a shielding layer. In Patent Document 1, conductive resin coated on the top and side surfaces of a singulated electronic component module is heated and hardened to form a shielding layer.

作為將附端子之半導體裝置以導電材料被覆並形成屏蔽層之方法，已知有濺鍍、離子鍍、噴塗等的方法。 As a method of covering a semiconductor device with a terminal with a conductive material and forming a shielding layer, methods such as sputtering, ion plating, and spray coating are known.

[先前技術文獻] [Prior technical literature]

[專利文獻] [Patent Document]

專利文獻1：日本特開2011-151372號公報。 Patent Document 1: Japanese Patent Application Publication No. 2011-151372.

專利文獻1所揭示之電子零件的製造方法，係在集合基板的裡面所設置之外部端子電極埋入黏著性片的狀態下塗布導電性樹脂。由於在黏著性片的預定的位置設置遮罩部，故可防止外部端子電極與電磁波屏蔽膜產生電性短路。 Patent Document 1 discloses a manufacturing method of electronic components in which conductive resin is coated in a state where external terminal electrodes provided on the back of a collective substrate are embedded in an adhesive sheet. Since the mask portion is provided at a predetermined position of the adhesive sheet, electrical short circuit between the external terminal electrode and the electromagnetic wave shielding film can be prevented.

然而，外部端子電極可能有無法充分埋入黏著性片的情況，或者，即使可埋入，可能隨著時間經過而產生浮起，而有外部端子電極與電磁波屏蔽膜產生電性短路之虞。此外，在黏著性片的預定的位置設置遮 罩部在步驟上很複雜。 However, the external terminal electrodes may not be fully embedded in the adhesive sheet, or even if they can be embedded, they may float over time, resulting in an electrical short circuit between the external terminal electrodes and the electromagnetic wave shielding film. In addition, a mask is provided at a predetermined position of the adhesive sheet The steps of the cover part are complicated.

因此，本發明的目的在於提供一種端子保護用膠帶，以及使用該膠帶之附電磁波屏蔽膜之半導體裝置的製造方法，係用於在附端子之半導體裝置形成電磁波屏蔽膜之步驟之端子保護用膠帶，即使是焊球等的具有凹凸而容易產生浮起的端子電極亦可埋入，且不產生浮起。 Therefore, an object of the present invention is to provide a terminal protection tape and a method for manufacturing a semiconductor device with an electromagnetic wave shielding film using the tape, which is a terminal protection tape used in the step of forming an electromagnetic wave shielding film on a semiconductor device with terminals. , even terminal electrodes such as solder balls that have unevenness and are prone to floating can be embedded without floating.

亦即本發明係提供以下的端子保護用膠帶以及使用該膠帶之附電磁波屏蔽膜之半導體裝置的製造方法。 That is, the present invention provides the following terminal protection tape and a method of manufacturing a semiconductor device with an electromagnetic wave shielding film using the tape.

[1]一種端子保護用膠帶，係用於在附端子之半導體裝置形成電磁波屏蔽膜之步驟；前述端子保護用膠帶具有黏彈性層；在前述黏彈性層的動態黏彈性測定之中，50℃之tanδ的值為0.2以上；對於前述黏彈性層，將直徑8mm、厚度約1mm的圓柱形狀的評價用試樣在50℃施加10%(36°)的一定的扭轉應變來測定鬆弛彈性模量時，從最大鬆弛彈性模量G(t)max(MPa)以及離測定前述最大鬆弛彈性模量G(t)max後至1秒後為止所測定之最小鬆弛彈性模量G(t)min(MPa)，根據下述式(1)所求出之鬆弛彈性模量變數X2係滿足下述式(2)：X2=logG(t)max-logG(t)min‧‧‧(1) [1] A terminal protection tape, which is used in the process of forming an electromagnetic wave shielding film on a semiconductor device with terminals; the terminal protection tape has a viscoelastic layer; in the dynamic viscoelasticity measurement of the viscoelastic layer, 50°C The value of tan δ is 0.2 or more; for the aforementioned viscoelastic layer, apply a certain torsional strain of 10% (36°) to a cylindrical evaluation sample with a diameter of 8 mm and a thickness of about 1 mm at 50°C to measure the relaxation elastic modulus. when , from the maximum relaxation elastic modulus G(t) max (MPa) and the minimum relaxation elastic modulus G(t) min measured up to 1 second after the measurement of the aforementioned maximum relaxation elastic modulus G(t) max ( MPa ) , the relaxation elastic modulus variable X2 calculated according to the following formula (1) satisfies the following formula (2):

0.12≦X2‧‧‧(2) 0.12≦X2‧‧‧(2)

[2]如前述[1]所記載之端子保護用膠帶，其中前述黏彈性層具有埋入層以及黏著劑層。 [2] The terminal protection tape according to the above [1], wherein the viscoelastic layer has an embedded layer and an adhesive layer.

[3]如前述[2]所記載之端子保護用膠帶，其中依序具有前述黏著劑層、前述埋入層、基材。 [3] The terminal protection tape according to the above [2], which has the above-mentioned adhesive layer, the above-mentioned embedded layer, and a base material in this order.

[4]如前述[3]所記載之端子保護用膠帶，係依序具有前述黏著劑層、前述埋入層、前述基材、第二黏著劑層之雙面膠帶。 [4] The terminal protection tape described in the above [3] is a double-sided tape having the above-mentioned adhesive layer, the above-mentioned buried layer, the above-mentioned base material, and a second adhesive layer in this order.

[5]一種附電磁波屏蔽膜之半導體裝置的製造方法，係包含：在如前述[1]至[4]之任1項所記載之端子保護用膠帶的黏彈性層埋設前述附端子之半導體裝置的端子之步驟；以及在未埋設在前述端子保護用膠帶的黏彈性層之前述附端子之半導體裝置的露出面形成電磁波屏蔽膜之步驟。 [5] A method of manufacturing a semiconductor device with an electromagnetic wave shielding film, which includes embedding the semiconductor device with terminals in the viscoelastic layer of the terminal protection tape described in any one of [1] to [4] above. The step of forming terminals; and the step of forming an electromagnetic wave shielding film on the exposed surface of the semiconductor device with terminals before being embedded in the viscoelastic layer of the terminal protective tape.

[6]一種附電磁波屏蔽膜之半導體裝置的製造方法，係包含：在如前述[1]至[4]之任1項所記載之端子保護用膠帶的黏彈性層埋設附端子之半導體裝置的端子之步驟；切割前述附端子之半導體裝置集合體，並將前述附端子之半導體裝置集合體作成端子埋設在前述端子保護用膠帶的黏彈性層之附端子之半導體裝置之步驟；以及在未埋設在前述端子保護用膠帶的黏彈性層之前述附端子之半導體裝置的露出面形成電磁波屏蔽膜之步驟。 [6] A method of manufacturing a semiconductor device with an electromagnetic wave shielding film, which includes embedding the semiconductor device with terminals in the viscoelastic layer of the terminal protection tape described in any one of [1] to [4] above. The step of terminals; the step of cutting the aforementioned semiconductor device assembly with terminals and forming the semiconductor device assembly with terminals into semiconductor devices with terminals embedded in the viscoelastic layer of the terminal protective tape; and in the case where the terminals are not buried The step of forming an electromagnetic wave shielding film on the exposed surface of the semiconductor device with terminals in front of the viscoelastic layer of the terminal protective tape.

藉由本發明，係提供了一種端子保護用膠帶、以及使用該膠帶之附電磁波屏蔽膜之半導體裝置的製造方法，該端子保護用膠帶係用於在附端子之半導體裝置形成電磁波屏蔽膜之步驟，即使為焊球等容易產生浮起的端子電極亦可埋入，且不產生浮起。 The present invention provides a terminal protection tape and a method for manufacturing a semiconductor device with an electromagnetic wave shielding film using the tape. The terminal protection tape is used in a step of forming an electromagnetic wave shielding film on a semiconductor device with a terminal. Even terminal electrodes that are prone to floating, such as solder balls, can be embedded without floating.

1、2、3:端子保護用膠帶 1, 2, 3: Terminal protection tape

6:附端子之半導體裝置集合體 6: Semiconductor device assembly with terminals

10:電磁波屏蔽膜 10: Electromagnetic wave shielding film

11:基材 11:Substrate

12:黏彈性層 12:Viscoelastic layer

13:埋入層 13: Buried layer

14:黏著劑層 14: Adhesive layer

15:第二黏著劑層(貼合黏著劑層) 15: Second adhesive layer (fitting adhesive layer)

20、21、22:剝離膜 20, 21, 22: peeling film

30:支撐體 30:Support

60:半導體裝置集合體 60: Semiconductor device assembly

60a、63a:端子形成面 60a, 63a: Terminal forming surface

61、62:電子零件 61, 62: Electronic parts

63:電路基板 63:Circuit substrate

64:密封樹脂層 64:Sealing resin layer

65:附端子之半導體裝置 65: Semiconductor device with terminals

66:附電磁波屏蔽膜之半導體裝置 66: Semiconductor device with electromagnetic wave shielding film

91:端子 91:Terminal

101:導電性樹脂 101:Conductive resin

圖1為示意性地表示本發明之端子保護用膠帶之一實施形態的截面圖。 FIG. 1 is a cross-sectional view schematically showing one embodiment of the terminal protective tape of the present invention.

圖2為示意性地表示本發明之端子保護用膠帶之其他實施形態的截面圖。 FIG. 2 is a cross-sectional view schematically showing another embodiment of the terminal protection tape of the present invention.

圖3為示意性地表示本發明之端子保護用膠帶之其他實施形態的截面圖。 3 is a cross-sectional view schematically showing another embodiment of the terminal protection tape of the present invention.

圖4為示意性地表示本發明之端子保護用膠帶之其他實施形態的截面圖。 4 is a cross-sectional view schematically showing another embodiment of the terminal protective tape of the present invention.

圖5為示意性地表示本發明之附電磁波屏蔽膜之半導體裝置的製造方法之一實施形態的截面圖。 5 is a cross-sectional view schematically showing one embodiment of a method for manufacturing a semiconductor device with an electromagnetic wave shielding film according to the present invention.

圖6為示意性地表示本發明之附電磁波屏蔽膜之半導體裝置的製造方法之其他實施形態的截面圖。 6 is a cross-sectional view schematically showing another embodiment of a method for manufacturing a semiconductor device with an electromagnetic wave shielding film according to the present invention.

圖7為示意性地表示比較例之附電磁波屏蔽膜之半導體裝置的製造方法之例的截面圖。 7 is a cross-sectional view schematically showing an example of a method of manufacturing a semiconductor device with an electromagnetic wave shielding film according to a comparative example.

圖1係示意性地表示本發明的端子保護用膠帶之一實施形態之截面圖。另外，以下的說明所使用之圖，為了容易理解本發明的特徴，為方便起見，有放大顯示主要部分之部分的情況，各組成要素的尺寸比率等不一定與實際相同。 FIG. 1 is a cross-sectional view schematically showing one embodiment of the terminal protective tape of the present invention. In addition, in the drawings used in the following description, in order to easily understand the features of the present invention, main parts may be shown enlarged for convenience, and the dimensional ratios of each component are not necessarily the same as the actual ones.

圖1所示之端子保護用膠帶1係用於在附端子之半導體裝置形成電磁波屏蔽膜之步驟之端子保護用膠帶1，具有由埋入層13以及黏著劑層14所構成之黏彈性層12。在黏彈性層12的動態黏彈性測定之中，50℃之tanδ的值為0.2以上。 The terminal protective tape 1 shown in Figure 1 is a terminal protective tape 1 used in the step of forming an electromagnetic wave shielding film on a semiconductor device with terminals, and has a viscoelastic layer 12 composed of an embedded layer 13 and an adhesive layer 14. . In the dynamic viscoelasticity measurement of the viscoelastic layer 12, the value of tan δ at 50° C. was 0.2 or more.

此外，對於前述黏彈性層，對直徑8mm、厚度約1mm(係指0.9mm至1.1mm)的圓柱形狀的評價用試樣在50℃施加10%(亦即36°)的一定的扭轉應變來測定鬆弛彈性模量時，從最大鬆弛彈性模量G(t)max(MPa)以及離測定前述最大鬆弛彈性模量G(t)max後至1秒後為止所測定之最小鬆弛彈性模量G(t)min(MPa)，根據下述式(1)所求出之鬆弛彈性模量變數X2係滿足下述式(2)：X2=logG(t)max-logG(t)min‧‧‧(1) In addition, for the aforementioned viscoelastic layer, the evaluation of a cylindrical shape with a diameter of 8 mm and a thickness of about 1 mm (referring to 0.9 mm to 1.1 mm) is performed by applying a certain torsional strain of 10% (i.e. 36°) to the sample at 50°C. When measuring the relaxation elastic modulus, the minimum relaxation elastic modulus G measured from the maximum relaxation elastic modulus G(t) max (MPa) to 1 second after the measurement of the maximum relaxation elastic modulus G(t) max (t) min (MPa), the relaxation elastic modulus variable X2 calculated according to the following formula (1) satisfies the following formula (2): X2=logG(t) max -logG(t) min ‧‧‧ (1)

0.12≦X2‧‧‧(2) 0.12≦X2‧‧‧(2)

本實施形態的端子保護用膠帶之黏彈性層亦可僅由埋入層 所構成，亦可具有埋入層以及黏著劑層。 The viscoelastic layer of the terminal protection tape of this embodiment may also be composed of only the embedded layer. It can also be composed of a buried layer and an adhesive layer.

本實施形態的端子保護用膠帶係如圖1所示，在黏彈性層12的埋入層13之側的最表層亦可具備剝離膜21，在黏彈性層12的黏著劑層14之側的最表層亦可具備剝離膜20。 The terminal protection tape of this embodiment is as shown in FIG. 1 . The outermost layer of the viscoelastic layer 12 on the side of the embedded layer 13 may also be provided with a peeling film 21 , and the outermost layer of the viscoelastic layer 12 on the side of the adhesive layer 14 The outermost layer may also be provided with a release film 20 .

實施形態的端子保護用膠帶1之中，黏彈性層12係由埋入層13以及黏著劑層14所構成，但只要黏彈性層12係具有埋入層13的機能，且50℃之tanδ的值以及鬆弛彈性模量變數X2在預定的值的範圍內，則黏彈性層12亦可僅由埋入層13所構成，本實施形態的端子保護用膠帶並不限定於圖1所示，只要在不損及本發明的效果的範圍內，可在圖1所示之中，變更、刪除或是追加一部分的構成。 In the terminal protection tape 1 of the embodiment, the viscoelastic layer 12 is composed of the embedded layer 13 and the adhesive layer 14. However, as long as the viscoelastic layer 12 has the function of the embedded layer 13 and the tan δ at 50°C is value and the relaxation elastic modulus variable Within the scope that does not impair the effects of the present invention, part of the structure shown in FIG. 1 may be changed, deleted, or added.

圖1所示之端子保護用膠帶1係可用於如下步驟：剝離兩者的剝離膜20、21，並裝載在支撐體之上，從其上將附端子之半導體裝置以端子之側朝下的方式壓裝，在黏彈性層12埋設端子，進而從其上形成電磁波屏蔽膜之步驟。前述黏彈性層的動態黏彈性測定之中，50℃之tanδ的值為0.2以上，故將附端子之半導體裝置的端子埋設在黏彈性層12時，即使焊球等的具有凹凸且容易產生浮起之端子電極亦可埋設，可將作為對象之附端子之半導體裝置的端子形成面密接於黏彈性層12。進而，由於黏彈性層12的鬆弛彈性模量變數X2在前述式(2)所示之預定的值的範圍內，故端子可以保持在被埋設的狀態且不產生浮起，並防止端子電極與電磁波屏蔽膜出現電性短路，且沒有必要設置步驟上複雜的遮罩部等。 The terminal protection tape 1 shown in FIG. 1 can be used in the following steps: peel off the two release films 20 and 21 and place it on a support, from which the semiconductor device with terminals is placed with the terminal side facing down. Press-fitting is used to embed terminals in the viscoelastic layer 12 and then form an electromagnetic wave shielding film thereon. In the dynamic viscoelasticity measurement of the viscoelastic layer mentioned above, the value of tan δ at 50°C is 0.2 or more. Therefore, when the terminals of the semiconductor device with terminals are buried in the viscoelastic layer 12, even if the solder balls, etc. have unevenness and are prone to floating, The raised terminal electrodes can also be buried, so that the terminal forming surface of the target semiconductor device with terminals can be closely connected to the viscoelastic layer 12 . Furthermore, since the relaxation elastic modulus variable The electromagnetic wave shielding film does not cause an electrical short circuit, and there is no need to install a complicated mask part or the like.

本實施形態的端子保護用膠帶係如圖2的端子保護用膠帶2所示，係依序具有黏著劑層14、埋入層13、基材11之構成，在黏彈性層12的黏著劑層14之側的最表層具備剝離膜20亦可。 The terminal protection tape of this embodiment is shown in the terminal protection tape 2 of FIG. 2 and is composed of an adhesive layer 14, an embedded layer 13, and a base material 11 in this order. The adhesive layer of the viscoelastic layer 12 The outermost layer on the side 14 may be provided with a release film 20 .

如圖2所示之端子保護用膠帶2係可用於如下步驟：將剝離膜 20加以剝離，將附端子之半導體裝置以端子之側朝下的方式壓裝在作為支撐體的基材11之上的黏彈性層12，在黏彈性層12埋設端子，進而從其上形成電磁波屏蔽膜之步驟。前述黏彈性層的動態黏彈性測定之中，50℃之tanδ的值為0.2以上，故將附端子之半導體裝置的端子埋設在黏彈性層12時，即使焊球等的具有凹凸且容易產生浮起之端子電極亦可埋設，可將作為對象之附端子之半導體裝置的端子形成面密接於黏彈性層12。進而，黏彈性層12的鬆弛彈性模量變數X2在如前述式(2)所示之預定的值的範圍內，故端子可以保持在被埋設的狀態且不產生浮起，並防止端子電極與電磁波屏蔽膜出現電性短路，且沒有必要設置步驟上複雜的遮罩部等。 The terminal protection tape 2 shown in Figure 2 can be used in the following steps: remove the peeling film 20 is peeled off, and the semiconductor device with terminals is pressed onto the viscoelastic layer 12 on the base material 11 as the support with the terminal side facing down, and the terminals are embedded in the viscoelastic layer 12, thereby forming electromagnetic waves thereon. Shielding film steps. In the dynamic viscoelasticity measurement of the viscoelastic layer mentioned above, the value of tan δ at 50°C is 0.2 or more. Therefore, when the terminals of the semiconductor device with terminals are buried in the viscoelastic layer 12, even if the solder balls, etc. have unevenness and are prone to floating, The raised terminal electrodes can also be buried, so that the terminal forming surface of the target semiconductor device with terminals can be closely connected to the viscoelastic layer 12 . Furthermore, the relaxation elastic modulus variable The electromagnetic wave shielding film does not cause an electrical short circuit, and there is no need to install a complicated mask part or the like.

本實施形態的端子保護用膠帶係如圖3的端子保護用膠帶3所示，係依序具有黏著劑層14、埋入層13、基材11之構成，在黏彈性層12的黏著劑層14之側的最表層具備剝離膜20亦可，在與基材11的黏彈性層12相反之側，亦可具備用以貼合支撐體之第二黏著劑層15(亦即貼合黏著劑層)，亦可為在第二黏著劑層15之側的最表層具備剝離膜22之雙面膠帶。 The terminal protection tape of this embodiment is shown in the terminal protection tape 3 of FIG. 3 and is composed of an adhesive layer 14, an embedded layer 13, and a base material 11 in this order. The adhesive layer of the viscoelastic layer 12 The outermost layer on the side 14 may be provided with a release film 20, and the side opposite to the viscoelastic layer 12 of the base material 11 may be provided with a second adhesive layer 15 for bonding to the support (that is, a bonding adhesive layer). layer), it may also be a double-sided tape having a release film 22 on the outermost layer on the side of the second adhesive layer 15 .

如圖3所示之端子保護用膠帶3係可用於如下步驟：將剝離膜22加以剝離，如圖4所示，固定在支撐體30，進而，將剝離膜20加以剝離，將附端子之半導體裝置以端子之側朝下的方式壓裝在黏彈性層12，在黏彈性層12埋設端子，進而從其上形成電磁波屏蔽膜之步驟。前述黏彈性層的動態黏彈性測定之中，50℃之tanδ的值為0.2以上，故附端子之半導體裝置的端子埋設在黏彈性層12時，即使焊球等的具有凹凸且容易產生浮起之端子電極亦可埋設，可將作為對象之附端子之半導體裝置的端子形成面密接於黏彈性層12。進而，黏彈性層12的鬆弛彈性模量變數X2在如前述式(2)所示之預定的值的範圍內，故端子可以保持在被埋設的狀態且不產生浮起，並防止端子電極與電磁波屏蔽膜出現電性短路，且沒有必要設置步驟 上複雜的遮罩部等。 The terminal protection tape 3 shown in Figure 3 can be used in the following steps: peel off the release film 22, and fix it on the support 30 as shown in Figure 4, and then peel off the release film 20 to remove the semiconductor with terminals. The device is press-fitted on the viscoelastic layer 12 with the terminal side facing down, the terminal is embedded in the viscoelastic layer 12, and an electromagnetic wave shielding film is formed thereon. In the dynamic viscoelasticity measurement of the viscoelastic layer mentioned above, the value of tan δ at 50°C is 0.2 or more. Therefore, when the terminals of the semiconductor device with terminals are buried in the viscoelastic layer 12, even if the solder balls, etc. have unevenness and are prone to floating, The terminal electrodes may also be buried, and the terminal formation surface of the target semiconductor device with terminals can be closely contacted with the viscoelastic layer 12 . Furthermore, the relaxation elastic modulus variable There is an electrical short circuit in the electromagnetic wave shielding film, and no installation steps are necessary. on complex masking parts, etc.

然後，對於構成本實施形態的端子保護用膠帶之各層進行說明。 Next, each layer constituting the terminal protective tape of this embodiment will be described.

◎黏彈性層 ◎Viscoelastic layer

本實施形態的端子保護用膠帶之中，黏彈性層係用以保護附端子之半導體裝置的端子形成面(換言之為電路面)、以及設置在該端子形成面上之端子，在黏彈性層的動態黏彈性測定之中，50℃之tanδ的值為0.2以上，對於前述黏彈性層，將直徑8mm、厚度約1mm的圓柱形狀的評價用試樣在50℃施加10%(亦即36°)的一定的扭轉應變來測定鬆弛彈性模量時，從最大鬆弛彈性模量G(t)max(MPa)以及離測定前述最大鬆弛彈性模量G(t)max後至1秒後為止所測定之最小鬆弛彈性模量G(t)min(MPa)，根據下述式(1)所求出之鬆弛彈性模量變數X2係滿足下述式(2)：X2=logG(t)max-logG(t)min‧‧‧(1) In the terminal protection tape of this embodiment, the viscoelastic layer is used to protect the terminal forming surface (in other words, the circuit surface) of the semiconductor device with terminals and the terminals provided on the terminal forming surface. In the dynamic viscoelasticity measurement, the value of tan δ at 50°C is 0.2 or more. For the aforementioned viscoelastic layer, a cylindrical evaluation sample with a diameter of 8 mm and a thickness of about 1 mm is applied at 50°C with a temperature of 10% (that is, 36°). When the relaxation elastic modulus is measured at a certain torsional strain, it is measured from the maximum relaxation elastic modulus G(t) max (MPa) and to 1 second after the measurement of the aforementioned maximum relaxation elastic modulus G(t) max . The minimum relaxation elastic modulus G(t) min (MPa), the relaxation elastic modulus variable X2 calculated according to the following formula (1) satisfies the following formula (2): X2=logG(t) max -logG( t) min ‧‧‧(1)

0.12≦X2‧‧‧(2) 0.12≦X2‧‧‧(2)

本說明書之中，「50℃之黏彈性層的tanδ」係可將50℃之黏彈性層的損失彈性模量G”(50℃)除以儲存彈性模量G’(50℃)而獲得。此外，後述的「25℃之黏彈性層的tanδ」係可將25℃之黏彈性層的損失彈性模量G”(25℃)除以儲存彈性模量G’(25℃)而獲得。 In this specification, "tan δ of the viscoelastic layer at 50°C" can be obtained by dividing the loss elastic modulus G" (50°C) of the viscoelastic layer at 50°C by the storage elastic modulus G' (50°C). In addition, the "tan δ of the viscoelastic layer at 25°C" described later can be obtained by dividing the loss elastic modulus G" (25°C) of the viscoelastic layer at 25°C by the storage elastic modulus G' (25°C).

此外，本說明書之中，黏彈性層的「損失彈性模量G”」以及「儲存彈性模量G’」，可在剪切黏度測定裝置設置厚度310μm的黏彈性層，以頻率：1Hz、升溫速度：10℃/min的測定條件，藉由從室溫升溫至100℃來測定而獲得。 In addition, in this specification, the "loss elastic modulus G" and "storage elastic modulus G'" of the viscoelastic layer can be measured by setting a viscoelastic layer with a thickness of 310 μm in the shear viscosity measuring device at a frequency of 1 Hz and a temperature rise Speed: Measurement conditions of 10°C/min are obtained by measuring from room temperature to 100°C.

本說明書之中，「最大鬆弛彈性模量G(t)max」係對於黏彈性層，準備直徑8mm、厚度約1mm的圓柱形狀的評價用試樣，設置在黏彈性 測定裝置(例如Anton paar公司製，製品名「MCR302」)，參考JIS K7244-7，以50℃旋轉治具並扭轉前述試樣，藉由裝置控制持續施加10%(亦即36°)的一定的扭轉應變，可由測定了鬆弛彈性模量G(t)之結果推導出。此外，本說明書之中，「最小鬆弛彈性模量G(t)min」係可由測定前述最大鬆弛彈性模量G(t)max1秒後為止所測定之鬆弛彈性模量G(t)推導出。 In this specification, "maximum relaxation elastic modulus G(t) max " means that for the viscoelastic layer, prepare a cylindrical evaluation sample with a diameter of 8 mm and a thickness of about 1 mm, and set it in a viscoelastic measuring device (for example, Anton Paar Co., Ltd. Manufactured, product name "MCR302"), refer to JIS K7244-7, rotate the jig at 50°C and twist the aforementioned sample, and continuously apply a certain torsional strain of 10% (that is, 36°) through device control. The measured The relaxation elastic modulus G(t) is derived from the results. In addition, in this specification, the "minimum relaxation elastic modulus G(t) min " can be deduced from the relaxation elastic modulus G(t) measured up to 1 second after measuring the aforementioned maximum relaxation elastic modulus G(t) max . .

黏彈性層12的一方的面，係黏著在半導體裝置的端子形成面。黏彈性層12之前述一方的面較佳為黏著劑層。因此，將附端子之半導體裝置貼附在黏著劑層14時的黏著力良好。 One surface of the viscoelastic layer 12 is adhered to the terminal formation surface of the semiconductor device. The aforementioned one side of the viscoelastic layer 12 is preferably an adhesive layer. Therefore, the adhesive force when the semiconductor device with terminals is attached to the adhesive layer 14 is good.

此外，鬆弛彈性模量變數X2需要為0.12以上，較佳為0.13以上，更佳為0.14以上。藉由鬆弛彈性模量變數X2為前述下限值以上，將附端子之半導體裝置貼附在黏著劑層14時端子保持在被埋設的狀態且不產生浮起。此外，鬆弛彈性模量變數X2較佳為0.42以下，更佳為0.35以下，尤佳為0.30以下。藉由鬆弛彈性模量變數X2為前述上限值以下，沒有過度埋設的風險，可獲得最適合的埋設性(以下亦稱為埋入性)。 In addition, the relaxation elastic modulus variable X2 needs to be 0.12 or more, preferably 0.13 or more, more preferably 0.14 or more. When the relaxation elastic modulus variable X2 is equal to or higher than the aforementioned lower limit value, when the semiconductor device with terminals is attached to the adhesive layer 14 , the terminals are maintained in a buried state and do not float. Furthermore, the relaxation elastic modulus variable X2 is preferably 0.42 or less, more preferably 0.35 or less, and particularly preferably 0.30 or less. When the relaxation elastic modulus variable X2 is equal to or less than the aforementioned upper limit, there is no risk of excessive embedding, and optimal embedding properties (hereinafter also referred to as embedding properties) can be obtained.

鬆弛彈性模量變數X2的上限值與下限值可以任意地組合。 The upper limit value and the lower limit value of the relaxation elastic modulus variable X2 can be combined arbitrarily.

例如，鬆弛彈性模量變數X2較佳為0.12以上至0.42以下，更佳為0.13以上至0.35以下，又更佳為0.14以上至0.30以下。 For example, the relaxation elastic modulus variable X2 is preferably from 0.12 to 0.42, more preferably from 0.13 to 0.35, and still more preferably from 0.14 to 0.30.

黏彈性層的動態黏彈性測定之中，50℃之tanδ的值為0.2以上，較佳為0.3以上，更佳為0.5以上。藉由50℃之tanδ的值為前述下限值以上，可確保對端子電極之追隨性與黏彈性層的流動性，故可提高端子電極的埋入性。50℃之tanδ的值可為6.5以下，可為6.0以下，可為5.4以下。 In the dynamic viscoelasticity measurement of the viscoelastic layer, the tan δ value at 50° C. is 0.2 or more, preferably 0.3 or more, and more preferably 0.5 or more. When the value of tan δ at 50° C. is equal to or higher than the aforementioned lower limit, the followability to the terminal electrode and the fluidity of the viscoelastic layer can be ensured, thereby improving the embedding property of the terminal electrode. The value of tan δ at 50°C may be 6.5 or less, 6.0 or less, or 5.4 or less.

50℃之tanδ的上限值與下限值可以任意地組合。 The upper limit and lower limit of tan δ at 50°C can be combined arbitrarily.

例如，50℃之tanδ較佳為0.2以上至6.5以下，更佳為0.3以上至6.0以下，又更佳為0.5以上至5.4以下。 For example, tan δ at 50° C. is preferably from 0.2 to 6.5, more preferably from 0.3 to 6.0, still more preferably from 0.5 to 5.4.

前述黏彈性層的50℃之儲存彈性模量G’(50℃)(MPa)較佳係滿足下述式(3)。 The 50°C storage elastic modulus G' (50°C) (MPa) of the viscoelastic layer preferably satisfies the following formula (3).

0.01MPa≦G’(50℃)≦15MPa‧‧‧(3) 0.01MPa≦G’(50℃)≦15MPa‧‧‧(3)

藉由滿足式(3)，即使是焊球等容易產生各種的形狀、大小的浮起之端子電極亦變得易於埋設。 By satisfying equation (3), even terminal electrodes such as solder balls that are prone to float in various shapes and sizes can be easily buried.

G’(50℃)較佳為0.01MPa至15MPa，更佳為0.02MPa至12.5MPa，又更佳為0.03MPa至10MPa。 G' (50°C) is preferably 0.01MPa to 15MPa, more preferably 0.02MPa to 12.5MPa, still more preferably 0.03MPa to 10MPa.

本實施形態的端子保護用膠帶較佳係前述黏彈性層的25℃之儲存彈性模量G’(25℃)(MPa)滿足下述式(4)。 In the terminal protection tape of this embodiment, it is preferable that the 25°C storage elastic modulus G' (25°C) (MPa) of the viscoelastic layer satisfies the following formula (4).

0.05MPa≦G’(25℃)≦20MPa‧‧‧(4) 0.05MPa≦G’(25℃)≦20MPa‧‧‧(4)

藉由滿足式(4)，易於保持常溫之端子保護用膠帶的形狀，且易於抑制對埋入層的端部之滲出。 By satisfying equation (4), it is easy to maintain the shape of the terminal protection tape at room temperature and to easily suppress bleeding to the end of the embedded layer.

G’(25℃)較佳為0.05MPa至20MPa，更佳為0.06MPa至15MPa，又更佳為0.07MPa至10MPa。 G' (25°C) is preferably 0.05MPa to 20MPa, more preferably 0.06MPa to 15MPa, still more preferably 0.07MPa to 10MPa.

黏彈性層的厚度d1可根據適用之半導體裝置的端子的高度h0而調整。黏彈性層的厚度較佳為80μm至800μm，更佳為100μm至790μm，尤佳為130μm至780μm。 The thickness d1 of the viscoelastic layer can be adjusted according to the height h0 of the terminal of the applicable semiconductor device. The thickness of the viscoelastic layer is preferably 80 μm to 800 μm, more preferably 100 μm to 790 μm, particularly preferably 130 μm to 780 μm.

黏彈性層的厚度為前述下限值以上，藉此即使為焊球等的端子電極亦可埋設。此外，埋入層的厚度為前述上限值以下，藉此可抑制端子保護用膠帶的厚度過剩。 The thickness of the viscoelastic layer is not less than the aforementioned lower limit, so that terminal electrodes such as solder balls can be embedded. Furthermore, by setting the thickness of the buried layer to be equal to or less than the upper limit, excessive thickness of the terminal protection tape can be suppressed.

此處，所謂「黏彈性層的厚度」，係指黏彈性層整體的厚度，由埋入層以及黏著劑層的複數層所構成之黏彈性層的厚度係指埋入層以及黏著劑層的合計的厚度。 Here, the "thickness of the viscoelastic layer" refers to the thickness of the entire viscoelastic layer, and the thickness of the viscoelastic layer composed of a plurality of buried layers and adhesive layers refers to the thickness of the buried layer and the adhesive layer. Total thickness.

本說明書之中，「層的厚度」係以隨機地選擇之5部位測定厚度之平均來表示之值，根據JIS K77130，使用定壓厚度測定器來測定。 In this specification, the "thickness of the layer" is a value expressed as the average of the measured thicknesses at five randomly selected locations, and is measured using a constant pressure thickness measuring device in accordance with JIS K77130.

前述黏彈性層的厚度d1(μm)較佳係和前述端子的高度h0(μm)之間滿足下述式(5)。 It is preferable that the thickness d1 (μm) of the viscoelastic layer and the height h0 (μm) of the terminal satisfy the following formula (5).

1.2≦d1/h0≦5.0‧‧‧(5) 1.2≦d1/h0≦5.0‧‧‧(5)

藉由滿足式(5)，即使是焊球等容易產生各種的形狀、大小的浮起之端子電極亦變得易於埋設。 By satisfying equation (5), even terminal electrodes such as solder balls that are prone to float in various shapes and sizes can be easily buried.

d1/h0較佳為1.2至5.0，更佳為1.3至5.0，又更佳為1.4至5.0。 d1/h0 is preferably 1.2 to 5.0, more preferably 1.3 to 5.0, still more preferably 1.4 to 5.0.

黏彈性層的動態黏彈性測定之中，25℃之tanδ的值可為0.2以上，亦可為0.10至1.4，較佳為0.20至1.0，更佳為0.30至0.8。 In the dynamic viscoelasticity measurement of the viscoelastic layer, the value of tan δ at 25° C. can be above 0.2, or between 0.10 and 1.4, preferably between 0.20 and 1.0, and more preferably between 0.30 and 0.8.

將附端子之半導體裝置的端子形成面密接黏彈性層12時，較佳係使附端子之半導體裝置的端子形成面直接密接黏彈性層12的黏著劑層14。 When the terminal forming surface of the semiconductor device with terminals is in close contact with the viscoelastic layer 12 , it is preferable that the terminal forming surface of the semiconductor device with terminals is directly in close contact with the adhesive layer 14 of the viscoelastic layer 12 .

此時，為了防止在端子形成面以及端子的殘膠，黏著劑層14較佳係設定為比埋入層13更硬。 At this time, in order to prevent adhesive residue on the terminal formation surface and the terminals, the adhesive layer 14 is preferably set to be harder than the embedded layer 13 .

○埋入層 ○Buried layer

本實施形態的端子保護用膠帶之中，埋入層係黏彈性層之中埋設附端子之半導體裝置的端子並保護之層。 In the terminal protection tape of this embodiment, the embedded layer is a layer that buries and protects the terminals of the semiconductor device with terminals in the viscoelastic layer.

埋入層為片狀或是膜狀，只要滿足前述條件的關係，其構成材料則並沒有特別限定。本說明書之中，所謂「片狀或是膜狀」，係指薄膜狀且面內的厚度不均小，具有可撓性。 The embedded layer is in the form of a sheet or a film, and its constituent material is not particularly limited as long as it satisfies the aforementioned conditions. In this specification, "sheet-like or film-like" means a film-like film with small in-plane thickness unevenness and flexibility.

例如，目的在於在覆蓋作為保護對象之附端子之半導體裝置的端子形成面之黏彈性層反映出存在於半導體表面之端子的形狀，藉此抑制黏彈性層變形的情況，作為前述埋入層較佳的構成材料，由更提高埋入 層的貼附性的觀點來看，可列舉如胺基甲酸酯(甲基)丙烯酸酯樹脂、丙烯酸系樹脂等。 For example, the purpose is to reflect the shape of the terminals existing on the surface of the semiconductor in the viscoelastic layer covering the terminal formation surface of the semiconductor device with terminals that is the object of protection, thereby suppressing the deformation of the viscoelastic layer. As the aforementioned embedded layer is relatively The best construction materials are embedded in the From the viewpoint of layer adhesion, examples include urethane (meth)acrylate resin, acrylic resin, and the like.

埋入層可僅為1層(單層)，亦可為2層以上的複數層，複數層的情況，這些複數層可彼此相同或不同，這些複數層的組合並沒有特別限定。 The buried layer may be only one layer (single layer), or may be a plurality of two or more layers. In the case of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.

另外，本說明書中，不限於埋入層的情況，所謂「複數層可彼此相同或不同」，係指「所有的層可相同、或所有的層不同亦可、亦可僅有一部分的層相同」，進而所謂「複數層彼此不同」，係指「各層的構成材料以及厚度之至少一者彼此不同」。 In addition, in this specification, it is not limited to the case of buried layers. The term "a plurality of layers may be the same or different from each other" means "all the layers may be the same, or all the layers may be different, or only part of the layers may be the same." ", and further, "the plurality of layers are different from each other" means "at least one of the constituent materials and thickness of each layer is different from each other."

埋入層的厚度係可根據作為保護對象之附端子之半導體裝置的端子形成面的端子的高度而適當調節，但由相對高度高的端子的影響亦可容易地吸收的觀點來看，黏彈性層的厚度為80μm至800μm的範圍，較佳係厚於黏著劑層，較佳為50μm至600μm，更佳為70μm至550μm，尤佳為80μm至500μm。藉由埋入層的厚度為前述下限值以上，可形成端子的保護性能更高的黏彈性層。此外，藉由埋入層的厚度為前述上限值以下，提高生產性與輥形狀之捲取適性。 The thickness of the embedded layer can be appropriately adjusted according to the height of the terminals on the terminal formation surface of the semiconductor device with terminals to be protected. However, from the viewpoint that the influence of terminals with a relatively high height can be easily absorbed, viscoelasticity The thickness of the layer is in the range of 80 μm to 800 μm, preferably thicker than the adhesive layer, preferably 50 μm to 600 μm, more preferably 70 μm to 550 μm, especially 80 μm to 500 μm. By setting the thickness of the buried layer above the aforementioned lower limit, a viscoelastic layer with higher protective performance for the terminal can be formed. In addition, when the thickness of the buried layer is equal to or less than the aforementioned upper limit, productivity and winding suitability of the roll shape are improved.

此處，「埋入層的厚度」係指埋入層整體的厚度，例如由複數層所構成之埋入層的厚度，係指構成埋入層之所有的層的合計的厚度。 Here, the "thickness of the buried layer" refers to the thickness of the entire buried layer. For example, the thickness of the buried layer composed of a plurality of layers refers to the total thickness of all the layers constituting the buried layer.

埋入層較佳係具有合適於埋設端子的柔軟性質，較佳係比黏著劑層更柔軟。 The embedded layer preferably has soft properties suitable for embedding terminals, and is preferably softer than the adhesive layer.

(埋入層形成用組成物) (Composition for buried layer formation)

埋入層係可使用含有該構成材料之埋入層形成用組成物來形成。 The buried layer can be formed using a buried layer forming composition containing this constituent material.

例如，在埋入層的形成對象面塗布埋入層形成用組成物，並根據需要使其乾燥，藉由能量線的照射使其硬化，藉此可在目的之部位形成埋入層。 此外，在剝離膜塗布埋入層形成用組成物，並根據需要使其乾燥，藉由能量線的照射使其硬化，藉此可形成目的之厚度的埋入層，亦可在目的之部位轉印埋入層。埋入層更具體的形成方法，與其它層的形成方法一起在之後詳細地說明。埋入層形成用組成物中在常溫不氣化之成分彼此的含量的比率，通常與埋入層的前述成分彼此的含量的比率相同。此處，所謂「常溫」，係指沒有特別冷或熱的溫度，亦即平常的溫度，可列舉例如15℃至30℃的溫度等。 For example, a buried layer-forming composition can be applied to the surface to be formed of the buried layer, dried if necessary, and hardened by irradiation with energy rays, whereby the buried layer can be formed at the desired location. In addition, by applying a composition for forming an embedded layer to the release film, drying it as necessary, and hardening it by irradiating energy rays, an embedded layer of the desired thickness can be formed, and the embedded layer can be transferred to the intended location. Print embedded layer. A more specific method of forming the embedded layer will be described in detail later along with the method of forming other layers. The content ratio of the components that do not vaporize at room temperature in the buried layer forming composition is generally the same as the content ratio of the aforementioned components in the buried layer. Here, "normal temperature" refers to a temperature that is not particularly cold or hot, that is, an ordinary temperature, and may include, for example, a temperature of 15°C to 30°C.

埋入層形成用組成物的塗布可以公知的方法進行即可，可列舉例如：氣刀塗布器、刮刀塗布器、棒塗布器、凹版塗布器、輥塗布器、輥刀塗布器、簾幕塗布器、模塗布器、刀塗布器、網印塗布器、線棒塗布器、模唇塗布器等使用各種塗布器的方法。 The buried layer forming composition may be coated by any known method, and examples thereof include: air knife coater, knife coater, rod coater, gravure coater, roller coater, roller knife coater, and curtain coater. Various applicator methods are used, such as die coater, knife coater, screen printing coater, wire rod coater, die lip coater, etc.

埋入層形成用組成物的乾燥條件並沒有特別限定，埋入層形成用組成物含有後述之溶劑的情況，較佳係加熱使其乾燥，該情況較佳係例如以70℃至130℃且10秒鐘至5分鐘的條件使其乾燥。 The drying conditions of the buried layer-forming composition are not particularly limited. When the buried layer-forming composition contains a solvent described below, it is preferred to dry it by heating. In this case, it is preferred to dry it at, for example, 70°C to 130°C and Condition it for 10 seconds to 5 minutes to dry.

埋入層形成用組成物具有能量線硬化性之情況，較佳係藉由能量線的照射使其硬化。 When the buried layer forming composition has energy ray curability, it is preferably hardened by irradiation with energy rays.

作為埋入層形成用組成物，可列舉例如含有丙烯酸系樹脂之埋入層形成用組成物(I)等。 Examples of the buried layer forming composition include the buried layer forming composition (I) containing an acrylic resin.

{埋入層形成用組成物(I)} {Composition (I) for buried layer formation}

埋入層形成用組成物(I)係含有丙烯酸系樹脂。 The embedded layer forming composition (I) contains an acrylic resin.

作為埋入層形成用組成物(I)，可將後述的第一黏著劑組成物(I-1)之中之含有由丙烯酸系樹脂之黏著性樹脂(I-1a)以及能量線硬化性化合物所構成之群組中所選擇之至少一種之組成物，以及第一黏著劑組成物(I-2)之中 之含有在丙烯酸系樹脂之黏著性樹脂(I-1a)之側鏈導入有不飽和基之能量線硬化性的黏著性樹脂(1-2a)之組成物用作埋入層形成用組成物(I)。 As the embedded layer forming composition (I), an adhesive resin (I-1a) containing an acrylic resin and an energy ray curable compound can be used as the first adhesive composition (I-1) described below. At least one selected composition from the group constituted, and the first adhesive composition (I-2) A composition containing an energy-beam curable adhesive resin (1-2a) in which an unsaturated group is introduced into the side chain of an acrylic resin adhesive resin (I-1a) is used as a buried layer forming composition ( I).

埋入層形成用組成物(I)中所使用之黏著性樹脂(I-1a)以及能量線硬化性化合物，係與後述之第一黏著劑組成物(I-1)所使用之黏著性樹脂(I-1a)以及能量線硬化性化合物的說明相同。 The adhesive resin (I-1a) and the energy ray curable compound used in the embedded layer forming composition (I) are the same as the adhesive resin used in the first adhesive composition (I-1) described below. The descriptions for (I-1a) and the energy ray curable compound are the same.

埋入層形成用組成物(I)中所使用之黏著性樹脂(I-2a)，係與後述之第一黏著劑組成物(I-2)中所使用之黏著性樹脂(I-2a)的說明相同。 The adhesive resin (I-2a) used in the embedded layer forming composition (I) is the same as the adhesive resin (I-2a) used in the first adhesive composition (I-2) described below. The instructions are the same.

埋入層形成用組成物(I)較佳係進而含有交聯劑。埋入層形成用組成物(I)中所使用之交聯劑，係與後述之第一黏著劑組成物(I-1)、第一黏著劑組成物(I-2)所使用之交聯劑的說明相同。 The buried layer forming composition (I) preferably further contains a crosslinking agent. The cross-linking agent used in the embedded layer forming composition (I) is the cross-linking agent used in the first adhesive composition (I-1) and the first adhesive composition (I-2) described below. The instructions for the agent are the same.

埋入層形成用組成物(I)亦可進而含有光聚合起始劑、其它添加劑。埋入層形成用組成物(I)中所使用之光聚合起始劑、其它添加劑，係與後述之第一黏著劑組成物(I-1)、第一黏著劑組成物(I-2)所使用之光聚合起始劑、其它添加劑的說明相同。 The buried layer forming composition (I) may further contain a photopolymerization initiator and other additives. The photopolymerization initiator and other additives used in the embedded layer forming composition (I) are the same as the first adhesive composition (I-1) and first adhesive composition (I-2) described below. The descriptions of the photopolymerization initiator and other additives used are the same.

埋入層形成用組成物(I)亦可含有溶劑。埋入層形成用組成物(I)、第一黏著劑組成物(I-2)中所使用之溶劑，係與後述之第一黏著劑組成物(I-1)所使用之溶劑的說明相同。 The buried layer forming composition (I) may contain a solvent. The solvent used in the embedded layer forming composition (I) and the first adhesive composition (I-2) is the same as the solvent used in the first adhesive composition (I-1) described below. .

埋入層形成用組成物(I)之中，藉由調整黏著性樹脂(I-1a)的分子量以及能量線硬化性化合物的分子量之任一者或是兩者，埋入層可設計為具有合適於埋設端子的柔軟性質。 In the buried layer forming composition (I), by adjusting either or both the molecular weight of the adhesive resin (I-1a) and the molecular weight of the energy ray curable compound, the buried layer can be designed to have Suitable for the soft nature of buried terminals.

此外，藉由調整埋入層形成用組成物(I)之中之交聯劑的含量，埋入層可設計為具有合適於埋設端子的柔軟性質。 In addition, by adjusting the content of the crosslinking agent in the buried layer forming composition (I), the buried layer can be designed to have soft properties suitable for buried terminals.

<<埋入層形成用組成物的製造方法>> <<Production method of composition for forming buried layer>>

埋入層形成用組成物(I)等的埋入層形成用組成物，可藉由調配用以構成該組成物之各成分而獲得。 A buried layer forming composition such as the buried layer forming composition (I) can be obtained by blending each component constituting the composition.

各成分的調配時之添加順序並沒有特別限定，亦可同時添加2種以上的成分。 The order in which each component is added is not particularly limited, and two or more components may be added at the same time.

使用溶劑之情況，亦可將溶劑與溶劑以外之任一調配成分混合而藉由將該調配成分預先稀釋來使用、亦可不將溶劑以外之任一調配成分預先稀釋而將溶劑與這些調配成分混合來使用。 When using a solvent, the solvent may be mixed with any preparation ingredients other than the solvent and used by diluting the preparation ingredients in advance, or the solvent may be mixed with these preparation ingredients without diluting any preparation ingredients other than the solvent in advance. to use.

調配時混合各成分之方法並沒有特別限定，可由以下公知的方法適當選擇即可：旋轉攪拌子或是攪拌葉片等來混合之方法；使用混合器來混合之方法；施加超音波來混合之方法等。 The method of mixing the ingredients during preparation is not particularly limited, and can be appropriately selected from the following known methods: mixing by rotating a stirrer or stirring blade, mixing by using a mixer, and mixing by applying ultrasonic waves. wait.

各成分的添加以及混合時的溫度以及時間，只要各調配成分未劣化則並沒有任何限定，適當調節即可，溫度較佳為15℃至30℃。 The temperature and time for adding and mixing each component are not limited as long as the components are not deteriorated and can be adjusted appropriately. The temperature is preferably 15°C to 30°C.

{埋入層的組成} {Composition of buried layer}

本實施形態之埋入層的組成，係從上述的埋入層形成用組成物(I)中去除溶劑者。 The composition of the buried layer in this embodiment is obtained by removing the solvent from the above-mentioned buried layer forming composition (I).

埋入層形成用組成物(I)係後述之第一黏著劑組成物(I-1)中之含有丙烯酸系樹脂之黏著性樹脂(I-1a)與能量線硬化性化合物之組成物之情況的埋入層(1)之埋入層(1)中，丙烯酸系樹脂之黏著性樹脂(I-1a)相對於埋入層(1)總質量的含有比率較佳為55質量%至99質量%，更佳為55質量%至95質量%，又更佳為60質量%至90質量%。本發明之另一方面，丙烯酸系樹脂之黏著性樹脂(I-1a)相對於埋入層(1)的總質量的含有比率可為45質量%至90質量%，亦可為50質量%至85質量%。此外，能量線硬化性化合物相對於埋入層(1)總質量的含有比率較佳為1質量%至50質量%，又更佳為5質量%至45質量%。埋入層(1)含有交聯劑的情況，交聯劑相對於埋入層(1)總質量的含 有比率較佳為0.1質量%至10質量%，更佳為0.2質量%至9質量%，又更佳為0.3質量%至8質量%。 The case where the buried layer forming composition (I) is a composition containing an acrylic resin adhesive resin (I-1a) and an energy ray curable compound in the first adhesive composition (I-1) described below. In the embedded layer (1) of the embedded layer (1), the content ratio of the acrylic resin adhesive resin (I-1a) relative to the total mass of the embedded layer (1) is preferably 55% by mass to 99% by mass. %, more preferably 55 mass % to 95 mass %, further preferably 60 mass % to 90 mass %. In another aspect of the present invention, the content ratio of the adhesive resin (I-1a) of the acrylic resin relative to the total mass of the embedded layer (1) may be 45% by mass to 90% by mass, or may be 50% by mass to 50% by mass. 85% by mass. In addition, the content ratio of the energy ray curable compound relative to the total mass of the embedded layer (1) is preferably 1 mass % to 50 mass %, and more preferably 5 mass % to 45 mass %. When the embedded layer (1) contains a cross-linking agent, the content of the cross-linking agent relative to the total mass of the embedded layer (1) The ratio is preferably 0.1 mass% to 10 mass%, more preferably 0.2 mass% to 9 mass%, and still more preferably 0.3 mass% to 8 mass%.

埋入層形成用組成物(I)係含有在丙烯酸系樹脂之黏著性樹脂(I-1a)之側鏈導入有不飽和基之能量線硬化性的黏著性樹脂(1-2a)之組成物之情況下的埋入層(2)中，在側鏈導入有不飽和基之能量線硬化性的黏著性樹脂(1-2a)相對於埋入層總質量的含有比率較佳為10質量%至70質量%，更佳為15質量%至65質量%，又更佳為20質量%至60質量%。此外，本發明的另一方面，丙烯酸系樹脂之黏著性樹脂(I-1a)相對於埋入層(2)總質量的含有比率亦可為10質量%至60質量%，亦可為15質量%至55質量%，亦可為20質量%至55質量%。埋入層(2)含有交聯劑之情況，交聯劑相對於埋入層(2)總質量的含有比率較佳為0.1質量%至10質量%，更佳為0.2質量%至9質量%，又更佳為0.3質量%至7.8質量%。此外，本實施形態的埋入層(2)亦可進而含有前述丙烯酸系樹脂之黏著性樹脂(I-1a)。該情況，丙烯酸系樹脂之黏著性樹脂(I-1a)相對於埋入層(2)總質量的含有比率較佳為35質量%至85質量%，更佳為40質量%至80質量%，又更佳為35質量%至75質量%。此外，本實施形態的埋入層(2)進而含有前述丙烯酸系樹脂之黏著性樹脂(I-1a)之情況，相對於前述黏著性樹脂(1-2a)100質量份，前述黏著性樹脂(1-1a)的含量較佳為40質量份至150質量份，更佳為50質量份至140質量份，又更佳為60質量份至130質量份。 The composition (I) for forming the buried layer is a composition containing an energy-beam curable adhesive resin (1-2a) in which an unsaturated group is introduced into the side chain of an acrylic resin adhesive resin (I-1a). In the embedded layer (2) in this case, the content ratio of the energy-beam curable adhesive resin (1-2a) having an unsaturated group introduced into the side chain relative to the total mass of the embedded layer is preferably 10% by mass. to 70 mass%, more preferably 15 mass% to 65 mass%, further preferably 20 mass% to 60 mass%. In addition, in another aspect of the present invention, the content ratio of the adhesive resin (I-1a) of the acrylic resin relative to the total mass of the embedded layer (2) may be 10 mass % to 60 mass %, or 15 mass %. % to 55 mass%, or 20 mass% to 55 mass%. When the embedded layer (2) contains a cross-linking agent, the content ratio of the cross-linking agent relative to the total mass of the embedded layer (2) is preferably 0.1 mass% to 10 mass%, more preferably 0.2 mass% to 9 mass%. , and more preferably 0.3% by mass to 7.8% by mass. In addition, the embedded layer (2) of this embodiment may further contain the adhesive resin (I-1a) of the acrylic resin. In this case, the content ratio of the adhesive resin (I-1a) of the acrylic resin relative to the total mass of the embedded layer (2) is preferably 35 mass% to 85 mass%, more preferably 40 mass% to 80 mass%. More preferably, it is 35 mass % to 75 mass %. In addition, when the embedded layer (2) of this embodiment further contains the adhesive resin (I-1a) of the acrylic resin, the adhesive resin (I-1a) is 100 parts by mass of the adhesive resin (1-2a). The content of 1-1a) is preferably 40 to 150 parts by mass, more preferably 50 to 140 parts by mass, and still more preferably 60 to 130 parts by mass.

埋入層(1)所含有之丙烯酸系樹脂之黏著性樹脂(I-1a)、能量線硬化性化合物、在埋入層(2)所含有之在黏著性樹脂(I-1a)之側鏈導入有不飽和基之能量線硬化性的黏著性樹脂(1-2a)的組成等，亦可與後述之第一黏著劑組成物(I-1)所使用之丙烯酸系樹脂之黏著性樹脂(I-1a)、能量線硬化性化合物、在黏著性樹脂(I-1a)之側鏈導入有不飽和基之能量線硬化性的黏著 性樹脂(1-2a)的說明相同。 The adhesive resin (I-1a) of the acrylic resin contained in the embedded layer (1), the energy ray curable compound, and the side chain of the adhesive resin (I-1a) contained in the embedded layer (2) The composition of the energy-beam curable adhesive resin (1-2a) into which unsaturated groups are introduced can also be used with the acrylic resin adhesive resin (1-2a) used in the first adhesive composition (I-1) described later. I-1a), energy ray curable compound, energy ray curable adhesive in which an unsaturated group is introduced into the side chain of the adhesive resin (I-1a) The description of the resin (1-2a) is the same.

本實施形態中，較佳係含有黏著性樹脂(1-2a)、黏著性樹脂(1-1a)、以及交聯劑之埋入層(2)。該情況，黏著性樹脂(1-1a)較佳係具有源自(甲基)丙烯酸烷基酯的構成單元、源自含羧基單體的單元之丙烯酸系聚合物。此外，黏著性樹脂(1-2a)較佳係如下之丙烯酸系聚合物：在具有源自(甲基)丙烯酸烷基酯的構成單元、源自含羥基單體的單元之丙烯酸系聚合物，與具有異氰酸酯基以及能量線聚合性不飽和基之含不飽和基化合物反應所獲得。交聯劑係可使用後述的第一黏著劑組成物(I-1)中所例示之化合物，尤佳係使用甲苯二異氰酸酯。 In this embodiment, the embedded layer (2) preferably contains an adhesive resin (1-2a), an adhesive resin (1-1a), and a cross-linking agent. In this case, the adhesive resin (1-1a) is preferably an acrylic polymer having a structural unit derived from an alkyl (meth)acrylate and a unit derived from a carboxyl group-containing monomer. Furthermore, the adhesive resin (1-2a) is preferably an acrylic polymer having a structural unit derived from an alkyl (meth)acrylate and a unit derived from a hydroxyl-containing monomer, Obtained by reacting with unsaturated group-containing compounds having isocyanate groups and energy-ray polymerizable unsaturated groups. As the cross-linking agent, compounds exemplified in the first adhesive composition (I-1) described below can be used, and toluene diisocyanate is particularly preferred.

源自(甲基)丙烯酸烷基酯的構成單元相對於黏著性樹脂(1-1a)總質量的含有比率較佳為75質量%至99質量%，更佳為80質量%至98質量%，又更佳為85質量%至97質量%。本發明的另一方面，源自(甲基)丙烯酸烷基酯的構成單元相對於黏著性樹脂(1-1a)總質量的含有比率可為70質量%至95質量%，亦可為80質量%至95質量%。含羧基單體的構成單元相對於黏著性樹脂(1-1a)總質量的含有比率較佳為1.0質量%至30質量%，更佳為2.0質量%至25質量%，又更佳為3.0質量%至20質量%。本發明的另一方面，含羧基單體的構成單元相對於黏著性樹脂(1-1a)總質量的含有比率可為3.0質量%至20質量%，亦可為5.0質量%至15質量%。黏著性樹脂(1-1a)之(甲基)丙烯酸烷基酯較佳係烷基的碳數為4至12，更佳為4至8。此外，黏著性樹脂(1-1a)中，較佳為丙烯酸烷基酯。其中前述(甲基)丙烯酸烷基酯尤佳為丙烯酸正丁酯。此外，作為黏著性樹脂(1-1a)之含羧基單體，可列舉如乙烯性不飽和單羧酸、乙烯性不飽和二羧酸、乙烯性不飽和二羧酸的酸酐等，其中較佳為乙烯性不飽和單羧酸，更佳為(甲基)丙烯酸，尤佳為丙烯酸。 The content ratio of the structural unit derived from the alkyl (meth)acrylate relative to the total mass of the adhesive resin (1-1a) is preferably 75 mass% to 99 mass%, more preferably 80 mass% to 98 mass%. More preferably, it is 85 mass % to 97 mass %. In another aspect of the present invention, the content ratio of the structural unit derived from alkyl (meth)acrylate relative to the total mass of the adhesive resin (1-1a) may be 70 mass % to 95 mass %, or may be 80 mass %. % to 95% by mass. The content ratio of the structural unit of the carboxyl group-containing monomer relative to the total mass of the adhesive resin (1-1a) is preferably 1.0 mass% to 30 mass%, more preferably 2.0 mass% to 25 mass%, and still more preferably 3.0 mass% % to 20% by mass. In another aspect of the present invention, the content ratio of the structural unit of the carboxyl group-containing monomer relative to the total mass of the adhesive resin (1-1a) may be 3.0 mass% to 20 mass%, or may be 5.0 mass% to 15 mass%. The alkyl (meth)acrylate of the adhesive resin (1-1a) preferably has an alkyl group with a carbon number of 4 to 12, more preferably 4 to 8. Furthermore, among the adhesive resins (1-1a), alkyl acrylate is preferred. Among them, the aforementioned alkyl (meth)acrylate is particularly preferably n-butyl acrylate. In addition, examples of the carboxyl group-containing monomer of the adhesive resin (1-1a) include ethylenically unsaturated monocarboxylic acid, ethylenically unsaturated dicarboxylic acid, anhydride of ethylenically unsaturated dicarboxylic acid, etc., among which the preferred ones are It is ethylenically unsaturated monocarboxylic acid, more preferably (meth)acrylic acid, especially acrylic acid.

本實施形態的黏著性樹脂(1-1a)的重量平均分子量較佳為100,000至800,000，更佳為150,000至700,000，又更佳為200,000至600,000。 The weight average molecular weight of the adhesive resin (1-1a) of this embodiment is preferably 100,000 to 800,000, more preferably 150,000 to 700,000, still more preferably 200,000 to 600,000.

另外，本說明書之中，所謂「重量平均分子量」，若無特別限定，係指藉由凝膠滲透層析(gel permeation chromatograph；GPC)法所測定之聚苯乙烯換算值。 In addition, in this specification, the so-called "weight average molecular weight" refers to the polystyrene-converted value measured by gel permeation chromatography (gel permeation chromatograph; GPC) method, unless otherwise specified.

源自(甲基)丙烯酸烷基酯的構成單元相對於黏著性樹脂(1-2a)總質量的含有比率較佳為1.0質量%至95質量%，更佳為2.0質量%至90質量%，又更佳為3.0質量%至85質量%。源自含羥基單體的單元相對於黏著性樹脂(1-2a)總質量的含有比率較佳為1.0質量%至50質量%，更佳為2.0質量%至45質量%，又更佳為3.0質量%至40質量%。黏著性樹脂(1-2a)之(甲基)丙烯酸烷基酯較佳係烷基的碳數為1至12，更佳為1至4。黏著性樹脂(1-2a)較佳係具有源自2種以上的(甲基)丙烯酸烷基酯的構成單元，更佳係具有(甲基)丙烯酸甲酯以及源自(甲基)丙烯酸正丁酯的構成單元，又更佳係具有源自甲基丙烯酸甲酯以及丙烯酸正丁酯的構成單元。作為黏著性樹脂(1-2a)之含羥基單體，可使用後述的第一黏著劑組成物(I-1)中所例示者，尤佳係使用丙烯酸2-羥乙酯。作為具有異氰酸酯基以及能量線聚合性不飽和基之含不飽和基化合物，可使用後述的第一黏著劑組成物(I-2)中所例示之化合物，尤佳係使用2-甲基丙烯醯氧乙基異氰酸酯。源自前述含羥基單體之全羥基為100mol時之前述具有異氰酸酯基以及能量線聚合性不飽和基之含不飽和基化合物的使用量較佳為10mol至150mol，更佳為20mol至140mol，又更佳為30mol至130mol。 The content ratio of the structural unit derived from the alkyl (meth)acrylate relative to the total mass of the adhesive resin (1-2a) is preferably 1.0 mass% to 95 mass%, more preferably 2.0 mass% to 90 mass%, More preferably, it is 3.0 mass % to 85 mass %. The content ratio of the unit derived from the hydroxyl-containing monomer relative to the total mass of the adhesive resin (1-2a) is preferably 1.0 mass % to 50 mass %, more preferably 2.0 mass % to 45 mass %, and still more preferably 3.0 mass% to 40 mass%. The (meth)acrylic acid alkyl ester of the adhesive resin (1-2a) preferably has a carbon number of 1 to 12 in the alkyl group, more preferably 1 to 4. The adhesive resin (1-2a) preferably has structural units derived from two or more alkyl (meth)acrylates, and more preferably has methyl (meth)acrylate and n-(meth)acrylic acid. The structural unit of butyl ester is more preferably a structural unit derived from methyl methacrylate and n-butyl acrylate. As the hydroxyl group-containing monomer of the adhesive resin (1-2a), those exemplified in the first adhesive composition (I-1) described later can be used, and 2-hydroxyethyl acrylate is particularly preferred. As the unsaturated group-containing compound having an isocyanate group and an energy ray polymerizable unsaturated group, compounds exemplified in the first adhesive composition (I-2) described later can be used, and 2-methacrylamide is particularly preferred. Oxyethyl isocyanate. When the total hydroxyl group derived from the aforementioned hydroxyl-containing monomer is 100 mol, the usage amount of the aforementioned unsaturated group-containing compound having an isocyanate group and an energy beam polymerizable unsaturated group is preferably 10 mol to 150 mol, more preferably 20 mol to 140 mol, and More preferably, it is 30 mol to 130 mol.

本實施形態的黏著性樹脂(1-2a)的重量平均分子量較佳為10,000至500,000，更佳為20,000至400,000，又更佳為30,000至300,000。 The weight average molecular weight of the adhesive resin (1-2a) of this embodiment is preferably 10,000 to 500,000, more preferably 20,000 to 400,000, still more preferably 30,000 to 300,000.

○黏著劑層 ○Adhesive layer

以下為使得構成黏彈性層之黏著劑層與後述的用以貼合至支撐體之第二黏著劑層有所區別，有時稱為「第一黏著劑層」。 The following is a distinction between the adhesive layer constituting the viscoelastic layer and the second adhesive layer used to bond to the support, which will be described later, and is sometimes referred to as the "first adhesive layer".

第一黏著劑層為片狀或是膜狀，且含有黏著劑。 The first adhesive layer is in the form of a sheet or film and contains adhesive.

作為前述黏著劑，可列舉例如：丙烯酸系樹脂(由具有(甲基)丙烯醯基之樹脂所構成之黏著劑)、胺基甲酸酯系樹脂(由具有胺基甲酸酯鍵之樹脂所構成之黏著劑)、橡膠系樹脂(由具有橡膠結構之樹脂所構成之黏著劑)、聚矽氧系樹脂(由具有矽氧烷鍵之樹脂所構成之黏著劑)、環氧系樹脂(由具有環氧基之樹脂所構成之黏著劑)、聚乙烯醚、聚碳酸酯等的黏著性樹脂，較佳為丙烯酸系樹脂。 Examples of the adhesive include acrylic resins (adhesives composed of resins having (meth)acrylyl groups) and urethane resins (adhesives composed of resins having urethane bonds). Adhesives composed of resins), rubber resins (adhesives composed of resins with rubber structures), polysilicone resins (adhesives composed of resins with siloxane bonds), epoxy resins (adhesives composed of resins with siloxane bonds) Adhesive resins composed of resins with epoxy groups), polyvinyl ether, polycarbonate, etc. are preferably acrylic resins.

另外，本發明之中，所謂「黏著性樹脂」，係指包含具有黏著性之樹脂、具有接著性之樹脂的兩者之概念，例如，不僅樹脂本身具有黏著性者，亦包含藉由併用添加劑等的其它成分而顯示黏著性之樹脂、或藉由熱或是水等的觸發因素的存在而顯示接著性之樹脂等。 In addition, in the present invention, the so-called "adhesive resin" refers to a concept that includes both resins with adhesiveness and resins with adhesiveness. For example, not only resins themselves have adhesiveness, but also resins that have adhesiveness through the combined use of additives. Resins that exhibit adhesive properties due to other components such as heat or water, or resins that exhibit adhesive properties due to the presence of trigger factors such as heat or water.

第一黏著劑層可僅為1層(單層)，亦可為2層以上的複數層，為複數層的情況，這些複數層可彼此相同或不同，這些複數層的組合並沒有特別限定。 The first adhesive layer may be only one layer (single layer), or may be a plurality of two or more layers. In the case of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.

第一黏著劑層的厚度較佳為1μm至1000μm，更佳為2μm至100μm，尤佳為8μm至20μm。 The thickness of the first adhesive layer is preferably 1 μm to 1000 μm, more preferably 2 μm to 100 μm, particularly preferably 8 μm to 20 μm.

此處，所謂「第一黏著劑層的厚度」，係指第一黏著劑層整體的厚度，例如，所謂由複數層所構成之第一黏著劑層的厚度，係指構成第一黏著劑層之所有的層的合計的厚度。 Here, the so-called "thickness of the first adhesive layer" refers to the thickness of the entire first adhesive layer. For example, the so-called thickness of the first adhesive layer composed of a plurality of layers refers to the thickness of the first adhesive layer. The total thickness of all layers.

第一黏著劑層可為使用能量線硬化性黏著劑所形成，亦可為使用非能量線硬化性黏著劑所形成。使用能量線硬化性的黏著劑所形成之第一黏著劑層，係可容易地調節硬化前以及硬化後之物性。 The first adhesive layer may be formed using an energy ray curable adhesive or may be formed using a non-energy ray curable adhesive. The first adhesive layer formed by using energy ray curable adhesive can easily adjust the physical properties before and after hardening.

本發明之中，所謂「能量線」，係指電磁波或是帶電粒子束之中具有能量量子者，作為該例，可列舉如紫外線、電子束等。 In the present invention, "energy rays" refer to electromagnetic waves or charged particle beams that have energy quanta. Examples thereof include ultraviolet rays and electron beams.

紫外線，係例如可以使用作為紫外線源之高壓汞燈、融合H燈或是氙氣燈等來照射。電子束係可藉由電子束加速器等來照射所產生者。 Ultraviolet rays can be irradiated using, for example, a high-pressure mercury lamp, a fused H lamp, a xenon lamp, etc. as an ultraviolet source. The electron beam system can be generated by irradiation with an electron beam accelerator or the like.

本發明之中，所謂「能量線硬化性」，係指照射能量線而藉此硬化之性質，所謂「非能量線硬化性」，係指即使照射能量線亦不會硬化之性質。 In the present invention, "energy ray hardenability" refers to the property of being hardened by irradiation with energy rays, and "non-energy ray hardenability" refers to the property of not being hardened even if energy rays are irradiated.

{{第一黏著劑組成物}} {{First adhesive composition}}

第一黏著劑層係可使用含有黏著劑之第一黏著劑組成物來形成。例如，在第一黏著劑層的形成對象面塗布第一黏著劑組成物，並根據需要使其乾燥，可藉此在目的之部位形成第一黏著劑層。此外，在剝離膜塗布第一黏著劑組成物，並根據需要使其乾燥，藉此可形成目的之厚度的第一黏著劑層，亦可在目的之部位轉印第一黏著劑層。第一黏著劑層之更具體的形成方法，與其它層的形成方法一起在之後詳細地說明。第一黏著劑組成物中在常溫不氣化之成分彼此的含量的比率，通常與第一黏著劑層的前述成分彼此的含量的比率相同。另外，本實施形態之中，所謂「常溫」，係指沒有特別冷或熱的溫度，亦即平常的溫度，可列舉例如15℃至25℃的溫度等。 The first adhesive layer can be formed using a first adhesive composition containing an adhesive. For example, the first adhesive layer can be formed at the target location by applying the first adhesive composition on the surface to be formed of the first adhesive layer and drying it as necessary. In addition, by applying the first adhesive composition to the release film and drying it as necessary, a first adhesive layer of a desired thickness can be formed, and the first adhesive layer can also be transferred to a desired location. A more specific formation method of the first adhesive layer will be described in detail later along with the formation methods of other layers. The ratio of the contents of the components that do not vaporize at room temperature in the first adhesive composition to each other is usually the same as the ratio of the contents of the aforementioned components to each other in the first adhesive layer. In addition, in this embodiment, "normal temperature" refers to a temperature that is not particularly cold or hot, that is, an ordinary temperature, and may include, for example, a temperature of 15°C to 25°C.

第一黏著劑組成物的塗布可以公知的方法進行即可，可列舉例如：氣刀塗布器、刮刀塗布器、棒塗布器、凹版塗布器、輥塗布器、輥刀塗布器、簾幕塗布器、模塗布器、刀塗布器、網印塗布器、線棒塗布器、模唇塗布器等使用各種塗布器的方法。 The first adhesive composition can be coated by a known method, and examples thereof include: air knife coater, knife coater, rod coater, gravure coater, roller coater, roller knife coater, curtain coater , die coater, knife coater, screen printing coater, wire rod coater, die lip coater and other methods using various coaters.

第一黏著劑組成物的乾燥條件並沒有特別限定，第一黏著劑組成物如含有後述之溶劑之情況，較佳係加熱使其乾燥，該情況，較佳係例如在70℃至130℃以10秒鐘至5分鐘的條件使其乾燥。 The drying conditions of the first adhesive composition are not particularly limited. If the first adhesive composition contains a solvent described later, it is preferably heated to dry it. In this case, it is preferably dried at 70°C to 130°C, for example. Condition it for 10 seconds to 5 minutes to dry.

第一黏著劑層為能量線硬化性之情況，含有能量線硬化性黏著劑之第一黏著劑組成物、亦即作為能量線硬化性的第一黏著劑組成物，可列舉例如：含有非能量線硬化性的黏著性樹脂(I-1a)(以下亦簡稱為「黏著性樹脂(I-1a)」)與能量線硬化性化合物之第一黏著劑組成物(I-1)；含有在非能量線硬化性的黏著性樹脂(I-1a)之側鏈導入有不飽和基之能量線硬化性的黏著性樹脂(I-2a)(以下亦簡稱為「黏著性樹脂(I-2a)」)之第一黏著劑組成物(I-2)；含有前述黏著性樹脂(I-2a)與能量線硬化性低分子化合物之第一黏著劑組成物(I-3)等。 When the first adhesive layer is energy ray curable, the first adhesive composition containing the energy ray curable adhesive, that is, the energy ray curable first adhesive composition, may include, for example: a non-energy ray curable first adhesive composition. The first adhesive composition (I-1) of linearly curable adhesive resin (I-1a) (hereinafter also referred to as "adhesive resin (I-1a)") and energy ray curable compound; contained in non- Energy ray curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the energy ray curable adhesive resin (I-1a) (hereinafter also referred to as "adhesive resin (I-2a)") ) first adhesive composition (I-2); first adhesive composition (I-3) containing the aforementioned adhesive resin (I-2a) and an energy ray curable low molecular compound, etc.

{第一黏著劑組成物(I-1)} {First adhesive composition (I-1)}

第一黏著劑組成物(I-1)係如上述含有非能量線硬化性的黏著性樹脂(I-1a)與能量線硬化性化合物。 The first adhesive composition (I-1) contains a non-energy ray curable adhesive resin (I-1a) and an energy ray curable compound as described above.

(黏著性樹脂(I-1a)) (Adhesive resin (I-1a))

前述黏著性樹脂(I-1a)較佳為丙烯酸系樹脂。 The adhesive resin (I-1a) is preferably an acrylic resin.

作為前述丙烯酸系樹脂，可列舉例如至少含有源自(甲基)丙烯酸烷基酯的構成單元之丙烯酸系聚合物。 Examples of the acrylic resin include an acrylic polymer containing at least a structural unit derived from an alkyl (meth)acrylate.

前述丙烯酸系樹脂所具有之構成單元，可僅為1種、亦可為2種以上，若為2種以上之情況，可任意地選擇這些組合以及比率。 The acrylic resin may have only one type of structural unit or two or more types. In the case of two or more types, these combinations and ratios may be arbitrarily selected.

作為前述(甲基)丙烯酸烷基酯，可列舉例如構成烷基酯之烷基的碳數為1至20者，前述烷基較佳係直鏈狀或是支鏈狀。 Examples of the (meth)acrylic acid alkyl ester include those in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms. The alkyl group is preferably linear or branched.

作為(甲基)丙烯酸烷基酯，更具體而言可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸二級丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正辛酯、(甲基)丙 烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一酯、(甲基)丙烯酸十二酯(亦稱為(甲基)丙烯酸月桂酯)、(甲基)丙烯酸十三酯、(甲基)丙烯酸十四酯(亦稱為(甲基)丙烯酸肉豆蔻酸酯)、(甲基)丙烯酸十五酯、(甲基)丙烯酸十六酯(亦稱為(甲基)丙烯酸棕櫚酸酯)、(甲基)丙烯酸十七酯、(甲基)丙烯酸十八酯(亦稱為(甲基)丙烯酸硬脂酸酯)、(甲基)丙烯酸十八酯、(甲基)丙烯酸二十酯等。 More specifically, the (meth)acrylic acid alkyl esters include: (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid n-propyl ester, (meth)acrylic acid isopropyl ester , n-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate )Hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, (meth)propyl n-nonyl acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (also known as lauryl (meth)acrylate ester), tridecyl (meth)acrylate, myristyl (meth)acrylate (also known as myristate (meth)acrylate), pentadecyl (meth)acrylate, tendecyl (meth)acrylate Hexaester (also known as (meth)acrylic acid palmitate), (meth)acrylic acid ester, stearyl (meth)acrylate (also known as (meth)acrylic acid stearate), (meth)acrylic acid stearate (Basyl)octadecyl acrylate, eicosyl (meth)acrylate, etc.

由提高第一黏著劑層的黏著力的觀點來看，前述丙烯酸系聚合物較佳係具有前述烷基的碳數為4以上之源自(甲基)丙烯酸烷基酯的構成單元。然後，由更提高第一黏著劑層的黏著力的觀點來看，前述烷基的碳數較佳為4至12，更佳為4至8。此外，前述烷基的碳數為4以上之(甲基)丙烯酸烷基酯，較佳為丙烯酸烷基酯。 From the viewpoint of improving the adhesive force of the first adhesive layer, the acrylic polymer preferably has a structural unit derived from an alkyl (meth)acrylate having a carbon number of 4 or more in the alkyl group. From the viewpoint of further improving the adhesive force of the first adhesive layer, the carbon number of the alkyl group is preferably 4 to 12, and more preferably 4 to 8. In addition, the (meth)acrylic acid alkyl ester having a carbon number of 4 or more in the alkyl group is preferably an acrylic acid alkyl ester.

前述丙烯酸系聚合物除了源自(甲基)丙烯酸烷基酯的構成單元以外，較佳係進而具有源自含官能基單體的構成單元。 The acrylic polymer preferably further has a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from a (meth)acrylic acid alkyl ester.

作為前述含官能基單體，可列舉如：藉由前述官能基與後述之交聯劑反應而成為交聯的起點、或是藉由前述官能基與含不飽和基化合物中的不飽和基反應而可在丙烯酸系聚合物之側鏈導入有不飽和基。 Examples of the functional group-containing monomer include: the functional group reacts with a cross-linking agent described later to become a starting point for cross-linking; or the functional group reacts with an unsaturated group in an unsaturated group-containing compound. An unsaturated group may be introduced into the side chain of the acrylic polymer.

作為含官能基單體中的前述官能基，可列舉例如：羥基、羧基、胺基、環氧基等。 Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxyl group, an amino group, an epoxy group, and the like.

亦即，作為含官能基單體，可列舉例如：含羥基單體、含羧基單體、含胺基單體、含環氧基單體等。 That is, examples of the functional group-containing monomer include hydroxyl group-containing monomers, carboxyl group-containing monomers, amine group-containing monomers, epoxy group-containing monomers, and the like.

作為前述含羥基單體，可列舉例如：(甲基)丙烯酸羥基甲酯、(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等的(甲基)丙烯酸羥基烷基酯；乙烯醇、丙烯醇等的非(甲基)丙烯 酸系不飽和醇(亦即不具有(甲基)丙烯醯基骨架之不飽和醇)等。 Examples of the hydroxyl-containing monomer include: (meth)acrylic acid hydroxymethyl ester, (meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid 2-hydroxypropyl, (meth)acrylic acid 3-hydroxyl Propyl ester, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyalkyl (meth)acrylates; vinyl alcohol, Non-(meth)propylene such as propylene alcohol Acid-based unsaturated alcohols (that is, unsaturated alcohols without (meth)acrylyl skeleton), etc.

作為前述含羧基單體，可列舉例如：(甲基)丙烯酸、巴豆酸等的乙烯性不飽和單羧酸(具有乙烯性不飽和鍵之單羧酸)；富馬酸、伊康酸、馬來酸、檸康酸等的乙烯性不飽和二羧酸(具有乙烯性不飽和鍵之二羧酸)；前述乙烯性不飽和二羧酸的酸酐；2-羧乙基甲基丙烯酸酯等的(甲基)丙烯酸羧基烷基酯等。 Examples of the carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, and martinic acid. Ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having an ethylenically unsaturated bond) such as lenic acid and citraconic acid; anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylate, etc. Carboxyalkyl (meth)acrylate, etc.

含官能基單體較佳為含羥基單體、含羧基單體，更佳為含羥基單體。 The functional group-containing monomer is preferably a hydroxyl group-containing monomer or a carboxyl group-containing monomer, and more preferably a hydroxyl group-containing monomer.

構成前述丙烯酸系聚合物之含官能基單體可僅為1種，亦可為2種以上，若為2種以上的情況，可任意地選擇這些組合以及比率。 The functional group-containing monomer constituting the acrylic polymer may be only one type, or may be two or more types. In the case of two or more types, these combinations and ratios may be selected arbitrarily.

前述丙烯酸系聚合物之中，源自含官能基單體的構成單元的含量，相對於構成單元的總量，較佳為1質量%至35質量%，更佳為3質量%至32質量%，尤佳為5質量%至30質量%。 In the acrylic polymer, the content of the structural units derived from the functional group-containing monomer is preferably 1 to 35 mass %, more preferably 3 to 32 mass % with respect to the total amount of the structural units. , especially preferably 5% by mass to 30% by mass.

前述丙烯酸系聚合物，除了源自(甲基)丙烯酸烷基酯的構成單元、以及源自含官能基單體的構成單元以外，亦可進而具有源自其它單體的構成單元。 The acrylic polymer may further have structural units derived from other monomers, in addition to structural units derived from alkyl (meth)acrylate and functional group-containing monomers.

前述其它單體只要是可與(甲基)丙烯酸烷基酯等共聚者則並沒有特別限定。 The aforementioned other monomers are not particularly limited as long as they are copolymerizable with alkyl (meth)acrylate and the like.

作為前述其它單體，可列舉例如：苯乙烯、α-甲基苯乙烯、乙烯基甲苯、甲酸乙烯、乙酸乙烯、丙烯腈、丙烯醯胺等。 Examples of the other monomers include styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide, and the like.

構成前述丙烯酸系聚合物之前述其它單體可僅為1種，亦可為2種以上，若為2種以上的情況，可任意地選擇這些組合以及比率。 The other monomers constituting the acrylic polymer may be only one type, or may be two or more types. In the case of two or more types, these combinations and ratios may be arbitrarily selected.

前述丙烯酸系聚合物係可用作為上述的非能量線硬化性的黏著性樹脂(I-1a)。 The acrylic polymer can be used as the non-energy ray curable adhesive resin (I-1a).

另一方面，在前述丙烯酸系聚合物中的官能基與具有能量線聚合性不飽和基(能量線聚合性基)之含不飽和基化合物反應者，可用作為上述的能量線硬化性的黏著性樹脂(I-2a)。 On the other hand, when the functional group in the acrylic polymer reacts with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group (energy ray polymerizable group), it can be used as the above-mentioned energy ray curable adhesive. Resin (I-2a).

另外，本發明之中，所謂「能量線聚合性」，係指藉由照射能量線而聚合之性質。 In addition, in the present invention, "energy ray polymerizability" refers to the property of polymerizing by irradiating energy rays.

第一黏著劑組成物(I-1)所含有之黏著性樹脂(I-1a)，亦可僅為1種、亦可為2種以上，若為2種以上的情況，可任意地選擇這些組合以及比率。 The adhesive resin (I-1a) contained in the first adhesive composition (I-1) may be only one type, or may be two or more types. In the case of two or more types, these may be selected arbitrarily. combinations and ratios.

第一黏著劑組成物(I-1)之中，黏著性樹脂(I-1a)的含量，相對於第一黏著劑組成物(I-1)的總質量，較佳為5質量%至99質量%，更佳為10質量%至95質量%，尤佳為15質量%至90質量%。 In the first adhesive composition (I-1), the content of the adhesive resin (I-1a) is preferably 5% by mass to 99% with respect to the total mass of the first adhesive composition (I-1). mass%, more preferably 10 mass% to 95 mass%, particularly preferably 15 mass% to 90 mass%.

(能量線硬化性化合物) (Energy ray curing compound)

作為第一黏著劑組成物(I-1)所含有之前述能量線硬化性化合物，可列舉如具有能量線聚合性不飽和基、且藉由能量線的照射而可硬化的單體或是低聚物。 Examples of the energy ray curable compound contained in the first adhesive composition (I-1) include monomers or low-energy ray curable compounds that have an energy ray polymerizable unsaturated group and are curable by irradiation with energy rays. Polymer.

能量線硬化性化合物之中，作為單體，可列舉例如：三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇(甲基)丙烯酸酯等的多元(甲基)丙烯酸酯；胺基甲酸酯(甲基)丙烯酸酯；聚酯(甲基)丙烯酸酯；聚醚(甲基)丙烯酸酯；環氧(甲基)丙烯酸酯等。 Among the energy ray curable compounds, examples of monomers include: trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Poly(meth)acrylates such as meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate; urethane ( Meth)acrylate; polyester (meth)acrylate; polyether (meth)acrylate; epoxy (meth)acrylate, etc.

能量線硬化性化合物之中，作為低聚物，可列舉例如上述所例示之單體經聚合之低聚物等。 Examples of the oligomer among the energy ray curable compounds include oligomers obtained by polymerizing the monomers exemplified above.

能量線硬化性化合物由分子量相對大、且不易降低第一黏著劑層的儲存彈性模量的觀點來看，較佳為胺基甲酸酯(甲基)丙烯酸酯、胺基甲酸酯(甲基)丙烯酸酯低聚物。 The energy ray curable compound is preferably a urethane (meth)acrylate or a urethane (meth)acrylate from the viewpoint of having a relatively large molecular weight and not easily reducing the storage elastic modulus of the first adhesive layer. base) acrylate oligomer.

本說明書之中，所謂「低聚物」，係指重量平均分子量或是式量為5,000以下的物質。 In this specification, the so-called "oligomer" refers to a substance with a weight average molecular weight or formula weight of 5,000 or less.

第一黏著劑組成物(I-1)所含有之前述能量線硬化性化合物，可僅為1種，亦可為2種以上，若為2種以上的情況，可任意地選擇這些組合以及比率。 The first adhesive composition (I-1) may contain only one type of energy ray curable compound or two or more types. In the case of two or more types, these combinations and ratios may be arbitrarily selected. .

第一黏著劑組成物(I-1)之中，前述能量線硬化性化合物的含量相對於第一黏著劑組成物(I-1)的總質量，較佳為1質量%至95質量%，更佳為5質量%至90質量%，尤佳為10質量%至85質量%。 In the first adhesive composition (I-1), the content of the energy ray curable compound is preferably 1 mass % to 95 mass % relative to the total mass of the first adhesive composition (I-1). More preferably, it is 5 mass % to 90 mass %, especially 10 mass % to 85 mass %.

(交聯劑) (cross-linking agent)

作為黏著性樹脂(I-1a)，若使用除了具有源自(甲基)丙烯酸烷基酯的構成單元以外，進而具有源自含官能基單體的構成單元之前述丙烯酸系聚合物之情況，第一黏著劑組成物(I-1)較佳係進而含有交聯劑。 As the adhesive resin (I-1a), when in addition to the structural unit derived from alkyl (meth)acrylate, the above-mentioned acrylic polymer having a structural unit derived from a functional group-containing monomer is used, The first adhesive composition (I-1) preferably further contains a cross-linking agent.

前述交聯劑係例如與前述官能基反應，且黏著性樹脂(I-1a)彼此交聯者。 The cross-linking agent is, for example, one that reacts with the functional group to cross-link the adhesive resins (I-1a) with each other.

作為交聯劑，可列舉例如：甲苯二異氰酸酯、六亞甲基二異氰酸酯、二甲苯二異氰酸酯、這些二異氰酸酯的加成物等的異氰酸酯系交聯劑(具有異氰酸酯基之交聯劑)；N,N'-(環己烷-1,3-二基雙亞甲基)雙(二縮水甘油基胺)、乙二醇縮水甘油基醚等的環氧系交聯劑(具有縮水甘油基之交聯劑)；六[1-(2-甲基)-氮丙啶]三磷三嗪等的氮丙啶系交聯劑(具有氮丙啶基之交聯劑)；鋁螯合物等的金屬螯合物系交聯劑(具有金屬螯合物結構之交聯劑)；異氰脲酸酯系交聯劑(具有異氰脲酸骨架之交聯劑)等。 Examples of the cross-linking agent include isocyanate-based cross-linking agents (cross-linking agents having an isocyanate group) such as toluene diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, and adducts of these diisocyanates; N ,N'-(cyclohexane-1,3-diyl bismethylene)bis(diglycidylamine), ethylene glycol glycidyl ether and other epoxy cross-linking agents (with glycidyl group Cross-linking agent); aziridine-based cross-linking agents (cross-linking agents with aziridine groups) such as hexa[1-(2-methyl)-aziridine]triphosphorus triazine; aluminum chelates, etc. The metal chelate is a cross-linking agent (a cross-linking agent with a metal chelate structure); the isocyanurate cross-linking agent (a cross-linking agent with an isocyanuric acid skeleton), etc.

由提高黏著劑的凝集力且提高第一黏著劑層的黏著力的觀點、以及容易取得等的觀點來看，交聯劑較佳為異氰酸酯系交聯劑。 The cross-linking agent is preferably an isocyanate-based cross-linking agent from the viewpoint of improving the cohesive force of the adhesive and improving the adhesive force of the first adhesive layer, and from the viewpoint of ease of acquisition.

第一黏著劑組成物(I-1)所含有之交聯劑可僅為1種、亦可為2種以上，若為2種以上之情況，可任意地選擇這些組合以及比率。 The cross-linking agent contained in the first adhesive composition (I-1) may be only one type, or may be two or more types. In the case of two or more types, these combinations and ratios may be selected arbitrarily.

第一黏著劑組成物(I-1)之中，交聯劑的含量相對於黏著性樹脂(I-1a)的含量100質量份，較佳為0.01質量份至50質量份，更佳為0.1質量份至20質量份，尤佳為1質量份至10質量份。 In the first adhesive composition (I-1), the content of the cross-linking agent is preferably 0.01 to 50 parts by mass, and more preferably 0.1 with respect to 100 parts by mass of the adhesive resin (I-1a). Parts by mass to 20 parts by mass, preferably 1 part by mass to 10 parts by mass.

(光聚合起始劑) (Photopolymerization initiator)

第一黏著劑組成物(I-1)亦可進而含有光聚合起始劑。含有光聚合起始劑之第一黏著劑組成物(I-1)，即使照射紫外線等的相對低能量的能量線，亦可充分地進行硬化反應。 The first adhesive composition (I-1) may further contain a photopolymerization initiator. The first adhesive composition (I-1) containing a photopolymerization initiator can fully proceed with the curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

作為前述光聚合起始劑，可列舉例如：安息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香異丁醚、安息香苯甲酸、安息香苯甲酸甲酯、安息香二甲基縮酮等安息香化合物；苯乙酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮等苯乙酮化合物；雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦等醯基氧化膦化合物；苄基苯基硫醚、一硫化四甲基秋蘭姆等硫醚化合物；1-羥基環己基苯基酮等α-縮酮化合物；偶氮雙異丁腈等偶氮化合物；二茂鈦等二茂鈦化合物；噻噸酮等噻噸酮化合物；過氧化物化合物；二乙醯等二酮化合物；苯偶醯、二苯偶醯、二苯甲酮、2,4-二乙基噻噸酮、1,2-二苯基甲烷、2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮、2-氯蒽醌等。 Examples of the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. ; Acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one and other phenylethanes Ketone compounds; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and other hydroxyphosphine oxide compounds; benzyl Phylphenyl sulfide, tetramethylthiuram monosulfide and other sulfide compounds; α-ketal compounds such as 1-hydroxycyclohexylphenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene and other dioxins Titanocene compounds; thioxanthone compounds such as thioxanthone; peroxide compounds; diketone compounds such as diethyl chloride; benzoyl chloride, diphenyl chloride, benzophenone, 2,4-diethylthioxanthone , 1,2-diphenylmethane, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone, 2-chloroanthraquinone, etc.

此外，作為前述光聚合起始劑，亦可使用例如：1-氯蒽醌等的醌化合物；胺等的光增感劑等。 In addition, as the photopolymerization initiator, for example, quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines, etc. can also be used.

第一黏著劑組成物(I-1)所含有之光聚合起始劑可僅為1種、 亦可為2種以上，若為2種以上之情況，可任意地選擇這些組合以及比率。 The first adhesive composition (I-1) may contain only one type of photopolymerization initiator, There may be two or more types. In the case of two or more types, these combinations and ratios can be selected arbitrarily.

第一黏著劑組成物(I-1)之中，光聚合起始劑的含量相對於前述能量線硬化性化合物的含量100質量份，較佳為0.01質量份至20質量份，更佳為0.03質量份至10質量份，尤佳為0.05質量份至5質量份。 In the first adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, and more preferably 0.03 parts by mass relative to 100 parts by mass of the energy ray curable compound. Parts by mass to 10 parts by mass, preferably 0.05 parts by mass to 5 parts by mass.

(其它添加劑) (Other additives)

第一黏著劑組成物(I-1)在不損及本發明的效果範圍內，亦可含有不屬於上述任一成分之其它添加劑。 The first adhesive composition (I-1) may also contain other additives that do not belong to any of the above components within the scope that does not impair the effects of the present invention.

作為前述其它添加劑，可列舉例如：抗靜電劑、抗氧化劑、軟化劑(塑化劑)、充填劑(填料)、防鏽劑、著色劑(顏料、染料)、增感劑、增黏劑，反應延遲劑，交聯促進劑(觸媒)等的公知的添加劑。 Examples of the aforementioned other additives include: antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, and tackifiers. Well-known additives such as reaction retardants and cross-linking accelerators (catalysts).

另外，所謂反應延遲劑，係例如藉由混入第一黏著劑組成物(I-1)中之觸媒的作用，而在保存中的第一黏著劑組成物(I-1)之中抑制非目的之交聯反應進行。作為反應延遲劑，可列舉例如藉由對觸媒之螯合而形成螯合錯合物，更具體而言，可列舉如在1分子中具有2個以上的羰基(-C(=O)-)。 In addition, the so-called reaction retardant suppresses non-uniform reaction in the first adhesive composition (I-1) during storage, for example, by the action of a catalyst mixed into the first adhesive composition (I-1). The cross-linking reaction for the purpose is carried out. Examples of the reaction retardant include chelate complexes formed by chelating a catalyst. More specifically, examples include chelate complexes having two or more carbonyl groups (-C(=O)- in one molecule). ).

第一黏著劑組成物(I-1)所含有之其它添加劑可僅為1種、亦可為2種以上，若為2種以上之情況，可任意地選擇這些組合以及比率。 The other additives contained in the first adhesive composition (I-1) may be only one type or two or more types. In the case of two or more types, these combinations and ratios can be arbitrarily selected.

第一黏著劑組成物(I-1)之中，其它添加劑的含量並沒有特別限定，可根據種類而適當選擇即可。 In the first adhesive composition (I-1), the content of other additives is not particularly limited and can be appropriately selected according to the type.

(溶劑) (solvent)

第一黏著劑組成物(I-1)亦可含有溶劑。第一黏著劑組成物(I-1)含有溶劑，藉此提高對塗布對象面之塗布適性。 The first adhesive composition (I-1) may also contain a solvent. The first adhesive composition (I-1) contains a solvent, thereby improving the coating suitability for the surface to be coated.

前述溶劑較佳為有機溶劑，作為前述有機溶劑，可列舉例如：甲乙酮、丙酮等的酮；乙酸乙酯等的酯(羧酸酯)；四氫呋喃、二噁烷等的醚；環己烷、正己烷等的脂肪烴；甲苯、二甲苯等的芳香烴；1-丙醇、 2-丙醇等的醇等。 The solvent is preferably an organic solvent. Examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; esters (carboxylic acid esters) such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; cyclohexane and n-hexane Aliphatic hydrocarbons such as alkanes; aromatic hydrocarbons such as toluene and xylene; 1-propanol, Alcohols such as 2-propanol, etc.

作為前述溶劑，例如可使得製造黏著性樹脂(I-1a)時所使用之溶劑不自黏著性樹脂(I-1a)去除而直接用於第一黏著劑組成物(I-1)，亦可將與製造黏著性樹脂(I-1a)時所使用之溶劑相同或是不同種類的溶劑在製造第一黏著劑組成物(I-1)時另外添加。 As the aforementioned solvent, for example, the solvent used in manufacturing the adhesive resin (I-1a) may be used directly in the first adhesive composition (I-1) without being removed from the adhesive resin (I-1a), or the solvent may be used directly in the first adhesive composition (I-1). The same or a different type of solvent as that used in producing the adhesive resin (I-1a) is additionally added when producing the first adhesive composition (I-1).

第一黏著劑組成物(I-1)所含有之溶劑可僅為1種、亦可為2種以上，若為2種以上之情況，可任意地選擇這些組合以及比率。 The solvent contained in the first adhesive composition (I-1) may be only one type, or may be two or more types. In the case of two or more types, these combinations and ratios may be selected arbitrarily.

第一黏著劑組成物(I-1)之中，溶劑的含量並沒有特別限定，適當調節即可。 In the first adhesive composition (I-1), the content of the solvent is not particularly limited and can be adjusted appropriately.

{第一黏著劑組成物(I-2)} {First adhesive composition (I-2)}

第一黏著劑組成物(I-2)係如上述含有在非能量線硬化性的黏著性樹脂(I-1a)之側鏈導入有不飽和基之能量線硬化性的黏著性樹脂(I-2a)。 The first adhesive composition (I-2) contains an energy ray curable adhesive resin (I-) in which an unsaturated group is introduced into the side chain of the non-energy ray curable adhesive resin (I-1a) as described above. 2a).

(黏著性樹脂(I-2a)) (Adhesive resin (I-2a))

前述黏著性樹脂(I-2a)係例如使得黏著性樹脂(I-1a)中的官能基與具有能量線聚合性不飽和基之含不飽和基化合物反應所獲得。 The adhesive resin (I-2a) is obtained, for example, by reacting a functional group in the adhesive resin (I-1a) with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group.

前述含不飽和基化合物係除了具有前述能量線聚合性不飽和基以外，進而具有可與黏著性樹脂(I-1a)中的官能基反應而與黏著性樹脂(I-1a)鍵結之基之化合物。 The aforementioned unsaturated group-containing compound has, in addition to the aforementioned energy-beam polymerizable unsaturated group, a group that can react with a functional group in the adhesive resin (I-1a) and bond with the adhesive resin (I-1a). of compounds.

作為前述能量線聚合性不飽和基，可列舉例如：(甲基)丙烯醯基、乙烯基(Vinyl，亦稱為Ethenyl)、烯丙基(亦稱為2-丙烯基)等，較佳為(甲基)丙烯醯基。 Examples of the energy ray polymerizable unsaturated group include: (meth)acrylyl group, vinyl (Vinyl, also called Ethenyl), allyl group (also called 2-propenyl), etc., and preferably (Meth)acrylyl.

作為可與黏著性樹脂(I-1a)中的官能基鍵結之基，可列舉例如：可與羥基或是胺基鍵結之異氰酸酯基以及縮水甘油基、以及可與羧基或是環氧基鍵結之羥基以及胺基等。 Examples of the group that can be bonded to the functional group in the adhesive resin (I-1a) include an isocyanate group and a glycidyl group that can be bonded to a hydroxyl group or an amine group, and a carboxyl group or an epoxy group. Bonded hydroxyl and amine groups, etc.

作為前述含不飽和基化合物，可列舉例如：(甲基)丙烯醯氧基乙基異氰酸酯、(甲基)丙烯醯基異氰酸酯、縮水甘油基(甲基)丙烯酸酯等，較佳為(甲基)丙烯醯氧基乙基異氰酸酯，其中尤佳為2-甲基丙烯醯氧乙基異氰酸酯。 Examples of the unsaturated group-containing compound include: (meth)acryloxyethyl isocyanate, (meth)acrylyl isocyanate, glycidyl (meth)acrylate, etc., and (meth)acryloxyethyl isocyanate is preferred. ) acryloxyethyl isocyanate, of which 2-methacryloxyethyl isocyanate is particularly preferred.

前述異氰酸酯化合物係可與黏著性樹脂(I-1a)中的羥基鍵結，設黏著性樹脂(I-1a)中的全羥基為100mol時，前述異氰酸酯化合物的使用量較佳為10mol至150mol，更佳為20mol至140mol，又更佳為30mol至130mol。 The aforementioned isocyanate compound can bond with the hydroxyl group in the adhesive resin (I-1a). When the total hydroxyl group in the adhesive resin (I-1a) is 100 mol, the usage amount of the aforementioned isocyanate compound is preferably 10 mol to 150 mol. More preferably, it is 20 mol to 140 mol, and still more preferably, it is 30 mol to 130 mol.

第一黏著劑組成物(I-2)所含有之黏著性樹脂(I-2a)可僅為1種、亦可為2種以上，若為2種以上之情況，可任意地選擇這些組合以及比率。 The adhesive resin (I-2a) contained in the first adhesive composition (I-2) may be only one type, or may be two or more types. In the case of two or more types, these combinations may be selected arbitrarily. ratio.

第一黏著劑組成物(I-2)之中，黏著性樹脂(I-2a)的含量相對於第一黏著劑組成物(I-2)的總質量，較佳為5質量%至99質量%，更佳為10質量%至95質量%，尤佳為10質量%至90質量%。 In the first adhesive composition (I-2), the content of the adhesive resin (I-2a) is preferably 5% by mass to 99% by mass relative to the total mass of the first adhesive composition (I-2). %, more preferably 10 mass% to 95 mass%, particularly preferably 10 mass% to 90 mass%.

(交聯劑) (cross-linking agent)

作為黏著性樹脂(I-2a)若使用例如與黏著性樹脂(I-1a)相同之具有源自含官能基單體的構成單元之前述丙烯酸系聚合物的情況，第一黏著劑組成物(I-2)亦可進而含有交聯劑。 If, for example, the aforementioned acrylic polymer having the same structural unit derived from a functional group-containing monomer as the adhesive resin (I-1a) is used as the adhesive resin (I-2a), the first adhesive composition ( I-2) may further contain a cross-linking agent.

作為第一黏著劑組成物(I-2)之前述交聯劑，可列舉與第一黏著劑組成物(I-1)之交聯劑相同者。 The cross-linking agent mentioned in the first adhesive composition (I-2) may be the same as the cross-linking agent in the first adhesive composition (I-1).

第一黏著劑組成物(I-2)所含有之交聯劑可僅為1種、亦可為2種以上，若為2種以上之情況，可任意地選擇這些組合以及比率。 The cross-linking agent contained in the first adhesive composition (I-2) may be only one type or two or more types. In the case of two or more types, these combinations and ratios may be selected arbitrarily.

第一黏著劑組成物(I-2)之中，交聯劑的含量相對於黏著性樹脂(I-2a)的含量100質量份，較佳為0.01質量份至50質量份，更佳為0.1質量份至20質量份，尤佳為1質量份至10質量份。 In the first adhesive composition (I-2), the content of the cross-linking agent is preferably 0.01 to 50 parts by mass, and more preferably 0.1 with respect to 100 parts by mass of the adhesive resin (I-2a). Parts by mass to 20 parts by mass, preferably 1 part by mass to 10 parts by mass.

(光聚合起始劑) (Photopolymerization initiator)

第一黏著劑組成物(I-2)係亦可進而含有光聚合起始劑。含有光聚合起始劑之第一黏著劑組成物(I-2)，即使照射紫外線等的相對低能量的能量線，亦可充分地進行硬化反應。 The first adhesive composition (I-2) may further contain a photopolymerization initiator. The first adhesive composition (I-2) containing a photopolymerization initiator can fully proceed with the curing reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.

作為第一黏著劑組成物(I-2)之前述光聚合起始劑，可列舉與第一黏著劑組成物(I-1)之光聚合起始劑相同者。 Examples of the photopolymerization initiator of the first adhesive composition (I-2) include the same photopolymerization initiator as the photopolymerization initiator of the first adhesive composition (I-1).

第一黏著劑組成物(I-2)所含有之光聚合起始劑可僅為1種、亦可為2種以上，若為2種以上之情況，可任意地選擇這些組合以及比率。 The photopolymerization initiator contained in the first adhesive composition (I-2) may be only one type, or may be two or more types. In the case of two or more types, these combinations and ratios may be selected arbitrarily.

第一黏著劑組成物(I-2)之中，光聚合起始劑的含量相對於黏著性樹脂(I-2a)的含量100質量份，較佳為0.01質量份至20質量份，更佳為0.03質量份至10質量份，尤佳為0.05質量份至5質量份。 In the first adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the adhesive resin (I-2a), and more preferably The amount is 0.03 parts by mass to 10 parts by mass, particularly preferably 0.05 parts by mass to 5 parts by mass.

(其它添加劑) (Other additives)

第一黏著劑組成物(I-2)，只要在不損及本發明的效果的範圍內，亦可含有不屬於上述任一成分之其它添加劑。 The first adhesive composition (I-2) may also contain other additives that do not belong to any of the above-mentioned components as long as the effects of the present invention are not impaired.

作為第一黏著劑組成物(I-2)之前述其它添加劑，可列舉與第一黏著劑組成物(I-1)之其它添加劑相同者。 Examples of the other additives mentioned above in the first adhesive composition (I-2) include the same additives as those in the first adhesive composition (I-1).

第一黏著劑組成物(I-2)所含有之其它添加劑可僅為1種、亦可為2種以上，若為2種以上之情況，可任意地選擇這些組合以及比率。 The other additives contained in the first adhesive composition (I-2) may be only one type, or may be two or more types. In the case of two or more types, these combinations and ratios may be selected arbitrarily.

第一黏著劑組成物(I-2)之中，其它添加劑的含量並沒有特別限定，可根據種類而適當選擇即可。 In the first adhesive composition (I-2), the content of other additives is not particularly limited and can be appropriately selected according to the type.

(溶劑) (solvent)

第一黏著劑組成物(I-2)亦可與第一黏著劑組成物(I-1)的情況同樣的目的而含有溶劑。 The first adhesive composition (I-2) may contain a solvent for the same purpose as the first adhesive composition (I-1).

作為第一黏著劑組成物(I-2)之前述溶劑，可列舉與第一黏著劑組成物(I-1)之溶劑相同者。 Examples of the solvent for the first adhesive composition (I-2) include the same solvent as the solvent for the first adhesive composition (I-1).

第一黏著劑組成物(I-2)所含有之溶劑可僅為1種、亦可為2種以上，若為2種以上之情況，可任意地選擇這些組合以及比率。 The solvent contained in the first adhesive composition (I-2) may be only one type, or may be two or more types. In the case of two or more types, these combinations and ratios may be selected arbitrarily.

第一黏著劑組成物(I-2)之中，溶劑的含量並沒有特別限定，適當調節即可。 In the first adhesive composition (I-2), the content of the solvent is not particularly limited and can be adjusted appropriately.

{第一黏著劑組成物(I-3)} {First adhesive composition (I-3)}

第一黏著劑組成物(I-3)係如上述含有前述黏著性樹脂(I-2a)與能量線硬化性低分子化合物。 The first adhesive composition (I-3) contains the adhesive resin (I-2a) and an energy ray curable low molecular compound as described above.

第一黏著劑組成物(I-3)之中，黏著性樹脂(I-2a)的含量相對於第一黏著劑組成物(I-3)的總質量，較佳為5質量%至99質量%，更佳為10質量%至95質量%，尤佳為15質量%至90質量%。 In the first adhesive composition (I-3), the content of the adhesive resin (I-2a) is preferably 5% by mass to 99% by mass relative to the total mass of the first adhesive composition (I-3). %, more preferably 10 mass% to 95 mass%, particularly preferably 15 mass% to 90 mass%.

(能量線硬化性低分子化合物) (Energy ray hardening low molecular compound)

作為第一黏著劑組成物(I-3)所含有之前述能量線硬化性低分子化合物，可舉出具有能量線聚合性不飽和基而可藉由照射能量線而硬化的單體以及低聚物。可舉出與第一黏著劑組成物(I-1)所含有之能量線硬化性化合物相同者。 Examples of the energy ray curable low molecular compound contained in the first adhesive composition (I-3) include monomers and oligomers that have an energy ray polymerizable unsaturated group and can be cured by irradiation with energy rays. things. Examples thereof include the same energy ray curable compound contained in the first adhesive composition (I-1).

第一黏著劑組成物(I-3)所含有之前述能量線硬化性低分子化合物可僅為1種、亦可為2種以上，若為2種以上之情況，可任意地選擇這些組合以及比率。 The energy ray curable low molecular compound contained in the first adhesive composition (I-3) may be only one type, or may be two or more types. In the case of two or more types, these combinations may be arbitrarily selected. ratio.

第一黏著劑組成物(I-3)之中，前述能量線硬化性低分子化合物的含量相對於黏著性樹脂(I-2a)的含量100質量份，較佳為0.01質量份至300質量份，更佳為0.03質量份至200質量份，尤佳為0.05質量份至100質量份。 In the first adhesive composition (I-3), the content of the energy ray curable low molecular compound is preferably 0.01 to 300 parts by mass relative to 100 parts by mass of the adhesive resin (I-2a). , more preferably 0.03 parts by mass to 200 parts by mass, particularly preferably 0.05 parts by mass to 100 parts by mass.

(光聚合起始劑) (Photopolymerization initiator)

第一黏著劑組成物(I-3)亦可進而含有光聚合起始劑。含有光聚合起始劑之第一黏著劑組成物(I-3)即使照射紫外線等的相對低能量的能量線，亦可充分地進行硬化反應。 The first adhesive composition (I-3) may further contain a photopolymerization initiator. The first adhesive composition (I-3) containing a photopolymerization initiator can fully proceed with the curing reaction even if it is irradiated with relatively low-energy energy rays such as ultraviolet rays.

作為第一黏著劑組成物(I-3)之前述光聚合起始劑，可列舉與第一黏著劑組成物(I-1)之光聚合起始劑相同者。 Examples of the photopolymerization initiator of the first adhesive composition (I-3) include the same photopolymerization initiator as the photopolymerization initiator of the first adhesive composition (I-1).

第一黏著劑組成物(I-3)所含有之光聚合起始劑可僅為1種、亦可為2種以上，若為2種以上之情況，可任意地選擇這些組合以及比率。 The photopolymerization initiator contained in the first adhesive composition (I-3) may be only one type, or may be two or more types. In the case of two or more types, these combinations and ratios may be selected arbitrarily.

第一黏著劑組成物(I-3)之中，光聚合起始劑的含量相對於黏著性樹脂(I-2a)以及前述能量線硬化性低分子化合物的總含量100質量份，較佳為0.01質量份至20質量份，更佳為0.03質量份至10質量份，尤佳為0.05質量份至5量部。 In the first adhesive composition (I-3), the content of the photopolymerization initiator is preferably 100 parts by mass relative to the total content of the adhesive resin (I-2a) and the energy ray curable low molecular compound. 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, particularly preferably 0.05 to 5 parts by mass.

(其它添加劑) (Other additives)

第一黏著劑組成物(I-3)，只要在不損及本發明的效果的範圍內，亦可含有不屬於上述任一成分之其它添加劑。 The first adhesive composition (I-3) may also contain other additives that do not belong to any of the above-mentioned components as long as the effects of the present invention are not impaired.

作為前述其它添加劑，可列舉與第一黏著劑組成物(I-1)之其它添加劑相同者。 Examples of the aforementioned other additives include the same additives as those used in the first adhesive composition (I-1).

第一黏著劑組成物(I-3)所含有之其它添加劑可僅為1種、亦可為2種以上，若為2種以上之情況，可任意地選擇這些組合以及比率。 The other additives contained in the first adhesive composition (I-3) may be only one type or two or more types. In the case of two or more types, these combinations and ratios may be selected arbitrarily.

第一黏著劑組成物(I-3)之中，其它添加劑的含量並沒有特別限定，可根據種類而適當選擇即可。 In the first adhesive composition (I-3), the content of other additives is not particularly limited and can be appropriately selected according to the type.

(溶劑) (solvent)

第一黏著劑組成物(I-3)可與第一黏著劑組成物(I-1)的情況同樣的目的而含有溶劑。 The first adhesive composition (I-3) may contain a solvent for the same purpose as the first adhesive composition (I-1).

作為第一黏著劑組成物(I-3)之前述溶劑，可列舉與第一黏著劑組成物(I-1)之溶劑相同者。 Examples of the solvent for the first adhesive composition (I-3) include the same solvent as the solvent for the first adhesive composition (I-1).

第一黏著劑組成物(I-3)所含有之溶劑可僅為1種、亦可為2種以上，若為2種以上之情況，可任意地選擇這些組合以及比率。 The solvent contained in the first adhesive composition (I-3) may be only one type, or may be two or more types. In the case of two or more types, these combinations and ratios may be selected arbitrarily.

第一黏著劑組成物(I-3)之中，溶劑的含量並沒有特別限定，適當調節即可。 In the first adhesive composition (I-3), the content of the solvent is not particularly limited and can be adjusted appropriately.

{第一黏著劑組成物(I-1)至(I-3)以外的第一黏著劑組成物} {First adhesive composition other than first adhesive compositions (I-1) to (I-3)}

以上主要對於第一黏著劑組成物(I-1)、第一黏著劑組成物(I-2)以及第一黏著劑組成物(I-3)進行說明，作為這些的含有成分所說明的，在這些3種的第一黏著劑組成物以外的所有的第一黏著劑組成物(本實施形態中，稱為「第一黏著劑組成物(I-1)至(I-3)以外的第一黏著劑組成物」)，亦可同樣地使用。 The above mainly describes the first adhesive composition (I-1), the first adhesive composition (I-2) and the first adhesive composition (I-3). As for the ingredients contained in these, All first adhesive compositions other than these three types of first adhesive compositions (in this embodiment, referred to as "first adhesive compositions (I-1) to (I-3)") "Adhesive composition") can also be used in the same way.

作為第一黏著劑組成物(I-1)至(I-3)以外的第一黏著劑組成物，除了能量線硬化性的第一黏著劑組成物以外，可列舉如非能量線硬化性的第一黏著劑組成物。 Examples of the first adhesive composition other than the first adhesive compositions (I-1) to (I-3) include, in addition to the energy ray curable first adhesive composition, non-energy ray curable first adhesive compositions. The first adhesive composition.

作為非能量線硬化性的第一黏著劑組成物，可列舉含有例如丙烯酸系樹脂(具有(甲基)丙烯醯基之樹脂)、胺基甲酸酯系樹脂(具有胺基甲酸酯鍵之樹脂)、橡膠系樹脂(具有橡膠結構之樹脂)、聚矽氧系樹脂(具有矽氧烷鍵之樹脂)、環氧系樹脂(具有環氧基之樹脂)、聚乙烯醚、或是聚碳酸酯等的黏著性樹脂者，較佳為含有丙烯酸系樹脂者。 Examples of the non-energy ray curable first adhesive composition include acrylic resins (resins having (meth)acryl groups) and urethane resins (resins having urethane bonds). Resin), rubber resin (resin with rubber structure), polysilicone resin (resin with siloxane bonds), epoxy resin (resin with epoxy group), polyvinyl ether, or polycarbonate Adhesive resins such as ester are preferably those containing acrylic resins.

第一黏著劑組成物(I-1)至(I-3)以外的第一黏著劑組成物較佳係含有1種或是2種以上的交聯劑，其含量可與上述的第一黏著劑組成物(I-1)等的情況相同。 The first adhesive composition other than the first adhesive compositions (I-1) to (I-3) preferably contains one or more cross-linking agents, and the content thereof can be equal to that of the above-mentioned first adhesive composition. The same is true for the agent composition (I-1) and the like.

<第一黏著劑組成物的製造方法> <Production method of first adhesive composition>

第一黏著劑組成物(I-1)至(I-3)等的前述第一黏著劑組成物係調配前述黏著劑、以及根據需要之前述黏著劑以外的成分等之用以構成第一黏著劑組成物之各成分而獲得。 The aforementioned first adhesive compositions such as the first adhesive compositions (I-1) to (I-3) are prepared by blending the aforementioned adhesive and, if necessary, components other than the aforementioned adhesive to form the first adhesive. obtained from each component of the composition.

各成分的調配時之添加順序並沒有特別限定，亦可同時添加2種以上的成分。 The order in which each component is added is not particularly limited, and two or more components may be added at the same time.

使用溶劑的情況，可將溶劑與溶劑以外之任一調配成分混合並將該調配成分預先稀釋來使用、亦可將溶劑以外之任一調配成分不預先稀釋而將溶劑混合這些調配成分來使用。 When using a solvent, the solvent may be mixed with any preparation ingredients other than the solvent and the preparation ingredients may be diluted in advance. Alternatively, the solvent may be mixed with any preparation ingredients other than the solvent without being diluted in advance and used.

在調配時混合各成分之方法並沒有特別限定，可由以下公知的方法來適當選擇即可：旋轉攪拌子或是攪拌葉片等並混合之方法；使用混合器來混合之方法；施加超音波來混合之方法等。 The method of mixing the ingredients during preparation is not particularly limited, and can be appropriately selected from the following known methods: mixing by rotating a stirrer or stirring blade, mixing with a mixer, and mixing by applying ultrasonic waves methods, etc.

各成分之添加以及混合時的溫度以及時間，只要各調配成分未劣化則並沒有特別限定，適當調節即可，溫度較佳為15℃至30℃。 The temperature and time during the addition and mixing of each component are not particularly limited as long as the components are not deteriorated and can be adjusted appropriately. The temperature is preferably 15°C to 30°C.

{第一黏著劑層的組成} {Composition of the first adhesive layer}

本實施形態之第一黏著劑層的組成係由上述的第一黏著劑層組成物除去溶劑者。 The composition of the first adhesive layer of this embodiment is obtained by removing the solvent from the above-mentioned first adhesive layer composition.

第一黏著劑層組成物為前述第一黏著劑組成物(I-1)之情況下，第一黏著劑層(I-1)中之黏著性樹脂(I-1a)相對於第一黏著劑層(I-1)總質量的含有比率較佳為50質量%至99質量%，更佳為55質量%至95質量%，又更佳為60質量%至90質量%。此外，本發明的另一方面，黏著性樹脂(I-1a)相對於第一黏著劑層(I-1)總質量的含有比率可為25質量%至80質量%，亦可為30質量%至75質量%，亦可為35質量%至70質量%。此外，能量線硬化性化合物相對於第一黏著劑層(I-1)總質量的含有比率較佳為1質量%至50質量%，更佳為2質量%至48質量%，又更佳為5質量%至45質量%。第一黏著劑層(I-1)含 有交聯劑之情況，交聯劑相對於第一黏著劑層(I-1)總質量的含有比率較佳為0.1質量%至10質量%，更佳為0.2質量%至9質量%，又更佳為0.3質量%至8質量%。 When the first adhesive layer composition is the aforementioned first adhesive composition (I-1), the adhesive resin (I-1a) in the first adhesive layer (I-1) is relatively The content ratio of the total mass of layer (I-1) is preferably 50 mass% to 99 mass%, more preferably 55 mass% to 95 mass%, further preferably 60 mass% to 90 mass%. In addition, in another aspect of the present invention, the content ratio of the adhesive resin (I-1a) relative to the total mass of the first adhesive layer (I-1) may be 25% by mass to 80% by mass, or may be 30% by mass. to 75% by mass, or 35% by mass to 70% by mass. In addition, the content ratio of the energy ray curable compound relative to the total mass of the first adhesive layer (I-1) is preferably 1 mass % to 50 mass %, more preferably 2 mass % to 48 mass %, and still more preferably 5% by mass to 45% by mass. The first adhesive layer (I-1) contains In the case where a cross-linking agent is present, the content ratio of the cross-linking agent relative to the total mass of the first adhesive layer (I-1) is preferably 0.1 mass % to 10 mass %, more preferably 0.2 mass % to 9 mass %, and More preferably, it is 0.3% by mass to 8% by mass.

第一黏著劑層組成物為前述第一黏著劑組成物(I-2)之情況下，第一黏著劑層(I-2)中之黏著性樹脂(I-2a)相對於第一黏著劑層(I-2)總質量的含有比率較佳為50質量%至99質量%，更佳為60質量%至98質量%，又更佳為70質量%至97質量%。第一黏著劑層(I-2)含有交聯劑之情況，交聯劑相對於第一黏著劑層(I-2)總質量的含有比率較佳為0.1質量%至10質量%，更佳為0.2質量%至9質量%，又更佳為0.3質量%至8質量%。 When the first adhesive layer composition is the aforementioned first adhesive composition (I-2), the adhesive resin (I-2a) in the first adhesive layer (I-2) is relatively The content ratio of the total mass of layer (I-2) is preferably 50 mass% to 99 mass%, more preferably 60 mass% to 98 mass%, still more preferably 70 mass% to 97 mass%. When the first adhesive layer (I-2) contains a cross-linking agent, the content ratio of the cross-linking agent relative to the total mass of the first adhesive layer (I-2) is preferably 0.1 mass % to 10 mass %, more preferably It is 0.2 mass% to 9 mass%, and more preferably, it is 0.3 mass% to 8 mass%.

第一黏著劑層組成物為前述第一黏著劑組成物(I-3)之情況下，第一黏著劑層(I-3)中之黏著性樹脂(I-2a)相對於第一黏著劑層(I-3)總質量的含有比率較佳為50質量%至99質量%，更佳為55質量%至95質量%，又更佳為60質量%至90質量%。此外，能量線硬化性低分子化合物相對於第一黏著劑層(I-3)總質量的含有比率較佳為1質量%至50質量%，更佳為2質量%至48質量%，又更佳為5質量%至45質量%。第一黏著劑層(I-3)含有交聯劑之情況，交聯劑相對於第一黏著劑層(I-3)總質量的含有比率較佳為0.1質量%至10質量%，更佳為0.2質量%至9質量%，又更佳為0.3質量%至8質量%。 When the first adhesive layer composition is the aforementioned first adhesive composition (I-3), the adhesive resin (I-2a) in the first adhesive layer (I-3) is relatively The content ratio of the total mass of layer (I-3) is preferably 50 mass% to 99 mass%, more preferably 55 mass% to 95 mass%, further preferably 60 mass% to 90 mass%. In addition, the content ratio of the energy ray curable low molecular compound relative to the total mass of the first adhesive layer (I-3) is preferably 1 mass % to 50 mass %, more preferably 2 mass % to 48 mass %, and more preferably Preferably, it is 5 mass % to 45 mass %. When the first adhesive layer (I-3) contains a cross-linking agent, the content ratio of the cross-linking agent relative to the total mass of the first adhesive layer (I-3) is preferably 0.1 mass % to 10 mass %, more preferably It is 0.2 mass% to 9 mass%, and more preferably, it is 0.3 mass% to 8 mass%.

本實施形態中，較佳係含有黏著性樹脂(1-2a)、以及交聯劑之第一黏著劑層(I-2)。該情況，黏著性樹脂(1-2a)較佳係使得具有源自(甲基)丙烯酸烷基酯的構成單元、源自含羥基單體的單元之丙烯酸系聚合物來和具有異氰酸酯基以及能量線聚合性不飽和基之含不飽和基化合物反應所獲得之丙烯酸系聚合物。交聯劑可使用第一黏著劑組成物(I-1)中所例示之化合物，尤佳係使用甲苯二異氰酸酯。 In this embodiment, it is preferable that the first adhesive layer (I-2) contains an adhesive resin (1-2a) and a cross-linking agent. In this case, the adhesive resin (1-2a) is preferably an acrylic polymer having a structural unit derived from an alkyl (meth)acrylate and a unit derived from a hydroxyl-containing monomer and having an isocyanate group and energy. Acrylic polymer obtained by reacting linearly polymerizable unsaturated group-containing compounds. As the cross-linking agent, the compounds exemplified in the first adhesive composition (I-1) can be used, and toluene diisocyanate is particularly preferred.

源自(甲基)丙烯酸烷基酯的構成單元相對於黏著性樹脂 (1-2a)總質量的含有比率較佳為50質量%至99質量%，更佳為60質量%至98質量%，又更佳為70質量%至97質量%。源自含羥基單體的單元相對於黏著性樹脂(1-2a)總質量的含有比率較佳為0.5質量%至15質量%，更佳為1.0質量%至10質量%，又更佳為2.0質量%至10質量%。黏著性樹脂(1-2a)之(甲基)丙烯酸烷基酯的烷基碳數較佳為1至12，更佳為1至4。 Structural units derived from alkyl (meth)acrylate relative to adhesive resin The content ratio of (1-2a) in the total mass is preferably 50 mass% to 99 mass%, more preferably 60 mass% to 98 mass%, and still more preferably 70 mass% to 97 mass%. The content ratio of the unit derived from the hydroxyl-containing monomer relative to the total mass of the adhesive resin (1-2a) is preferably 0.5 mass % to 15 mass %, more preferably 1.0 mass % to 10 mass %, and still more preferably 2.0 mass% to 10 mass%. The alkyl carbon number of the (meth)acrylic acid alkyl ester of the adhesive resin (1-2a) is preferably 1 to 12, more preferably 1 to 4.

黏著性樹脂(1-2a)較佳係具有源自2種以上的(甲基)丙烯酸烷基酯的構成單元，更佳係具有(甲基)丙烯酸甲酯以及源自(甲基)丙烯酸正丁酯的構成單元，又更佳係具有源自甲基丙烯酸甲酯以及丙烯酸正丁酯的構成單元。作為黏著性樹脂(1-2a)之含羥基單體，可使用前述的第一黏著劑組成物(I-1)中所例示者，尤佳係使用丙烯酸2-羥乙酯。作為具有異氰酸酯基以及能量線聚合性不飽和基之含不飽和基化合物，可使用第一黏著劑組成物(I-2)中所例示之化合物，尤佳係使用2-甲基丙烯醯氧乙基異氰酸酯。設源自前述含羥基單體之全羥基為100mol時，具有前述異氰酸酯基以及能量線聚合性不飽和基之含不飽和基化合物的使用量較佳為20mol至80mol，更佳為25mol至75mol，又更佳為30mol至70mol。 The adhesive resin (1-2a) preferably has structural units derived from two or more alkyl (meth)acrylates, and more preferably has methyl (meth)acrylate and n-(meth)acrylic acid. The structural unit of butyl ester is more preferably a structural unit derived from methyl methacrylate and n-butyl acrylate. As the hydroxyl-containing monomer of the adhesive resin (1-2a), those exemplified in the aforementioned first adhesive composition (I-1) can be used, and 2-hydroxyethyl acrylate is particularly preferred. As the unsaturated group-containing compound having an isocyanate group and an energy ray polymerizable unsaturated group, the compounds exemplified in the first adhesive composition (I-2) can be used, and 2-methacryloxyethyl is particularly preferred. isocyanate. When the total hydroxyl group derived from the aforementioned hydroxyl-containing monomer is 100 mol, the usage amount of the unsaturated group-containing compound having the aforementioned isocyanate group and energy beam polymerizable unsaturated group is preferably 20 mol to 80 mol, more preferably 25 mol to 75 mol. More preferably, it is 30 mol to 70 mol.

◎基材 ◎Substrate

基材為片狀或是膜狀，作為該構成材料，可列舉例如各種樹脂。 The base material is in the form of a sheet or film, and examples of the constituent material include various resins.

作為前述樹脂，可列舉例如：低密度聚乙烯(亦稱為LDPE；Low Density Polyethylene)、直鏈低密度聚乙烯(亦稱為LLDPE；Linear Low Density Polyethylene)、高密度聚乙烯(亦稱為HDPE；High Density Polyethylene)等的聚乙烯；聚丙烯、聚丁烯、聚丁二烯、聚甲基戊烯、降冰片烯樹脂等的聚乙烯以外的聚烯烴；乙烯-乙酸乙烯酯共聚物(亦稱為EVA；Ethylene Vinyl Acetate)、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯共聚物、乙烯-降冰片烯共聚物等的乙烯系共聚物(亦即作為單體使用乙烯所獲得之共聚 物)；聚氯乙烯、氯乙烯共聚物等的氯乙烯系樹脂(亦即作為單體使用氯乙烯所獲得之樹脂)；聚苯乙烯；聚環烯烴；聚對苯二甲酸乙二酯(亦稱為PET；polyethylene terephthalate)、聚萘二甲酸乙二酯、聚對苯二甲酸丁二酯、聚間苯二甲酸乙二酯、聚乙烯-2,6-萘二甲酸乙二酯、所有的構成單元具有芳香族環式基之全芳香族聚酯等的聚酯；2種以上的前述聚酯的共聚物；聚(甲基)丙烯酸酯；聚胺基甲酸酯；聚胺基甲酸酯丙烯酸酯；聚醯亞胺；聚醯胺；聚碳酸酯；氟樹脂；聚縮醛；改質聚伸苯醚；聚苯硫醚；聚碸；聚醚酮等。 Examples of the resin include low-density polyethylene (also called LDPE; Low Density Polyethylene), linear low-density polyethylene (also called LLDPE; Linear Low Density Polyethylene), and high-density polyethylene (also called HDPE). ; High Density Polyethylene) and other polyethylene; polyolefins other than polyethylene such as polypropylene, polybutylene, polybutadiene, polymethylpentene, norbornene resin; ethylene-vinyl acetate copolymer (also Ethylene copolymers (called EVA; Ethylene Vinyl Acetate), ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, ethylene-norbornene copolymer, etc. (that is, used as monomers copolymerization of ethylene ); vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (that is, resins obtained by using vinyl chloride as a monomer); polystyrene; polycyclic olefins; polyethylene terephthalate (also Known as PET (polyethylene terephthalate), polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalate, all Polyesters such as fully aromatic polyesters having aromatic ring groups as structural units; copolymers of two or more of the aforementioned polyesters; poly(meth)acrylate; polyurethane; polyurethane Ester acrylate; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; polyethylene; polyetherketone, etc.

此外，作為前述樹脂，可列舉例如前述聚酯與該聚酯以外的樹脂的混合物等的聚合物合金。前述聚酯與該聚酯以外的樹脂的聚合物合金較佳係聚酯以外的樹脂的量相對少量。 Examples of the resin include polymer alloys such as a mixture of the polyester and a resin other than the polyester. The polymer alloy of the polyester and the resin other than the polyester preferably contains a relatively small amount of the resin other than the polyester.

此外，作為前述樹脂，可列舉例如以上所例示之前述樹脂的1種或是2種以上經交聯之交聯樹脂；使用了以上所例示之前述樹脂的1種或是2種以上之離聚物等的改質樹脂。 In addition, examples of the resin include cross-linked resins that are one or more of the above-exemplified resins; and ionomers that use one or two or more of the above-exemplified resins. Modified resins for materials, etc.

另外，本說明書之中，所謂「(甲基)丙烯酸」，係包含「丙烯酸」以及「甲基丙烯酸」的兩者之概念。對於與(甲基)丙烯酸類似的用語也相同，例如所謂「(甲基)丙烯酸酯」，係包含「丙烯酸酯」以及「甲基丙烯酸酯」的兩者之概念，所謂「(甲基)丙烯醯基」，係包含「丙烯醯基」以及「甲基丙烯醯基」的兩者之概念。 In addition, in this specification, the term "(meth)acrylic acid" includes the concept of both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth)acrylic acid. For example, the so-called "(meth)acrylate" includes the concepts of both "acrylate" and "methacrylate". The so-called "(meth)acrylate" "Cyl group" is a concept that includes both "acryl group" and "methacryl group".

構成基材之樹脂可僅為1種、亦可為2種以上，若為2種以上之情況，可任意地選擇這些組合以及比率。 The resin constituting the base material may be only one type, or may be two or more types. In the case of two or more types, these combinations and ratios may be selected arbitrarily.

基材可僅為1層(單層)，亦可為2層以上的複數層，若為複數層之情況，這些複數層可彼此相同或不同，這些複數層的組合並沒有特別限定。 The base material may have only one layer (single layer), or may have a plurality of two or more layers. In the case of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.

基材的厚度較佳為5μm至1000μm，更佳為10μm至500μm， 又更佳為15μm至300μm，尤佳為20μm至150μm。 The thickness of the substrate is preferably 5 μm to 1000 μm, more preferably 10 μm to 500 μm. It is more preferably 15 μm to 300 μm, even more preferably 20 μm to 150 μm.

此處，所謂「基材的厚度」，係指基材整體的厚度，例如，所謂由複數層所構成之基材的厚度，係指構成基材之所有的層的合計的厚度。 Here, the "thickness of the base material" refers to the thickness of the entire base material. For example, the thickness of the base material composed of a plurality of layers means the total thickness of all the layers constituting the base material.

基材較佳係厚度的精度高，亦即不分部位之厚度的不均被抑制。上述的構成材料之中，構成這種厚度的精度高的基材所可使用的材料，可列舉例如：聚乙烯、聚乙烯以外的聚烯烴、聚對苯二甲酸乙二酯、乙烯-乙酸乙烯酯共聚物(EVA)等。 It is preferable that the base material has high thickness accuracy, that is, unevenness in thickness regardless of location is suppressed. Among the above-mentioned constituent materials, materials that can be used to form a substrate with such a high thickness accuracy include, for example, polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate. Ester copolymer (EVA), etc.

基材除了前述樹脂等為主的構成材料以外，亦可含有充填材、著色劑、抗靜電劑、抗氧化劑、有機潤滑劑、觸媒、軟化劑(可塑劑)等的公知的各種添加劑。 In addition to the aforementioned resin-based structural materials, the base material may also contain various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and softeners (plasticizers).

基材可為透明，亦可為不透明，亦可根據目的而著色，其它層亦可被蒸鍍。 The substrate can be transparent or opaque, or it can be colored according to the purpose, and other layers can also be evaporated.

前述黏彈性層為能量線硬化性之情況，基材較佳係使能量線透射者。 When the aforementioned viscoelastic layer is energy ray hardenable, the base material is preferably one that transmits energy rays.

基材係可以公知的方法來製造。例如，含有樹脂之基材，可以藉由成形含有前述樹脂之樹脂組成物來製造。 The base material can be produced by a known method. For example, a base material containing a resin can be produced by molding a resin composition containing the aforementioned resin.

◎剝離膜 ◎Peel-off film

前述剝離膜可為該領域所公知者。 The aforementioned release film may be one known in this field.

作為較佳的前述剝離膜，例如為聚對苯二甲酸乙二酯等的樹脂製膜之至少一方的表面藉由聚矽氧處理等而經剝離處理者；膜的至少一方的表面為以聚烯烴所構成之剝離面者等。 As the preferred release film, for example, a film made of a resin such as polyethylene terephthalate has at least one surface thereof subjected to a release treatment by polysiloxane treatment or the like; at least one surface of the film is made of polyethylene terephthalate or the like. The peeling surface composed of olefins, etc.

剝離膜的厚度較佳係與基材的厚度相同。 The thickness of the release film is preferably the same as the thickness of the base material.

◎第二黏著劑層 ◎Second adhesive layer

第二黏著劑層(亦即貼合黏著劑層)係用以將本實施形態的端子保護用膠帶貼合至支撐體之黏著劑層。 The second adhesive layer (that is, the bonding adhesive layer) is an adhesive layer used to bond the terminal protection tape of this embodiment to the support.

前述第二黏著劑層可為該領域所公知者，可由上述的第一黏著劑層所說明者配合支撐體而適當選擇。 The aforementioned second adhesive layer may be one well-known in the field, and may be appropriately selected based on the description of the aforementioned first adhesive layer and the support.

用以形成第二黏著劑層的第二黏著劑組成物，係與前述第一黏著劑組成物相同，第二黏著劑組成物的製造方法，亦與前述第一黏著劑組成物的製造方法相同。 The second adhesive composition used to form the second adhesive layer is the same as the first adhesive composition. The manufacturing method of the second adhesive composition is also the same as the manufacturing method of the first adhesive composition. .

◇端子保護用膠帶的製造方法 ◇How to manufacture terminal protection tape

前述端子保護用膠帶係可將上述的各層以成為對應之位置關係的方式依序積層來製造。各層的形成方法係如先前說明。 The terminal protection tape can be manufactured by sequentially stacking the above-mentioned layers so as to have a corresponding positional relationship. Each layer is formed as previously described.

例如，在剝離膜的剝離處理面上塗布上述的埋入層形成用組成物，根據需要使其乾燥，藉此積層埋入層。在另外的剝離膜的剝離處理面上，塗布上述的第一黏著劑組成物，根據需要使其乾燥，藉此積層第一黏著劑層。將剝離膜上的埋入層與另外的剝離膜上的第一黏著劑層貼合，藉此獲得依序積層有剝離膜、埋入層、第一黏著劑層以及剝離膜之端子保護用膠帶。剝離膜只要在使用端子保護用膠帶時除去即可。 For example, the buried layer is laminated by applying the above-mentioned embedded layer forming composition to the release-treated surface of the release film and drying it if necessary. The above-mentioned first adhesive composition is applied to the release-processed surface of another release film and dried if necessary, thereby laminating the first adhesive layer. The embedded layer on the release film is bonded to the first adhesive layer on another release film, thereby obtaining a terminal protection tape in which the release film, the embedded layer, the first adhesive layer and the release film are laminated in this order. . The peeling film only needs to be removed when using the terminal protection tape.

此外，在基材上依序以埋入層以及第一黏著劑層而在這些的厚度方向所積層之端子保護用膠帶，係可以以下所示之方法來製造。 In addition, a terminal protective tape in which a buried layer and a first adhesive layer are sequentially laminated on a base material in the thickness direction thereof can be produced by the method shown below.

例如，將依序積層上述的剝離膜、埋入層、第一黏著劑層以及剝離膜之端子保護用膠帶的埋入層之側的剝離膜剝離，藉由將其與基材貼合，可獲得在基材上依序積層有埋入層、第一黏著劑層以及剝離膜之端子保護用膠帶。剝離膜可在使用端子保護用膠帶時除去即可。 For example, the peeling film on the side of the embedded layer of the terminal protection tape that is laminated in this order on the peeling film, the embedded layer, the first adhesive layer, and the peeling film can be peeled off and bonded to the base material. A terminal protection tape was obtained in which a buried layer, a first adhesive layer, and a release film were sequentially laminated on a base material. The peeling film can be removed when using the terminal protection tape.

此外，例如，對於基材，將埋入層形成用組成物擠出成形，藉此在基材上積層埋入層。在剝離膜的剝離處理面上塗布上述的第一黏著劑組成物，根據需要使其乾燥，積層第一黏著劑層。然後，可將該剝離膜上的第一黏著劑層與基材上的埋入層貼合，藉此也可獲得在基材上依序積 層有埋入層、第一黏著劑層以及剝離膜之端子保護用膠帶。剝離膜可在使用端子保護用膠帶時除去即可。 Furthermore, for example, a buried layer is laminated on the base material by extruding the composition for forming the buried layer on the base material. The above-mentioned first adhesive composition is applied to the release-processed surface of the release film, dried as necessary, and the first adhesive layer is laminated. Then, the first adhesive layer on the release film can be bonded to the embedded layer on the base material, thereby also obtaining sequential deposition on the base material. The terminal protection tape consists of a buried layer, a first adhesive layer and a release film. The peeling film can be removed when using the terminal protection tape.

此外，依序以第二黏著劑層、基材、埋入層以及第一黏著劑層而在這些的厚度方向所積層之雙面膠帶的形態的端子保護用膠帶係可以以下所示之方法來製造。 In addition, a terminal protection tape in the form of a double-sided tape in which the second adhesive layer, the base material, the buried layer, and the first adhesive layer are sequentially laminated in the thickness direction can be produced by the method shown below. manufacturing.

例如，準備上述在基材上依序積層有埋入層、第一黏著劑層以及剝離膜之端子保護用膠帶。在另外的剝離膜的剝離處理面上塗布上述的第二黏著劑組成物，並根據需要使其乾燥，來積層第二黏著劑層。然後，將該剝離膜上的第二黏著劑層與前述端子保護用膠帶的基材貼合，可獲得依序積層有剝離膜、第二黏著劑層、基材、埋入層、第一黏著劑層以及剝離膜之端子保護用膠帶。剝離膜可在使用端子保護用膠帶時除去即可。 For example, prepare the above-mentioned terminal protection tape in which an embedded layer, a first adhesive layer, and a release film are sequentially laminated on a base material. The above-mentioned second adhesive composition is applied to the release-processed surface of another release film and dried if necessary to laminated a second adhesive layer. Then, the second adhesive layer on the release film is bonded to the base material of the terminal protection tape to obtain a release film, a second adhesive layer, a base material, an embedded layer, and a first adhesive layer laminated in sequence. The adhesive layer and the peel-off film are used for terminal protection tape. The peeling film can be removed when using the terminal protection tape.

具備上述的各層以外的其它層之端子保護用膠帶，在上述的製造方法之中，以前述其它層的積層位置成為適切的位置的方式，藉由適宜追加前述其它層的形成步驟以及積層步驟之任一者或是兩者來製造。 In the above-mentioned manufacturing method, the terminal protective tape having layers other than the above-mentioned layers is appropriately added with one of the forming steps and the laminating steps of the other layers so that the lamination positions of the other layers become appropriate positions. Make either or both.

◇附電磁波屏蔽膜之半導體裝置的製造方法 ◇Method for manufacturing semiconductor device with electromagnetic wave shielding film

本實施形態的端子保護用膠帶係例如可用於以下的附電磁波屏蔽膜之半導體裝置的製造方法。 The terminal protection tape of this embodiment can be used, for example, in the following method of manufacturing a semiconductor device with an electromagnetic wave shielding film.

圖5係本實施形態的附電磁波屏蔽膜之半導體裝置的製造方法，係示意性表示將依序具有黏著劑層14、埋入層13、基材11之端子保護用膠帶3固定在如圖4所示之支撐體30所進行之附電磁波屏蔽膜之半導體裝置的製造方法之一實施形態的截面圖。 FIG. 5 is a schematic diagram of the manufacturing method of a semiconductor device with an electromagnetic wave shielding film according to this embodiment. It is a schematic representation of fixing the terminal protection tape 3 having the adhesive layer 14, the embedded layer 13, and the base material 11 in this order on the surface of FIG. 4 A cross-sectional view of an embodiment of a method for manufacturing a semiconductor device with an electromagnetic wave shielding film using the support 30 shown.

首先，如圖5(a)、(b)所示，在端子保護用膠帶的黏彈性層12將附端子之半導體裝置65以端子91之側、亦即電路基板63的端子形成面63a朝下的方式壓裝，在黏彈性層12埋設端子91。 First, as shown in FIGS. 5(a) and (b) , the semiconductor device 65 with terminals is placed on the viscoelastic layer 12 of the terminal protection tape with the terminal 91 side, that is, the terminal formation surface 63a of the circuit board 63 facing downward. The terminal 91 is embedded in the viscoelastic layer 12 by press-fitting.

此時，使附端子之半導體裝置65的端子91接觸黏彈性層12，並在端子保護用膠帶壓裝附端子之半導體裝置65。藉此，將黏彈性層12的黏著劑層14之側的最表面依序壓接在端子91的表面以及電路基板63的端子形成面63a。此時，將黏彈性層12加熱，藉此黏彈性層12軟化，且以覆蓋端子91的方式在端子91間擴展，密接在端子形成面63a，並且覆蓋端子91的表面、尤其端子形成面63a的附近部位的表面，並埋設端子91。 At this time, the terminals 91 of the semiconductor device with terminals 65 are brought into contact with the viscoelastic layer 12 , and the semiconductor device with terminals 65 is press-fitted on the terminal protection tape. Thereby, the outermost surface of the viscoelastic layer 12 on the adhesive layer 14 side is pressed and bonded to the surface of the terminal 91 and the terminal formation surface 63 a of the circuit substrate 63 in sequence. At this time, the viscoelastic layer 12 is heated, thereby softening the viscoelastic layer 12, and expands between the terminals 91 to cover the terminals 91, is in close contact with the terminal forming surface 63a, and covers the surface of the terminals 91, especially the terminal forming surface 63a. The terminal 91 is buried on the surface of the nearby part.

作為在端子保護用膠帶壓接附端子之半導體裝置65之方法，可適用以各種片材壓接貼附在對象物之公知的方法，可列舉例如使用積層輥或真空積層機之方法等。 As a method of crimping the semiconductor device 65 with terminals attached to the terminal protection tape, a known method of crimping and affixing various sheets to an object can be applied, and examples thereof include methods using a lamination roller or a vacuum laminator.

將附端子之半導體裝置65壓接在端子保護用膠帶時的壓力並沒有特別限定，較佳為0.1MPa至1.5MPa，更佳為0.3MPa至1.3MPa。加熱溫度較佳為30℃至70℃，更佳為35℃至65℃，尤佳為40℃至60℃。此外，較佳係將黏彈性層12的第一黏著劑層14貼合至端子形成面63a。 The pressure when crimping the semiconductor device 65 with terminals to the terminal protection tape is not particularly limited, but is preferably 0.1MPa to 1.5MPa, and more preferably 0.3MPa to 1.3MPa. The heating temperature is preferably 30°C to 70°C, more preferably 35°C to 65°C, and particularly preferably 40°C to 60°C. In addition, it is preferable to bond the first adhesive layer 14 of the viscoelastic layer 12 to the terminal formation surface 63a.

在附端子之半導體裝置65的露出面塗布導電性樹脂101(圖5(c))，進而使其熱硬化，形成由導電材料所構成之電磁波屏蔽膜10(圖5(d))。作為以導電材料被覆且形成電磁波屏蔽膜10之方法，亦可使用濺鍍、離子鍍、噴塗等的方法。 The conductive resin 101 is coated on the exposed surface of the semiconductor device 65 with terminals (Fig. 5(c)) and then thermally cured to form the electromagnetic wave shielding film 10 made of the conductive material (Fig. 5(d)). As a method of covering the electromagnetic wave shielding film 10 with a conductive material, methods such as sputtering, ion plating, spray coating, etc. may also be used.

前述端子保護用膠帶係黏彈性層12的鬆弛彈性模量變數X2在前述式(2)所示之預定的值的範圍內，故附端子之半導體裝置的端子埋設在黏彈性層12時，即使是焊球等的具有凹凸而容易產生浮起的端子電極亦可埋入，且不產生浮起，可將電路基板63的端子形成面63a密接在黏彈性層12。進而，端子保持在被埋設的狀態，並防止端子電極之端子91與電磁波屏蔽膜10出現電性短路，且沒有必要設置步驟上複雜的遮罩部等。 The relaxation elastic modulus variable Terminal electrodes such as solder balls, which have unevenness and are prone to floating, can be buried without floating, and the terminal forming surface 63 a of the circuit board 63 can be closely connected to the viscoelastic layer 12 . Furthermore, the terminals are kept in a buried state, and electrical short circuits between the terminals 91 of the terminal electrodes and the electromagnetic wave shielding film 10 are prevented, and there is no need to provide a mask part or the like that is complicated in steps.

由具有黏彈性層12之端子保護用膠帶3拾取(pick up)附電磁 波屏蔽膜之半導體裝置66，藉此可取出以電磁波屏蔽膜10所被覆之附端子之半導體裝置65(圖5(e))。 The electromagnet is attached by picking up the terminal protection tape 3 having the viscoelastic layer 12 The semiconductor device 66 of the wave shielding film can thereby take out the semiconductor device 65 with terminals covered with the electromagnetic wave shielding film 10 (Fig. 5(e)).

圖5所示之附電磁波屏蔽膜之半導體裝置的製造方法，作為電磁波屏蔽的對象之附端子之半導體裝置65可為個別製造之附端子之半導體裝置65，亦可為藉由切割法而經單片化之附端子之半導體裝置65。 In the method of manufacturing a semiconductor device with an electromagnetic wave shielding film shown in FIG. 5 , the semiconductor device with a terminal 65 that is an object of electromagnetic wave shielding may be a semiconductor device with a terminal 65 that is manufactured individually, or it may be individually manufactured by a cutting method. Chip-based semiconductor device 65 with terminals.

如圖5所示之附電磁波屏蔽膜之半導體裝置的製造方法，雖表示了針對經單片化之各別的電子零件61、62被密封樹脂64所密封後之附端子之半導體裝置65，使用端子保護用膠帶3進行電磁波屏蔽之方法，但如下所示，亦可從單片化前的附端子之半導體裝置集合體6開始就使用端子保護用膠帶2來將附端子之半導體裝置65予以電磁波屏蔽。 The method of manufacturing a semiconductor device with an electromagnetic wave shielding film as shown in FIG. 5 shows a semiconductor device with a terminal 65 in which the individual electronic components 61 and 62 are singulated and sealed with a sealing resin 64. The terminal protection tape 3 is a method for shielding electromagnetic waves. However, as shown below, the terminal protection tape 2 can also be used from the semiconductor device assembly 6 with terminals before singulation to shield the semiconductor devices 65 with terminals from electromagnetic waves. shield.

圖6係本實施形態的附電磁波屏蔽膜之半導體裝置的製造方法，係示意性表示使用依序具有黏著劑層14、埋入層13、基材11之端子保護用膠帶2來對附端子之半導體裝置65進行電磁波屏蔽之方法的其它實施形態之截面圖。 FIG. 6 is a schematic diagram of the manufacturing method of a semiconductor device with an electromagnetic wave shielding film according to this embodiment, and schematically shows the use of a terminal protective tape 2 having an adhesive layer 14, a buried layer 13, and a base material 11 in this order to attach the terminals. A cross-sectional view of another embodiment of a method for shielding the semiconductor device 65 from electromagnetic waves.

首先，如圖6(a)、(b)所示，在端子保護用膠帶的黏彈性層12將電路基板63所連結之附端子之半導體裝置集合體6以端子91之側、亦即電路基板63的端子形成面63a朝下的方式壓裝，與前述圖5(a)、(b)之時相同，在黏彈性層12埋設端子91。 First, as shown in FIGS. 6(a) and (b) , the viscoelastic layer 12 of the terminal protective tape connects the semiconductor device assembly 6 with terminals to the circuit board 63 on the side of the terminal 91, that is, the circuit board. 63 is press-fitted with the terminal forming surface 63a facing downward, and the terminal 91 is embedded in the viscoelastic layer 12 in the same manner as in the aforementioned FIGS. 5(a) and (b) .

此時，在附端子之半導體裝置集合體6一邊由上側施加壓力，一邊如前述圖5(a)、(b)時同樣地在端子保護用膠帶的黏彈性層12埋設端子91。 At this time, while applying pressure from the upper side of the semiconductor device assembly 6 with terminals, terminals 91 are embedded in the viscoelastic layer 12 of the terminal protective tape in the same manner as in FIGS. 5(a) and (b) .

此外，藉由一邊加熱黏彈性層12一邊進行貼合，可使黏彈性層12軟化，並使黏彈性層12密接在電路基板63的端子形成面63a。將附端子之半導體裝置集合體6壓接在端子保護用膠帶時的壓力並沒有特別限定，較 佳為0.1MPa至1.5MPa，更佳為0.3MPa至1.3MPa。加熱溫度較佳為30℃至70℃，更佳為35℃至65℃，尤佳為40℃至60℃。此外，較佳係將黏彈性層12的第一黏著劑層14貼合至端子形成面63a。 In addition, by laminating the viscoelastic layer 12 while heating, the viscoelastic layer 12 can be softened and the viscoelastic layer 12 can be brought into close contact with the terminal formation surface 63 a of the circuit board 63 . The pressure when crimping the semiconductor device assembly 6 with terminals to the terminal protection tape is not particularly limited. Preferably, it is 0.1MPa to 1.5MPa, and more preferably, it is 0.3MPa to 1.3MPa. The heating temperature is preferably 30°C to 70°C, more preferably 35°C to 65°C, and particularly preferably 40°C to 60°C. In addition, it is preferable to bond the first adhesive layer 14 of the viscoelastic layer 12 to the terminal formation surface 63a.

然後，切割附端子之半導體裝置集合體6，作為附端子之半導體裝置65(圖6(c))。用於形成電磁波屏蔽膜之步驟之本實施形態的端子保護用膠帶，係可兼作為附端子之半導體裝置集合體6的切割膠帶。然後，如圖5所示之附電磁波屏蔽膜之半導體裝置的製造方法之中，作為電磁波屏蔽的對象之附端子之半導體裝置65係藉由切割法而經單片化之附端子之半導體裝置65時，需要有拾取切割膠帶上的附端子之半導體裝置，改貼在端子保護用膠帶之作業(圖5(a))。另一方面，如圖6所示之附電磁波屏蔽膜之半導體裝置的製造方法，可省略將切割膠帶上的附端子之半導體裝置65改貼在端子保護用膠帶之作業。 Then, the semiconductor device assembly 6 with terminals is cut to form a semiconductor device 65 with terminals (Fig. 6(c)). The terminal protection tape of this embodiment used in the step of forming the electromagnetic wave shielding film can also be used as a dicing tape for the semiconductor device assembly 6 with terminals. Then, in the method of manufacturing a semiconductor device with an electromagnetic wave shielding film as shown in FIG. 5 , the semiconductor device with a terminal 65 that is an object of electromagnetic wave shielding is a semiconductor device with a terminal 65 that is singulated by a dicing method. When doing so, it is necessary to pick up the semiconductor device with terminals on the cutting tape and replace it with terminal protection tape (Figure 5(a)). On the other hand, the method of manufacturing a semiconductor device with an electromagnetic shielding film as shown in FIG. 6 can omit the operation of attaching the semiconductor device with terminals 65 on the dicing tape to the terminal protection tape.

在附端子之半導體裝置65的露出面塗布導電性樹脂101(圖6(d))。此時，附端子之半導體裝置集合體6的各附端子之半導體裝置65的邊界部分之導電性樹脂101的分離不充分的情況，亦可使用擴展裝置等來延伸端子保護用膠帶。可在經單片化之附端子之半導體裝置65之各自之側面塗布了導電性樹脂101之狀態下，將各別的附端子之半導體裝置65加以單片化。進而，將塗布在經單片化之附端子之半導體裝置65的頂面以及側面之導電性樹脂101加熱使其硬化，在附端子之半導體裝置65的露出面形成由導電材料所構成之電磁波屏蔽膜10(圖6(e))。亦可在附端子之半導體裝置65(圖6(c))直接濺鍍導電材料，形成電磁波屏蔽膜10(圖6(e))。 The conductive resin 101 is applied to the exposed surface of the semiconductor device 65 with terminals (Fig. 6(d)). At this time, if separation of the conductive resin 101 at the boundary portion of each terminal-attached semiconductor device 65 in the terminal-attached semiconductor device assembly 6 is insufficient, an expansion device or the like may be used to extend the terminal protection tape. Each of the semiconductor devices with terminals 65 can be singulated in a state where the conductive resin 101 is coated on the side surfaces of the semiconductor devices with terminals 65 . Furthermore, the conductive resin 101 coated on the top and side surfaces of the singulated semiconductor device with terminals 65 is heated and hardened, and an electromagnetic wave shield composed of the conductive material is formed on the exposed surface of the semiconductor device with terminals 65 . Membrane 10 (Fig. 6(e)). The conductive material can also be directly sputtered on the semiconductor device 65 with terminals (Fig. 6(c)) to form the electromagnetic wave shielding film 10 (Fig. 6(e)).

黏彈性層12的鬆弛彈性模量變數X2係在如前述式(2)所示之預定的值的範圍內，故將附端子之半導體裝置集合體6的端子埋設在黏彈性層12時，即使是焊球等容易產生浮起的端子電極亦可埋設且不產生浮起， 使電路基板63的端子形成面63a密接在黏彈性層12。結果可防止端子電極之端子91與電磁波屏蔽膜10出現電性短路，且沒有必要設置步驟上複雜的遮罩部等。 The relaxation elastic modulus variable Terminal electrodes such as solder balls that are prone to floating can also be buried without floating. The terminal formation surface 63a of the circuit board 63 is brought into close contact with the viscoelastic layer 12. As a result, an electrical short circuit between the terminal 91 of the terminal electrode and the electromagnetic wave shielding film 10 can be prevented, and there is no need to provide a complicated mask part or the like.

藉由從具有黏彈性層12之端子保護用膠帶拾取附電磁波屏蔽膜之半導體裝置66，可取出以電磁波屏蔽膜10被覆之附端子之半導體裝置65(圖6(f))。 By picking up the semiconductor device 66 with the electromagnetic wave shielding film from the terminal protection tape having the viscoelastic layer 12, the semiconductor device 65 with the terminal covered with the electromagnetic wave shielding film 10 can be taken out (Fig. 6(f)).

本實施形態的端子保護用膠帶之中，端子91的高度h0較佳係低於黏彈性層12的厚度d1，較佳為1.2≦d1/h0≦5.0。具體而言，較佳為50μm至300μm，更佳為60μm至270μm，尤佳為80μm至240μm。端子91的高度為前述下限值以上，可藉此更提高端子91的機能。此外，端子91的高度為前述上限值以下，藉此可更提高抑制端子91上部之黏彈性層12的殘留的效果。 In the terminal protection tape of this embodiment, the height h0 of the terminal 91 is preferably lower than the thickness d1 of the viscoelastic layer 12, and is preferably 1.2≦d1/h0≦5.0. Specifically, 50 μm to 300 μm is preferred, 60 μm to 270 μm is more preferred, and 80 μm to 240 μm is particularly preferred. The height of the terminal 91 is above the aforementioned lower limit, thereby further improving the function of the terminal 91 . In addition, the height of the terminal 91 is below the aforementioned upper limit, thereby further improving the effect of suppressing the remaining viscoelastic layer 12 on the upper portion of the terminal 91 .

另外，本說明書之中，所謂「端子的高度」，係指在端子之中，存在於距離端子形成面最高的位置之部位的高度。附端子之半導體裝置集合體6以及附端子之半導體裝置半導體裝置65具有複數的端子91的情況，端子91的高度h0可以為這些的平均。端子的高度係例如可藉由非接觸型3維光干涉式表面粗度計(日本Veeco公司製，商品名：Wyko NT1100)來測定。 In addition, in this specification, the "height of the terminal" refers to the height of the part located at the highest position from the terminal formation surface among the terminals. When the semiconductor device assembly 6 with terminals and the semiconductor device 65 with terminals have a plurality of terminals 91 , the height h0 of the terminals 91 may be an average of these. The height of the terminal can be measured, for example, with a non-contact three-dimensional optical interference surface roughness meter (manufactured by Veeco Japan, trade name: Wyko NT1100).

端子91的寬度並沒有特別限定，較佳為170μm至350μm，更佳為200μm至320μm，尤佳為230μm至290μm。端子91的寬度為前述下限值以上，可藉此更提高端子91的機能。此外，端子91的高度為前述上限值以下，可藉此更提高抑制在端子91上部之黏彈性層12的殘留的效果。 The width of the terminal 91 is not particularly limited, but is preferably 170 μm to 350 μm, more preferably 200 μm to 320 μm, and particularly preferably 230 μm to 290 μm. The width of the terminal 91 is above the aforementioned lower limit, thereby further improving the function of the terminal 91 . In addition, the height of the terminal 91 is below the aforementioned upper limit, thereby further improving the effect of suppressing the remaining viscoelastic layer 12 on the upper portion of the terminal 91 .

另外，本說明書之中，所謂「端子的寬度」，係指由相對於端子形成面呈垂直的方向往下看端子而成為俯視時，端子表面上不同的2點間以直線 連結所獲得之線段的最大值。端子為球形、或是半球形時，所謂「端子的寬度」，係往下看端子而成為俯視時該端子的最大直徑(端子直徑)。 In addition, in this specification, the so-called "width of the terminal" refers to the straight line between two different points on the surface of the terminal when the terminal is viewed from above in a direction perpendicular to the surface where the terminal is formed. The maximum value of the line segments obtained by connecting them. When the terminal is spherical or hemispherical, the "width of the terminal" is the maximum diameter (terminal diameter) of the terminal when viewed from above when looking down at the terminal.

相鄰之端子91間的距離(亦即端子間節距)並沒有特別限定，較佳為250μm至800μm，更佳為300μm至600μm，尤佳為350μm至500μm。前述距離為前述下限值以上，可更提高端子91的埋入性。此外，前述距離為前述上限值以下，可更提高抑制在端子91上部之黏彈性層12的殘留之效果。 The distance between adjacent terminals 91 (ie, the pitch between terminals) is not particularly limited, but is preferably 250 μm to 800 μm, more preferably 300 μm to 600 μm, and particularly preferably 350 μm to 500 μm. When the distance is equal to or greater than the lower limit, the embedding property of the terminal 91 can be further improved. In addition, if the distance is below the upper limit, the effect of preventing the viscoelastic layer 12 from remaining on the upper portion of the terminal 91 can be further improved.

另外，本說明書之中，所謂「相鄰之端子間的距離」，係指相鄰之端子彼此D表面間的距離的最小值。 In addition, in this specification, the so-called "distance between adjacent terminals" refers to the minimum value of the distance between the D surfaces of adjacent terminals.

[實施例] [Example]

以下藉由具體的實施例，對於本發明進行更詳細地說明。但本發明並不限於以下所示之實施例。 The present invention will be described in more detail below through specific examples. However, the present invention is not limited to the embodiments shown below.

<單體> <Single>

簡稱之單體的正式名稱係如下所示。 The official name of the abbreviated monomer is as follows.

HEA：丙烯酸2-羥乙酯 HEA: 2-hydroxyethyl acrylate

BA：丙烯酸正丁酯 BA: n-butyl acrylate

MMA：甲基丙烯酸甲酯 MMA: methyl methacrylate

AAc：丙烯酸 AAc: Acrylic

(貼合黏著劑層形成用組成物A的製造) (Production of composition A for bonding adhesive layer formation)

添加由BA91質量份以及AAc9質量份所構成之丙烯酸系共聚物(重量平均分子量(Mw)400,000)33.6質量份、作為溶劑之乙基甲基酮66.4質量份、作為交聯劑之多元環氧化合物(MITSUBISHI GAS CHEMICAL COMPANY,INC.製，製品名「TETRAD-C」，濃度5%的N,N'-(環己烷-1,3- 二基雙亞甲基)雙(二縮水甘油基胺))0.2質量份，進行30分鐘攪拌而製備貼合黏著劑層形成用組成物A。 33.6 parts by mass of an acrylic copolymer (weight average molecular weight (Mw) 400,000) consisting of 91 parts by mass of BA and 9 parts by mass of AAc, 66.4 parts by mass of ethyl methyl ketone as a solvent, and a polyvalent epoxy compound as a cross-linking agent were added (Made by MITSUBISHI GAS CHEMICAL COMPANY, INC., product name "TETRAD-C", concentration 5% N,N'-(cyclohexane-1,3- Diylbis(methylene)bis(diglycidylamine)) 0.2 parts by mass, and stirred for 30 minutes to prepare composition A for forming a bonding adhesive layer.

(貼合黏著劑層A的製造) (Production of bonding adhesive layer A)

於藉由聚矽氧處理將聚對苯二甲酸乙二酯製膜之單面進行剝離處理而成的剝離膜(琳得科(Lintec)公司製造之「SP-PET381031」，厚度38μm)之剝離處理面，塗敷前述貼合黏著劑層形成用組成物A，於100℃加熱乾燥1分鐘，藉此製造厚度20μm之貼合黏著劑層A。 Peeling of a release film ("SP-PET381031" manufactured by Lintec, thickness 38 μm) made by peeling one side of a polyethylene terephthalate film through polysiloxane treatment On the treated surface, the aforementioned composition A for forming a bonding adhesive layer was applied and heated and dried at 100° C. for 1 minute to produce a bonding adhesive layer A with a thickness of 20 μm.

(黏著劑層形成用組成物B的製造) (Production of composition B for adhesive layer formation)

製備對由BA 74質量份、MMA 20質量份及HEA 6質量份所構成之丙烯酸系共聚物加成2-甲基丙烯醯氧基乙基異氰酸酯(以下簡稱為「MOI」)(相對於HEA而為約50莫耳%)而成的樹脂之溶液(黏著劑主劑，固形物為35質量%)。相對於該黏著劑主劑100質量份，添加作為交聯劑之甲苯二異氰酸酯(東洋化學(Toyo-Chem)股份有限公司製造，製品名「BHS-8515」，固形物濃度：37.5%)0.5質量份，進行30分鐘攪拌而製備黏著劑層形成用組成物B。 Preparation of 2-methacryloyloxyethyl isocyanate (hereinafter referred to as "MOI") added to an acrylic copolymer consisting of 74 parts by mass of BA, 20 parts by mass of MMA and 6 parts by mass of HEA (relative to HEA A resin solution (main agent of adhesive, solid content is 35 mass%) composed of approximately 50 mol%). To 100 parts by mass of the main adhesive agent, 0.5 mass parts of toluene diisocyanate (manufactured by Toyo-Chem Co., Ltd., product name "BHS-8515", solid concentration: 37.5%) was added as a cross-linking agent. portion and stirred for 30 minutes to prepare composition B for forming an adhesive layer.

(黏著劑層14的製造) (Production of adhesive layer 14)

於藉由聚矽氧處理將聚對苯二甲酸乙二酯製膜之單面進行剝離處理而成的剝離膜(琳得科(Lintec)公司製造之「SP-PET381031」，厚度38μm)之剝離處理面，塗敷前述貼合黏著劑層形成用組成物B，於100℃加熱乾燥1分鐘，藉此製造厚度10μm之貼合黏著劑層14。 Peeling of a release film ("SP-PET381031" manufactured by Lintec, thickness 38 μm) made by peeling one side of a polyethylene terephthalate film through polysiloxane treatment The above-described bonding adhesive layer forming composition B was applied to the treated surface, and heated and dried at 100° C. for 1 minute to produce a bonding adhesive layer 14 with a thickness of 10 μm.

(埋入層形成用組成物A的製造) (Production of buried layer forming composition A)

添加由BA91質量份以及AAc9質量份所構成之丙烯酸系共聚物(重量平均分子量(Mw)400,000)的溶液(固形物33.6質量%)100質量份、在由BA62質量份、MMA10質量份以及HEA28質量份所構成丙烯酸系共聚物以相對於HEA100mol%而加成率成為80mol%的方式加成有2-甲基丙烯醯氧乙基異 氰酸酯而成的樹脂(平均重量分子量(Mw)100,000)的溶液(固形物45質量%)93.5質量份、作為交聯劑之甲苯二異氰酸酯(東洋化學(Toyo-Chem)股份有限公司製，製品名「BHS-8515」，固形物濃度：37.5%)2.5質量份、多元環氧化合物(MITSUBISHI GAS CHEMICAL COMPANY,INC.製，製品名「TETRAD-C」，濃度5%的N,N'-(環己烷-1,3-二基雙亞甲基)雙(二縮水甘油基胺))2.5質量份，進行30分鐘攪拌而製備埋入層形成用組成物。 Add 100 parts by mass of a solution (33.6 mass % solids) of an acrylic copolymer (weight average molecular weight (Mw) 400,000) consisting of 91 parts by mass of BA and 9 parts by mass of AAc, and 62 parts by mass of BA, 10 parts by mass of MMA and 28 parts by mass of HEA. The acrylic copolymer comprised of 93.5 parts by mass of a solution (solid content 45% by mass) of a cyanate ester resin (average molecular weight (Mw) 100,000), and toluene diisocyanate (manufactured by Toyo-Chem Co., Ltd.) as a cross-linking agent. Product name "BHS-8515", solid concentration: 37.5%) 2.5 parts by mass, polyvalent epoxy compound (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC., product name "TETRAD-C", concentration 5% N,N'- (Cyclohexane-1,3-diylbismethylene)bis(diglycidylamine)) 2.5 parts by mass, and stirred for 30 minutes to prepare a buried layer forming composition.

(埋入層形成用組成物B的製造) (Production of buried layer forming composition B)

添加由BA91質量份以及AAc9質量份所構成之丙烯酸系共聚物(重量平均分子量(Mw)400,000)的溶液(固形物33.6質量%)100質量份、在由BA62質量份、MMA10質量份以及HEA28質量份所構成之丙烯酸系共聚物以相對於HEA100mol%而加成率成為80mol%的方式加成有2-甲基丙烯醯氧乙基異氰酸酯而成的樹脂(平均重量分子量(Mw)100,000)的溶液(固形物45質量%)75質量份、作為交聯劑之甲苯二異氰酸酯(東洋化學(Toyo-Chem)股份有限公司製，製品名「BHS-8515」，固形物濃度：37.5%)15質量份，進行30分鐘攪拌而製備埋入層形成用組成物B。 Add 100 parts by mass of a solution (33.6 mass % solids) of an acrylic copolymer (weight average molecular weight (Mw) 400,000) consisting of 91 parts by mass of BA and 9 parts by mass of AAc, and 62 parts by mass of BA, 10 parts by mass of MMA and 28 parts by mass of HEA. A solution of a resin (average molecular weight (Mw) 100,000) in which 2-methacryloyloxyethyl isocyanate is added to an acrylic copolymer consisting of 100 mol% HEA so that the addition rate becomes 80 mol%. (solids 45% by mass) 75 parts by mass, 15 parts by mass of toluene diisocyanate (manufactured by Toyo-Chem Co., Ltd., product name "BHS-8515", solids concentration: 37.5%) as a cross-linking agent , stir for 30 minutes to prepare buried layer forming composition B.

(埋入層形成用組成物C的製造) (Production of buried layer forming composition C)

添加由BA91質量份以及AAc9質量份所構成之丙烯酸系共聚物(重量平均分子量(Mw)400,000)的溶液(固形物33.6質量%)100質量份、在由BA62質量份、MMA10質量份以及HEA28質量份所構成之丙烯酸系共聚物以相對於HEA100mol%而加成率成為80mol%的方式加成有2-甲基丙烯醯氧乙基異氰酸酯而成的樹脂(平均重量分子量(Mw)100,000)的溶液(固形物45質量%)75質量份、作為交聯劑之甲苯二異氰酸酯(東洋化學(Toyo-Chem)股份有限公司製，製品名「BHS-8515」，固形物濃度：37.5%)2.5質量份，進行30分鐘攪拌而製備埋入層形成用組成物C。 Add 100 parts by mass of a solution (33.6 mass % solids) of an acrylic copolymer (weight average molecular weight (Mw) 400,000) consisting of 91 parts by mass of BA and 9 parts by mass of AAc, and 62 parts by mass of BA, 10 parts by mass of MMA and 28 parts by mass of HEA. A solution of a resin (average molecular weight (Mw) 100,000) in which 2-methacryloyloxyethyl isocyanate is added to an acrylic copolymer consisting of 100 mol% HEA so that the addition rate becomes 80 mol%. (solids 45% by mass) 75 parts by mass, 2.5 parts by mass of toluene diisocyanate (manufactured by Toyo-Chem Co., Ltd., product name "BHS-8515", solids concentration: 37.5%) as a cross-linking agent , stir for 30 minutes to prepare buried layer forming composition C.

(埋入層形成用組成物D的製造) (Production of buried layer forming composition D)

添加由BA91質量份以及AAc9質量份所構成之丙烯酸系共聚物(重量平均分子量(Mw)400,000)的溶液(固形物33.6質量%)100質量份、在由BA62質量份、MMA10質量份以及HEA28質量份所構成之丙烯酸系共聚物以相對於HEA100mol%而加成率成為80mol%的方式加成有2-甲基丙烯醯氧乙基異氰酸酯而成的樹脂(平均重量分子量(Mw)100,000)的溶液(固形物45質量%)75質量份、作為交聯劑之甲苯二異氰酸酯(東洋化學(Toyo-Chem)股份有限公司製，製品名「BHS-8515」、固形物濃度：37.5%)8.75質量份、多元環氧化合物(MITSUBISHI GAS CHEMICAL COMPANY,INC.製，製品名「TETRAD-C」，濃度5%的N,N'-(環己烷-1,3-二基雙亞甲基)雙(二縮水甘油基胺))2.5質量份，進行30分鐘攪拌而製備埋入層形成用組成物D。 Add 100 parts by mass of a solution (33.6 mass % solids) of an acrylic copolymer (weight average molecular weight (Mw) 400,000) consisting of 91 parts by mass of BA and 9 parts by mass of AAc, and 62 parts by mass of BA, 10 parts by mass of MMA and 28 parts by mass of HEA. A solution of a resin (average molecular weight (Mw) 100,000) in which 2-methacryloyloxyethyl isocyanate is added to an acrylic copolymer consisting of 100 mol% HEA so that the addition rate becomes 80 mol%. (solids 45% by mass) 75 parts by mass, 8.75 parts by mass of toluene diisocyanate as a cross-linking agent (manufactured by Toyo-Chem Co., Ltd., product name "BHS-8515", solids concentration: 37.5%) , polyvalent epoxy compound (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC., product name "TETRAD-C", concentration 5% N,N'-(cyclohexane-1,3-diyl bis-methylene) bis( Diglycidylamine)) 2.5 parts by mass, and stirred for 30 minutes to prepare a buried layer forming composition D.

(埋入層形成用組成物E的製造) (Production of buried layer forming composition E)

添加由BA91質量份以及AAc9質量份所構成之丙烯酸系共聚物(重量平均分子量(Mw)400,000)的溶液(固形物33.6質量%)100質量份、在由BA62質量份、MMA10質量份以及HEA28質量份所構成之丙烯酸系共聚物以相對於HEA100mol%而加成率成為80mol%的方式加成有2-甲基丙烯醯氧乙基異氰酸酯而成的樹脂(平均重量分子量(Mw)100,000)的溶液(固形物45質量%)75質量份、作為交聯劑之甲苯二異氰酸酯(東洋化學(Toyo-Chem)股份有限公司製，製品名「BHS-8515」，固形物濃度：37.5%)15質量份、多元環氧化合物(MITSUBISHI GAS CHEMICAL COMPANY,INC.製，製品名「TETRAD-C」，濃度5%的N,N'-(環己烷-1,3-二基雙亞甲基)雙(二縮水甘油基胺))5.0質量份，進行30分鐘攪拌而製備埋入層形成用組成物E。 Add 100 parts by mass of a solution (33.6 mass % solids) of an acrylic copolymer (weight average molecular weight (Mw) 400,000) consisting of 91 parts by mass of BA and 9 parts by mass of AAc, and 62 parts by mass of BA, 10 parts by mass of MMA and 28 parts by mass of HEA. A solution of a resin (average molecular weight (Mw) 100,000) in which 2-methacryloyloxyethyl isocyanate is added to an acrylic copolymer consisting of 100 mol% HEA so that the addition rate becomes 80 mol%. (solids 45% by mass) 75 parts by mass, 15 parts by mass of toluene diisocyanate (manufactured by Toyo-Chem Co., Ltd., product name "BHS-8515", solids concentration: 37.5%) as a cross-linking agent , polyvalent epoxy compound (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC., product name "TETRAD-C", concentration 5% N,N'-(cyclohexane-1,3-diyl bis-methylene) bis( Diglycidylamine)) 5.0 parts by mass, and stirred for 30 minutes to prepare a buried layer forming composition E.

(埋入層形成用組成物F的製造) (Production of buried layer forming composition F)

添加由BA91質量份以及AAc9質量份所構成之丙烯酸系共聚物(重量平均分子量(Mw)400,000)的溶液(固形物33.6質量%)100質量份、在由BA62質量份、MMA10質量份以及HEA28質量份所構成之丙烯酸系共聚物以相對於HEA100mol%而加成率成為80mol%的方式加成有2-甲基丙烯醯氧乙基異氰酸酯而成的樹脂(平均重量分子量(Mw)100,000)的溶液(固形物45質量%)75質量份、作為交聯劑之甲苯二異氰酸酯(東洋化學(Toyo-Chem)股份有限公司製，製品名「BHS-8515」，固形物濃度：37.5%)2.5質量份、多元環氧化合物(MITSUBISHI GAS CHEMICAL COMPANY,INC.製，製品名「TETRAD-C」，濃度5%的N,N'-(環己烷-1,3-二基雙亞甲基)雙(二縮水甘油基胺))5.0質量份，進行30分鐘攪拌而製備埋入層形成用組成物E。 Add 100 parts by mass of a solution (33.6 mass % solids) of an acrylic copolymer (weight average molecular weight (Mw) 400,000) consisting of 91 parts by mass of BA and 9 parts by mass of AAc, and 62 parts by mass of BA, 10 parts by mass of MMA and 28 parts by mass of HEA. A solution of a resin (average molecular weight (Mw) 100,000) in which 2-methacryloyloxyethyl isocyanate is added to an acrylic copolymer consisting of 100 mol% HEA so that the addition rate becomes 80 mol%. (solids 45% by mass) 75 parts by mass, 2.5 parts by mass of toluene diisocyanate (manufactured by Toyo-Chem Co., Ltd., product name "BHS-8515", solids concentration: 37.5%) as a cross-linking agent , polyvalent epoxy compound (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC., product name "TETRAD-C", concentration 5% N,N'-(cyclohexane-1,3-diyl bis-methylene) bis( Diglycidylamine)) 5.0 parts by mass, and stirred for 30 minutes to prepare a buried layer forming composition E.

(基材) (Substrate)

將聚對苯二甲酸乙二酯(PET)膜(製品名「Cosmoshine A4100」，厚度50μm，東洋紡公司製造)用於基材11。 A polyethylene terephthalate (PET) film (product name "Cosmoshine A4100", thickness 50 μm, manufactured by Toyobo Co., Ltd.) was used as the base material 11 .

(附端子之半導體裝置的準備) (Preparation of semiconductor device with terminals)

評價實施例以及比較例的端子保護用膠帶的埋入性時，準備以下之附端子之半導體裝置。 To evaluate the embedding properties of the terminal protection tapes of Examples and Comparative Examples, the following semiconductor devices with terminals were prepared.

‧附端子之半導體裝置(1) ‧Semiconductor device with terminals (1)

半導體裝置的大小：10mm×10mm Semiconductor device size: 10mm×10mm

端子的高度：200μm Terminal height: 200μm

端子直徑：250μm Terminal diameter: 250μm

端子間節距：400μm Pitch between terminals: 400μm

端子的數量：10×10=100個 Number of terminals: 10×10=100

<動態黏彈性(剪切儲存彈性模量)測定方法> <Measurement method of dynamic viscoelasticity (shear storage elastic modulus)>

對於黏彈性層，使用動態機械分析裝置(TA Instruments.公司製，製品名「DMA Q800」)，以升溫速度10℃/分的條件升溫至150℃，測定儲存彈性模量G’與損失彈性模量G”，求得這些的50℃之比(G”/G’)之tanδ的值。 For the viscoelastic layer, a dynamic mechanical analysis device (manufactured by TA Instruments, product name "DMA Q800") was used to raise the temperature to 150°C at a heating rate of 10°C/min, and the storage elastic modulus G' and loss elastic modulus were measured. Measure G" and find the tan δ value of the ratio of these at 50°C (G"/G').

<應力鬆弛性的測定方法> <Measurement method of stress relaxation>

圖1所示之形態的端子保護用膠帶1之中，剝離兩方的剝離膜，藉由複數層積層黏彈性層12，形成厚度約1mm的黏彈性層。然後製作直徑8mm、厚度約1mm的圓柱形狀的評價用試樣。 In the terminal protection tape 1 of the form shown in FIG. 1 , the release films on both sides are peeled off, and the viscoelastic layer 12 is laminated in a plurality of layers to form a viscoelastic layer with a thickness of approximately 1 mm. Then, a cylindrical evaluation sample with a diameter of 8 mm and a thickness of approximately 1 mm was prepared.

對於上述樣品，參考JIS K7244-7，使用黏彈性測定裝置(Anton paar公司製，製品名「MCR302」)，在50℃旋轉治具並扭轉評價用試樣藉由裝置控制持續施加10%(亦即36°)的一定的扭轉應變，測定鬆弛彈性模量G(t)(MPa)。由該測定結果推導出最大鬆弛彈性模量G(t)max(MPa)，並且推導出離測定前述最大鬆弛彈性模量G(t)max後至1秒後為止所測定之最小鬆弛彈性模量G(t)min(MPa)。 For the above-mentioned sample, refer to JIS K7244-7, use a viscoelasticity measuring device (manufactured by Anton Paar Co., Ltd., product name "MCR302"), rotate the jig at 50°C, and twist the evaluation sample to continuously apply 10% (also That is, a certain torsional strain of 36°), and the relaxation elastic modulus G(t) (MPa) is measured. The maximum relaxation elastic modulus G(t) max (MPa) is deduced from the measurement results, and the minimum relaxation elastic modulus measured up to 1 second after the measurement of the maximum relaxation elastic modulus G(t) max is deduced. G(t) min (MPa).

測定溫度：50℃ Measuring temperature: 50℃

由所獲得之最大鬆弛彈性模量G(t)max(MPa)以及最小鬆弛彈性模量G(t)min(MPa)根據下述式(1)來算出鬆弛彈性模量變數X2=△logG(t)。 From the obtained maximum relaxation elastic modulus G(t) max (MPa) and the minimum relaxation elastic modulus G(t) min (MPa), the relaxation elastic modulus variable X2=ΔlogG ( t).

X2=logG(t)max-logG(t)min‧‧‧(1) X2=logG(t) max -logG(t) min ‧‧‧(1)

<剛壓製後的埋入性評價方法> <Method for evaluation of embedability immediately after pressing>

將圖3之形態的端子保護用膠帶3的貼合黏著劑層15側之剝離膜22剝離，並接著於SUS(Stainless Steel；不銹鋼)板30上，製作圖4之形態的埋入性評價用的試樣，剝離黏著劑層14側的剝離膜20，將該SUS板30之側朝下的方式設置於溫度調節至50℃之加熱板上。然後，如圖5(a)所示，將前述附端子之半導體裝置的端子之側朝下的方式，使用真空積層機，以壓製壓 力(負重1.1MPa)、壓製時間40s、加熱溫度50℃而按壓於該黏彈性層12。對9個附端子之半導體裝置實施該埋入性評價。 Peel off the release film 22 on the adhesive layer 15 side of the terminal protective tape 3 in the form of Figure 3 and adhere it to the SUS (Stainless Steel; stainless steel) plate 30 to produce a embedability evaluation tool in the form of Figure 4 For the sample, peel off the release film 20 on the adhesive layer 14 side, and place the SUS plate 30 side down on a hot plate adjusted to 50°C. Then, as shown in FIG. 5(a) , the semiconductor device with terminals is pressed with the terminal side facing down using a vacuum laminator. The viscoelastic layer 12 is pressed with force (load 1.1MPa), pressing time 40s, and heating temperature 50°C. This embedding property evaluation was performed on nine semiconductor devices with terminals.

於剛壓製後，橫向觀察而確認埋入性，將所有附端子之半導體裝置之下側面接著於端子保護用膠帶，端子隱蔽於端子保護用膠帶而無法觀察到之情況評價為剛壓製後的埋入性良好(5)。將半導體裝置的內側雖確認到一部分的端子浮起，但半導體裝置外周部隱蔽於端子保護用膠帶而無法觀察到端子之情況評價為剛壓製後的埋入性良好(4)。將半導體裝置外周部的一部分由端子保護用膠帶剝離，可觀察到端子之比率為50%以下者評價為剛壓製後的埋入性普通(3)。將半導體裝置外周部的一部分由端子保護用膠帶剝離，可觀察到端子之比率為50%以上者評價為剛壓製後的埋入性(2)。將至少一個附端子之半導體裝置之下側面自端子保護用膠帶浮起，於端子保護用膠帶與半導體裝置本體之間全部可觀察到端子之情況評價為剛壓製後的埋入性不良(1)。 Immediately after pressing, observe laterally to confirm the embeddability, and attach the lower side of all semiconductor devices with terminals to the terminal protection tape. If the terminals are hidden by the terminal protection tape and cannot be observed, the condition is evaluated as embedment immediately after pressing. Good penetration (5). Although it was confirmed that some terminals were floating on the inside of the semiconductor device, but the outer peripheral part of the semiconductor device was hidden by the terminal protection tape and the terminals could not be observed, the embedding property immediately after pressing was evaluated as good (4). When a part of the outer peripheral part of the semiconductor device was peeled off from the terminal protection tape, and the ratio of terminals was observed to be 50% or less, the embedding property immediately after pressing was evaluated as average (3). A part of the outer peripheral part of the semiconductor device was peeled off from the terminal protection tape, and if the terminal ratio was 50% or more, the embedding property immediately after pressing was evaluated (2). When the lower side of at least one semiconductor device with terminals is raised from the terminal protection tape and all terminals are visible between the terminal protection tape and the semiconductor device body, it is evaluated as poor embedding performance immediately after pressing (1) .

<壓製1日後的浮起的評價方法> <Method for evaluating the rise after 1 day of suppression>

之後，對於放冷至常溫之1日後的附端子之半導體裝置，橫向觀察而確認浮起，將所有的附端子之半導體裝置的下側面接著端子保護用膠帶，端子隱蔽於端子保護用膠帶而無法觀察到之情況評價為浮起良好(5)。將半導體裝置的內側雖確認到一部分的端子浮起，但半導體裝置外周部隱蔽於端子保護用膠帶而無法觀察到端子之情況評價為浮起良好(4)。將半導體裝置外周部的一部分由端子保護用膠帶剝離，可觀察到端子之比率為50%以下者評價為浮起普通(3)。將半導體裝置外周部的一部分由端子保護用膠帶剝離，可觀察到端子之比率為50%以上者評價為浮起略不良(2)。將附端子之半導體裝置之下側面自端子保護用膠帶浮起，於端子保護用膠帶與半導體裝置本體之間全部可觀察到端子之情況評價為浮起不良(1)。 After that, after one day of cooling to normal temperature, the semiconductor devices with terminals were observed laterally to confirm that they were floating, and terminal protective tape was attached to the lower surfaces of all semiconductor devices with terminals. The terminals were hidden by the terminal protective tape so that they could not be exposed. The observation was evaluated as good floating (5). Although it was confirmed that some terminals were lifted inside the semiconductor device, but the outer peripheral part of the semiconductor device was hidden by the terminal protection tape and the terminals could not be observed, it was evaluated as good floating (4). When a part of the outer peripheral part of the semiconductor device was peeled off from the terminal protection tape and the ratio of observed terminals was 50% or less, it was evaluated as floating normal (3). When a part of the outer peripheral part of the semiconductor device was peeled off from the terminal protection tape and the proportion of terminals was observed to be 50% or more, it was evaluated as slightly defective (2). When the lower side of a semiconductor device with terminals is lifted from the terminal protection tape, and all terminals are visible between the terminal protection tape and the semiconductor device body, it is evaluated as floating failure (1).

[實施例1] [Example 1]

<端子保護用膠帶的製造> <Manufacturing of terminal protection tape>

於藉由聚矽氧處理將聚對苯二甲酸乙二酯製膜之單面進行剝離處理而成的剝離膜(琳得科(Lintec)公司製造之「SP-PET381031」，厚度38μm)之剝離處理面塗敷埋入層形成用組成物A，於100℃加熱乾燥1分鐘後，於埋入層形成用組成物A之上層壓藉由聚矽氧處理將聚對苯二甲酸乙二酯製膜之單面進行剝離處理而成的剝離膜(琳得科(Lintec)公司製造之「SP-PET382150」，厚度38μm)之剝離處理面，製造厚度50μm之埋入層。 Peeling of a release film ("SP-PET381031" manufactured by Lintec, thickness 38 μm) made by peeling one side of a polyethylene terephthalate film through polysiloxane treatment The treated surface is coated with the embedded layer forming composition A, and after heating and drying at 100°C for 1 minute, the embedded layer forming composition A is laminated onto the treated surface. Polyethylene terephthalate is processed by polysiloxane treatment. An embedded layer with a thickness of 50 μm was produced on the peel-treated surface of a release film ("SP-PET382150" manufactured by Lintec, thickness 38 μm) that was peeled off on one side of the film.

將前述埋入層中的將所層壓之剝離膜剝去的面彼此貼合，製作厚度100μm之埋入層。同樣地將埋入層貼合而積層，製作厚度300μm之埋入層A。 The surfaces of the embedded layers from which the laminated release films were peeled off were bonded together to prepare an embedded layer with a thickness of 100 μm. The buried layers were bonded and laminated in the same manner to prepare a buried layer A with a thickness of 300 μm.

於厚度10μm之黏著劑層14貼合厚度300μm之埋入層A，製造具有圖1所示之形態的厚度310μm之黏彈性層12的實施例1之端子保護用膠帶1。 The embedded layer A with a thickness of 300 μm was bonded to the adhesive layer 14 with a thickness of 10 μm to produce the terminal protection tape 1 of Example 1 having a viscoelastic layer 12 with a thickness of 310 μm as shown in FIG. 1 .

<應力鬆弛性的測定> <Measurement of Stress Relaxation>

對於實施例1的端子保護用膠帶1，算出鬆弛彈性模量變數X2=△logG(t)。結果如表1所示。 Regarding the terminal protection tape 1 of Example 1, the relaxation elastic modulus variable X2=ΔlogG(t) was calculated. The results are shown in Table 1.

<黏彈性層的剪切儲存彈性模量測定> <Measurement of shear storage elastic modulus of viscoelastic layer>

對於實施例1的端子保護用膠帶1，求得50℃之tanδ(損失彈性模量G”/儲存彈性模量G’)。結果如表1所示。 For the terminal protection tape 1 of Example 1, the tan δ (loss elastic modulus G"/storage elastic modulus G') at 50°C was determined. The results are shown in Table 1.

<埋入性的評價> <Evaluation of embeddedness>

將實施例1的端子保護用膠帶1的埋入層A之側的剝離膜剝離，與基材之聚對苯二甲酸乙二酯(PET)膜(製品名「Cosmoshine A4100」，厚度50μm，東洋紡公司製造)的易接著處理側貼合，製造具有如圖2所示之基材11/埋入層13/黏著劑層14的形態的黏彈性層12之實施例1的端子保護用膠帶2。 Peel off the release film on the buried layer A side of the terminal protective tape 1 of Example 1, and separate it from the polyethylene terephthalate (PET) film (product name "Cosmoshine A4100", thickness 50 μm, Toyobo) as the base material Co., Ltd.), the terminal protection tape 2 of Example 1 having the viscoelastic layer 12 in the form of base material 11/embedded layer 13/adhesive layer 14 as shown in Figure 2 was produced.

進而在實施例1的端子保護用膠帶2的基材的埋入層A相反側，積層前述貼合黏著劑層A，製造具有如圖3所示之形態的黏彈性層12之實施例1的端子保護用膠帶3。 Furthermore, the above-mentioned bonding adhesive layer A was laminated on the side opposite to the buried layer A of the base material of the terminal protective tape 2 of Example 1, and the viscoelastic layer 12 of Example 1 having the form shown in FIG. 3 was produced. Tape for terminal protection3.

對於實施例1的端子保護用膠帶3之剛壓製後的埋入性進行評價。結果如表1所示。 The embedding properties of the terminal protective tape 3 of Example 1 immediately after pressing were evaluated. The results are shown in Table 1.

<浮起的評價> <Floating evaluation>

之後，對於放冷至常溫之1日後的附端子之半導體裝置評價浮起。結果如表1所示。 Thereafter, the semiconductor device with terminals was evaluated one day after being cooled to normal temperature. The results are shown in Table 1.

[實施例2] [Example 2]

<端子保護用膠帶的製造> <Manufacturing of terminal protection tape>

實施例1之中，將埋入層形成用組成物A變更為埋入層形成用組成物B，其它以與實施例1相同的方式，製造具有如圖1所示之形態的厚度310μm的黏彈性層12之實施例1的端子保護用膠帶1。 In Example 1, the buried layer forming composition A was changed to the buried layer forming composition B, and in the same manner as in Example 1, an adhesive with a thickness of 310 μm having the form shown in Figure 1 was produced. The terminal protection tape 1 of the elastic layer 12 of Example 1.

與實施例1相同的方式，對於實施例2的端子保護用膠帶1之中黏彈性層12求得50℃之tanδ(損失彈性模量G”/儲存彈性模量G’)。此外，算出50℃之鬆弛彈性模量變數X2=△logG(t)。結果如表1所示。 In the same manner as in Example 1, the tan δ (loss elastic modulus G"/storage elastic modulus G') at 50°C was calculated for the viscoelastic layer 12 in the terminal protective tape 1 of Example 2. In addition, 50 was calculated The relaxation elastic modulus variable X2=△logG(t) at ℃. The results are shown in Table 1.

與實施例1相同的方式，使用實施例2的端子保護用膠帶1，製造具有如圖2所示之形態的黏彈性層12之實施例2的端子保護用膠帶2、以及具有如圖3所示之形態的黏彈性層12之實施例2的端子保護用膠帶3。 In the same manner as in Example 1, the terminal protective tape 1 of Example 2 was used to manufacture the terminal protective tape 2 of Example 2 having the viscoelastic layer 12 in the form shown in Figure 2, and the terminal protective tape 2 having the viscoelastic layer 12 as shown in Figure 3. The terminal protection tape 3 of Example 2 has the viscoelastic layer 12 in the form shown.

對於實施例2的端子保護用膠帶3，與實施例1同樣地評價剛壓製後的埋入性、以及浮起。結果如表1所示。 Regarding the terminal protection tape 3 of Example 2, the embedding properties and floating properties immediately after pressing were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[實施例3] [Example 3]

<端子保護用膠帶的製造> <Manufacturing of terminal protection tape>

實施例1之中，將埋入層形成用組成物A變更為埋入層形成用組成物C，其它以與實施例1相同的方式，製造具有如圖1所示之形態的厚度310μm的黏彈性層12之實施例3的端子保護用膠帶1。 In Example 1, the buried layer forming composition A was changed to the buried layer forming composition C, and in the same manner as in Example 1, an adhesive with a thickness of 310 μm having the form shown in Figure 1 was produced. The terminal protection tape 1 of Example 3 of the elastic layer 12.

與實施例1相同的方式，對於實施例3的端子保護用膠帶1之中黏彈性層12求得50℃之tanδ(損失彈性模量G”/儲存彈性模量G’)。此外，算出50℃之鬆弛彈性模量變數X2=△logG(t)。結果如表1所示。 In the same manner as in Example 1, the tan δ (loss elastic modulus G"/storage elastic modulus G') at 50°C was calculated for the viscoelastic layer 12 in the terminal protective tape 1 of Example 3. In addition, 50 was calculated The relaxation elastic modulus variable X2=△logG(t) at ℃. The results are shown in Table 1.

與實施例1相同的方式，使用實施例3的端子保護用膠帶1，製造具有如圖2所示之形態的黏彈性層12之實施例3的端子保護用膠帶2、以及具有如圖3所示之形態的黏彈性層12之實施例3的端子保護用膠帶3。 In the same manner as in Example 1, the terminal protective tape 1 of Example 3 was used to manufacture the terminal protective tape 2 of Example 3 having the viscoelastic layer 12 in the form shown in Figure 2, and the terminal protective tape 2 having the viscoelastic layer 12 as shown in Figure 3. The terminal protection tape 3 of Example 3 has the viscoelastic layer 12 in the form shown.

對於實施例3的端子保護用膠帶3，與實施例1同樣地評價剛壓製後的埋入性、以及浮起。結果如表1所示。 Regarding the terminal protection tape 3 of Example 3, the embedding properties and floating properties immediately after pressing were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[比較例1] [Comparative example 1]

<端子保護用膠帶的製造> <Manufacturing of terminal protection tape>

實施例1之中，將埋入層形成用組成物A變更為埋層形成用組成物D，其它以與實施例1相同的方式，製造具有如圖1所示之形態的厚度310μm的黏彈性層12之比較例1的端子保護用膠帶1。 In Example 1, the buried layer forming composition A was changed to the buried layer forming composition D, and otherwise in the same manner as in Example 1, a viscoelastic layer with a thickness of 310 μm having the form shown in Figure 1 was produced. Layer 12 of the terminal protection tape 1 of Comparative Example 1.

與實施例1相同的方式，對於比較例1的端子保護用膠帶1之中黏彈性層12求得50℃之tanδ(損失彈性模量G”/儲存彈性模量G’)。此外，算出50℃之鬆弛彈性模量變數X2=△logG(t)。結果如表1所示。 In the same manner as in Example 1, the tan δ (loss elastic modulus G"/storage elastic modulus G') at 50° C. of the viscoelastic layer 12 in the terminal protective tape 1 of Comparative Example 1 was calculated. In addition, 50 The relaxation elastic modulus variable X2=△logG(t) at ℃. The results are shown in Table 1.

與實施例1相同的方式，使用比較例1的端子保護用膠帶1，製造具有如圖2所示之形態的黏彈性層12之比較例1的端子保護用膠帶2、以及具有如圖3所示之形態的黏彈性層12之比較例1的端子保護用膠帶3。 In the same manner as in Example 1, the terminal protective tape 1 of Comparative Example 1 was used to produce the terminal protective tape 2 of Comparative Example 1 having the viscoelastic layer 12 as shown in Figure 2, and the terminal protective tape 2 having the viscoelastic layer 12 as shown in Figure 3. The terminal protection tape 3 of Comparative Example 1 has the viscoelastic layer 12 in the form shown.

對於比較例1的端子保護用膠帶3，與實施例1同樣地評價剛壓製後的埋入性、以及浮起。結果如表1所示。 Regarding the terminal protection tape 3 of Comparative Example 1, the embedding properties and floating properties immediately after pressing were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[比較例2] [Comparative example 2]

<端子保護用膠帶的製造> <Manufacturing of terminal protection tape>

實施例1之中，將埋入層形成用組成物A變更為埋入層形成用組成物E，其它以與實施例1相同的方式，製造具有如圖1所示之形態的厚度310μm的黏彈性層12之比較例2的端子保護用膠帶1。 In Example 1, the buried layer forming composition A was changed to the buried layer forming composition E, and in the same manner as in Example 1, an adhesive with a thickness of 310 μm having the form shown in Figure 1 was produced. Terminal protective tape 1 of Comparative Example 2 of the elastic layer 12.

與實施例1相同的方式，對於比較例2的端子保護用膠帶1之中黏彈性層12求得50℃之tanδ(損失彈性模量G”/儲存彈性模量G’)。此外，算出50℃之鬆弛彈性模量變數X2=△logG(t)。結果如表1所示。 In the same manner as in Example 1, the tan δ (loss elastic modulus G"/storage elastic modulus G') at 50° C. of the viscoelastic layer 12 in the terminal protective tape 1 of Comparative Example 2 was calculated. In addition, 50 The relaxation elastic modulus variable X2=△logG(t) at ℃. The results are shown in Table 1.

與實施例1相同的方式，使用比較例2的端子保護用膠帶1，製造如圖2所示之形態的黏彈性層12之比較例2的端子保護用膠帶2、以及具有如圖3所示之形態的黏彈性層12之比較例2的端子保護用膠帶3。 In the same manner as in Example 1, the terminal protective tape 1 of Comparative Example 2 was used to produce the terminal protective tape 2 of Comparative Example 2 with the viscoelastic layer 12 in the form shown in Figure 2, and the terminal protective tape 2 with the viscoelastic layer 12 as shown in Figure 3. The terminal protection tape 3 of Comparative Example 2 has a viscoelastic layer 12 in the form of the following.

對於比較例2的端子保護用膠帶3，與實施例1同樣地評價剛壓製後的埋入性、以及浮起。結果如表1所示。 Regarding the terminal protection tape 3 of Comparative Example 2, the embedding properties and floating properties immediately after pressing were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[比較例3] [Comparative example 3]

<端子保護用膠帶的製造> <Manufacturing of terminal protection tape>

實施例1之中，將埋入層形成用組成物A變更為埋入層形成用組成物F，其它以與實施例1相同的方式，製造具有如圖1所示之形態的厚度310μm的黏彈性層12之比較例3的端子保護用膠帶1。 In Example 1, the buried layer forming composition A was changed to the buried layer forming composition F, and in the same manner as in Example 1, an adhesive with a thickness of 310 μm having the form shown in Figure 1 was produced. Terminal protective tape 1 of Comparative Example 3 of the elastic layer 12.

與實施例1相同的方式，對於比較例3的端子保護用膠帶1之中黏彈性層12求得50℃之tanδ(損失彈性模量G”/儲存彈性模量G’)。此外，算出50℃之鬆弛彈性模量變數X2=△logG(t)。結果如表1所示。 In the same manner as in Example 1, the tan δ (loss elastic modulus G"/storage elastic modulus G') at 50° C. of the viscoelastic layer 12 in the terminal protective tape 1 of Comparative Example 3 was calculated. In addition, 50 The relaxation elastic modulus variable X2=△logG(t) at ℃. The results are shown in Table 1.

與實施例1相同的方式，使用比較例3的端子保護用膠帶1，製造具有如圖2所示之形態的黏彈性層12之比較例3的端子保護用膠帶2、以及具有如圖3所示之形態的黏彈性層12之比較例3的端子保護用膠帶3。 In the same manner as in Example 1, the terminal protective tape 1 of Comparative Example 3 was used to manufacture the terminal protective tape 2 of Comparative Example 3 having the viscoelastic layer 12 as shown in Figure 2, and the terminal protective tape 2 having the viscoelastic layer 12 as shown in Figure 3. The terminal protection tape 3 of Comparative Example 3 has the viscoelastic layer 12 in the form shown.

對於比較例3的端子保護用膠帶3，與實施例1同樣地評價剛壓製後的埋入性、以及浮起。結果如表1所示。 Regarding the terminal protection tape 3 of Comparative Example 3, the embedding properties and floating properties immediately after pressing were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Figure 108128166-A0305-02-0058-1
Figure 108128166-A0305-02-0058-1

如表1所示之結果，比較例之端子保護用膠帶，係埋入性不良(比較例2)，或是在壓製1日後產生浮起(圖7(c))，在對附端子之半導體裝置進行電磁波屏蔽時，在形成電磁波屏蔽膜時，可能有端子電極與電磁波屏蔽膜出現電性短路之虞(圖7(f))。 As shown in the results shown in Table 1, the terminal protection tape of the comparative example had poor embedding properties (Comparative Example 2) or floated after 1 day of pressing (Fig. 7(c)). When the device performs electromagnetic wave shielding, when the electromagnetic wave shielding film is formed, there may be an electrical short circuit between the terminal electrode and the electromagnetic wave shielding film (Figure 7(f)).

本實施形態的實施例之端子保護用膠帶中，可將容易產生浮起之凸塊埋設於黏彈性層12，使半導體裝置的端子形成面密接在黏彈性層，1日後亦不會產生浮起。因此，使用本實施形態的端子保護用膠帶，對附端子之半導體裝置進行電磁波屏蔽時，在形成電磁波屏蔽膜時，可防止端子電極之凸塊與電磁波屏蔽膜出現電性短路且沒有必要設置步驟上複雜的遮罩部等。 In the terminal protection tape of this embodiment, bumps that are prone to floating can be embedded in the viscoelastic layer 12 so that the terminal formation surface of the semiconductor device is in close contact with the viscoelastic layer and floating will not occur even after one day. . Therefore, when the terminal protective tape of this embodiment is used to shield a semiconductor device with terminals from electromagnetic waves, it is possible to prevent an electrical short circuit between the bumps of the terminal electrodes and the electromagnetic wave shielding film when forming the electromagnetic wave shielding film, and no installation step is necessary. on complex masking parts, etc.

(產業可利用性) (industrial availability)

本實施形態之端子保護用膠帶可用於在對附端子之半導體裝置進行電磁波屏蔽時，保護附端子之半導體裝置之端子的用途。可使用本實施形態之端子保護用膠帶對附端子之半導體裝置進行電磁波屏蔽，可製造附電磁波屏蔽膜之半導體裝置。 The terminal protection tape of this embodiment can be used to protect the terminals of the semiconductor device with terminals when shielding the semiconductor device with terminals from electromagnetic waves. The terminal protection tape of this embodiment can be used to shield a semiconductor device with terminals from electromagnetic waves, and a semiconductor device with an electromagnetic wave shielding film can be manufactured.

1:端子保護用膠帶 1: Tape for terminal protection

12:黏彈性層 12:Viscoelastic layer

13:埋入層 13: Buried layer

14:黏著劑層 14: Adhesive layer

20、21:剝離膜 20, 21: peeling film

Claims (5)

一種端子保護用膠帶，係用於在附端子之半導體裝置形成電磁波屏蔽膜之步驟；前述端子保護用膠帶具有由埋入層以及黏著劑層所構成之黏彈性層；前述埋入層係由丙烯酸系樹脂所構成，前述黏著劑層係由丙烯酸系樹脂所構成；在前述黏彈性層的動態黏彈性測定之中，50℃之tanδ的值為0.2以上；對於前述黏彈性層，將直徑8mm、厚度約1mm的圓柱形狀的評價用試樣在50℃施加10%(36°)的一定的扭轉應變來測定鬆弛彈性模量時，從最大鬆弛彈性模量G(t)max(MPa)以及離測定前述最大鬆弛彈性模量G(t)max後至1秒後為止所測定之最小鬆弛彈性模量G(t)min(MPa)，根據下述式(1)所求出之鬆弛彈性模量變數X2係滿足下述式(2)：X2=logG(t)max-logG(t)min‧‧‧(1) 0.12≦X2‧‧‧(2)。 A terminal protection tape, which is a step for forming an electromagnetic wave shielding film on a semiconductor device with terminals; the terminal protection tape has a viscoelastic layer composed of an embedded layer and an adhesive layer; the embedded layer is made of acrylic It is composed of resin, and the aforementioned adhesive layer is composed of acrylic resin; in the dynamic viscoelasticity measurement of the aforementioned viscoelastic layer, the value of tan δ at 50°C is more than 0.2; for the aforementioned viscoelastic layer, the diameter is 8 mm, When measuring the relaxation elastic modulus of a cylindrical evaluation sample with a thickness of about 1 mm by applying a constant torsional strain of 10% (36°) at 50°C, the maximum relaxation elastic modulus G(t) max (MPa) and the distance The minimum relaxation modulus G(t) min (MPa) measured from the maximum relaxation modulus G(t) max to 1 second later is the relaxation modulus calculated from the following formula (1). The variable X2 satisfies the following formula ( 2 ): 如請求項1所記載之端子保護用膠帶，其中依序具有前述黏著劑層、前述埋入層、基材。 The terminal protection tape according to claim 1, which has the adhesive layer, the embedded layer and the base material in this order. 如請求項2所記載之端子保護用膠帶，係依序具有前述黏著劑層、前述埋入層、前述基材、第二黏著劑層之雙面膠帶。 The terminal protection tape described in Claim 2 is a double-sided tape having the aforementioned adhesive layer, the aforementioned buried layer, the aforementioned base material, and a second adhesive layer in this order. 一種附電磁波屏蔽膜之半導體裝置的製造方法，係包含：在如請求項1至3之任1項所記載之端子保護用膠帶的黏彈性層埋設前述附端子之半導體裝置的端子之步驟；在未埋設在前述端子保護用膠帶的黏彈性層之前述附端子之半導體裝置的露出面形成電磁波屏蔽膜之步驟。 A method of manufacturing a semiconductor device with an electromagnetic wave shielding film, which includes the step of burying terminals of the aforementioned semiconductor device with terminals in the viscoelastic layer of the terminal protection tape described in any one of claims 1 to 3; A step of forming an electromagnetic wave shielding film on the exposed surface of the semiconductor device with terminals that is not embedded in the viscoelastic layer of the terminal protective tape. 一種附電磁波屏蔽膜之半導體裝置的製造方法，係包含： 在如請求項1至3之任1項所記載之端子保護用膠帶的黏彈性層埋設附端子之半導體裝置的端子之步驟；切割前述附端子之半導體裝置集合體，並將前述附端子之半導體裝置集合體作成端子埋設在前述端子保護用膠帶的黏彈性層之附端子之半導體裝置之步驟；在未埋設在前述端子保護用膠帶的黏彈性層之前述附端子之半導體裝置的露出面形成電磁波屏蔽膜之步驟。 A method of manufacturing a semiconductor device with an electromagnetic wave shielding film, which includes: The step of embedding the terminals of the semiconductor device with terminals in the viscoelastic layer of the terminal protection tape as described in any one of claims 1 to 3; cutting the semiconductor device assembly with terminals, and placing the semiconductor device with terminals A step of forming a device assembly into a semiconductor device with terminals in which terminals are embedded in the viscoelastic layer of the terminal protective tape; forming an electromagnetic wave on an exposed surface of the semiconductor device with terminals before being embedded in the viscoelastic layer of the terminal protective tape; Shielding film steps.
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