TWI712670B - Sheet for forming protective film and method of manufacturing tip having protective film - Google Patents

Sheet for forming protective film and method of manufacturing tip having protective film Download PDF

Info

Publication number
TWI712670B
TWI712670B TW108128902A TW108128902A TWI712670B TW I712670 B TWI712670 B TW I712670B TW 108128902 A TW108128902 A TW 108128902A TW 108128902 A TW108128902 A TW 108128902A TW I712670 B TWI712670 B TW I712670B
Authority
TW
Taiwan
Prior art keywords
protective film
sheet
film forming
laminate
forming
Prior art date
Application number
TW108128902A
Other languages
Chinese (zh)
Other versions
TW201940622A (en
Inventor
山本大輔
佐伯尚哉
米山裕之
Original Assignee
日商琳得科股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日商琳得科股份有限公司 filed Critical 日商琳得科股份有限公司
Publication of TW201940622A publication Critical patent/TW201940622A/en
Application granted granted Critical
Publication of TWI712670B publication Critical patent/TWI712670B/en

Links

Images

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/50—Working by transmitting the laser beam through or within the workpiece
    • B23K26/53—Working by transmitting the laser beam through or within the workpiece for modifying or reforming the material inside the workpiece, e.g. for producing break initiation cracks
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • 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 at least one potential-jump barrier or surface barrier, e.g. 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
    • H01L21/70—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
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/8319—Arrangement of the layer connectors prior to mounting
    • H01L2224/83192—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on another item or body to be connected to the semiconductor or solid-state body

Abstract

A sheet for forming a protective film which includes a first supporting sheet and a film for forming a protective film laminated on a first surface side of the first supporting sheet, wherein the film for forming the protective film is composed of a curable material and has following properties: when the film for forming the protective film is cured to form the protective film, the breaking strain of the protective film at 50°C is 20% or less and the peak temperature T1 of the loss tangent is 25 to 60°C.

Description

保護膜形成用片以及附有保護膜的晶片的製造方法Sheet for forming protective film and method for manufacturing wafer with protective film

本發明係關於一種可於半導體晶圓等工件或對前述工件加工所得之加工物（例如半導體晶片）形成保護膜之保護膜形成用片。 本案係根據2014年8月22日在日本申請之日本專利特願2014-169266號及日本專利特願2014-169267號主張優先權，且將其內容引用於本文中。The present invention relates to a protective film forming sheet that can form a protective film on a workpiece such as a semiconductor wafer or a processed product (such as a semiconductor wafer) obtained by processing the aforementioned workpiece. This case claims priority based on Japanese Patent Application No. 2014-169266 and Japanese Patent Application No. 2014-169267 filed in Japan on August 22, 2014, and the contents of which are incorporated herein.

近年來係利用稱為面朝下（face-down）方式之安裝法而製造半導體裝置。該方法中，當安裝具有形成有凸塊等電極之電路面之半導體晶片時，將半導體晶片之電路面側接合於引線框架等晶片搭載部。因此，成為未形成電路之半導體晶片之背面側露出之構造。In recent years, semiconductor devices have been manufactured using a mounting method called a face-down method. In this method, when mounting a semiconductor wafer having a circuit surface on which electrodes such as bumps are formed, the circuit surface side of the semiconductor wafer is bonded to a chip mounting portion such as a lead frame. Therefore, it becomes a structure in which the back side of the semiconductor chip without a circuit is exposed.

專利文獻1及2揭示保護膜形成/切割一體型片（即保護膜形成用片），係將可形成上述保護膜之保護膜形成層（即保護膜形成膜）形成於黏著片上而成。該保護膜形成/切割一體型片中，上述保護膜形成膜藉由加熱處理進行硬化，而形成上述保護膜。即，藉由上述保護膜形成/切割一體型片，則可進行切割半導體晶圓及對半導體晶片形成保護膜兩者，而可獲得附有保護膜之半導體晶片。Patent Documents 1 and 2 disclose a protective film forming/cutting integrated sheet (that is, a protective film forming sheet), which is formed by forming a protective film forming layer (that is, a protective film forming film) capable of forming the above-mentioned protective film on an adhesive sheet. In this protective film forming/cutting integrated sheet, the protective film forming film is cured by heat treatment to form the protective film. That is, by the above-mentioned protective film forming/dicing integrated sheet, both the dicing of the semiconductor wafer and the formation of the protective film on the semiconductor wafer can be performed, and the semiconductor wafer with the protective film can be obtained.

另一方面，當自半導體晶圓等工件製造包含半導體晶片等片狀體之加工物時，以往通常進行刀切割加工，係一面對工件吹送以清洗等為目的之液體，一面利用旋轉刀將工件切割而獲得片狀體。然而，近年來係採用能以乾式分割成片狀體之隱形切割（stealth dicing）（註冊商標；以下相同）加工（專利文獻3）。On the other hand, when manufacturing processed objects including semiconductor wafers and other flakes from workpieces such as semiconductor wafers, conventionally, knife cutting is usually performed. While blowing liquid for cleaning or the like against the workpiece, the rotary knife The workpiece is cut to obtain flakes. However, in recent years, stealth dicing (registered trademark; the same below) processing that can be divided into slices in a dry manner has been adopted (Patent Document 3).

例如，專利文獻3中揭示一種隱形切割法，係將積層黏著片（即積層兩層包含基材與黏著劑層之黏著片而成者）貼附於極薄之半導體晶圓，自積層黏著片側透過積層黏著片對半導體晶圓照射雷射光，而於半導體晶圓之內部形成改質部之後，使黏著片延伸，藉此而沿著切割線分割半導體晶圓，而生產半導體晶片。 [先前技術文獻] [專利文獻]For example, Patent Document 3 discloses a stealth dicing method, which attaches a laminated adhesive sheet (that is, a laminate consisting of two layers of an adhesive sheet containing a substrate and an adhesive layer) to an extremely thin semiconductor wafer, from the laminated adhesive sheet side The semiconductor wafer is irradiated with laser light through the laminated adhesive sheet, and after a modified part is formed inside the semiconductor wafer, the adhesive sheet is extended to divide the semiconductor wafer along the cutting line to produce the semiconductor wafer. [Prior Technical Literature] [Patent Literature]

專利文獻1：日本專利特開2012-33637號公報。 專利文獻2：日本專利特開2011-151362號公報。 專利文獻3：日本專利第3762409號公報。Patent Document 1: Japanese Patent Laid-Open No. 2012-33637. Patent Document 2: Japanese Patent Laid-Open No. 2011-151362. Patent Document 3: Japanese Patent No. 3762409.

[發明所欲解決之課題][The problem to be solved by the invention]

如上所述，隱形切割係使黏著片延伸而分割半導體晶圓，因此有將位於黏著片與半導體晶圓之間的構件亦與半導體晶圓同樣地分割之較佳情形。於此種構件為保護膜形成膜時，為了實現恰當之分割，亦有對保護膜形成膜進行冷卻之情形。As described above, invisible dicing is to extend the adhesive sheet to divide the semiconductor wafer. Therefore, it is preferable to divide the member between the adhesive sheet and the semiconductor wafer in the same way as the semiconductor wafer. When such a member is a protective film forming film, in order to realize proper division, the protective film forming film may be cooled.

本發明之目的在於提供一種具備保護膜形成膜之保護膜形成用片，係於隱形切割中，當位於黏著片與半導體晶圓等工件之間的構件為由保護膜形成膜所形成之保護膜時，在使黏著片延伸時可恰當地分割保護膜。另外，作為另一形態，本發明之目的在於提供一種使用該保護膜形成用片而製造附有保護膜之半導體晶片等加工物的方法。 [用以解決課題的手段]The object of the present invention is to provide a protective film forming sheet with a protective film forming film, which is used in invisible dicing, when the member located between the adhesive sheet and a workpiece such as a semiconductor wafer is a protective film formed by the protective film forming film When extending the adhesive sheet, the protective film can be divided appropriately. In addition, as another aspect, an object of the present invention is to provide a method of manufacturing a processed product such as a semiconductor wafer with a protective film using the protective film forming sheet. [Means to solve the problem]

為了達成上述目的而提供之本發明包含以下之態樣。 （1）一種保護膜形成用片，係具備第1支撐片及積層於前述第1支撐片之第1面側之保護膜形成膜，前述保護膜形成膜包含硬化性材料，使前述保護膜形成膜硬化而成之保護膜於50℃之斷裂應變為20%以下，且損耗正切之峰值溫度T1處於25℃至60℃之範圍內。The present invention provided in order to achieve the above object includes the following aspects. (1) A sheet for forming a protective film, comprising a first support sheet and a protective film forming film laminated on the first surface side of the first support sheet, the protective film forming film includes a curable material, and the protective film is formed The protective film formed by the hardening of the film has a breaking strain of less than 20% at 50°C, and the peak temperature T1 of the loss tangent is in the range of 25°C to 60°C.

（2）如上述（1）所記載之保護膜形成用片，其中前述保護膜於25℃之儲存模數為5.0×109 Pa以上。(2) The sheet for forming a protective film as described in (1) above, wherein the storage modulus of the protective film at 25° C. is 5.0×10 9 Pa or more.

（3）如上述（1）或（2）所記載之保護膜形成用片，其中前述保護膜於25℃之損耗正切為0.4以下。(3) The sheet for forming a protective film as described in (1) or (2) above, wherein the loss tangent of the protective film at 25° C. is 0.4 or less.

（4）如上述（1）至（3）中任一項所記載之保護膜形成用片，其中前述保護膜之波長為1064 nm之透光率為40%以上。(4) The protective film formation sheet as described in any one of (1) to (3) above, wherein the protective film has a wavelength of 1064 nm and a light transmittance of 40% or more.

（5）如上述（1）至（4）中任一項所記載之保護膜形成用片，其中前述保護膜形成用片具備第2支撐片，係積層於前述保護膜形成膜中與面對前述第1支撐片之面相反的面側。(5) The sheet for forming a protective film as described in any one of (1) to (4) above, wherein the sheet for forming a protective film includes a second supporting sheet, which is laminated on the protective film forming film and facing The surface of the first support piece is opposite to the surface.

（6）一種附有保護膜之晶片之製造方法，其具備：貼附步驟，係使如上述（1）至（5）中任一項所記載之保護膜形成用片所具備的前述保護膜形成膜中與面對前述第1支撐片之面為相反側之面露出，將前述面貼附於工件之一面上，而獲得具備前述保護膜形成用片與前述工件之第1積層體；第1硬化步驟，係使前述第1積層體之前述保護膜形成用片所具備之前述保護膜形成膜硬化，而獲得前述保護膜；第1分割步驟，係於將經過前述第1硬化步驟之前述第1積層體之前述保護膜形成用片所具備的前述保護膜之溫度T2保持在40℃至70℃之範圍內之狀態下，使前述保護膜形成用片所具備之前述第1支撐片伸長，將前述保護膜與前述工件一起分割，而獲得第2積層體，該第2積層體係於前述第1支撐片之一面上配置有將前述工件與前述保護膜之積層體分割而成之複數個附有保護膜之晶片；及第1拾取步驟，係將前述第2積層體所具備之前述複數個附有保護膜之晶片分別自前述第1支撐片分離，而獲得前述附有保護膜之晶片作為加工物；且進行改質層形成步驟，係於開始前述第1分割步驟之前，以聚焦於設定在前述工件內部之焦點的方式照射紅外線區域之雷射光，而於前述工件內部形成改質層。(6) A method of manufacturing a wafer with a protective film, comprising: an attaching step of making the protective film included in the protective film forming sheet described in any one of (1) to (5) above The surface of the formed film opposite to the surface facing the first support sheet is exposed, and the surface is attached to one surface of the work to obtain a first laminate including the protective film forming sheet and the work; 1. The curing step is to harden the protective film forming film of the protective film forming sheet of the first laminate to obtain the protective film; the first dividing step is to perform the first curing step While maintaining the temperature T2 of the protective film included in the protective film forming sheet of the first laminate in the range of 40°C to 70°C, the first supporting sheet included in the protective film forming sheet is extended , The protective film and the work are divided together to obtain a second laminate. The second laminate system is arranged on one surface of the first support sheet with a plurality of laminates of the work and the protective film. Chip with protective film; and the first picking step is to separate the plurality of chips with protective film included in the second laminate from the first support sheet to obtain the chip with protective film As a processed object; and the modified layer forming step is performed, before starting the first division step, laser light in the infrared region is irradiated to focus on the focal point set in the workpiece, and the modified layer is formed inside the workpiece .

（7）如上述（6）所記載之附有保護膜之晶片之製造方法，其中前述溫度T2為前述溫度T1以上。(7) The method for manufacturing a wafer with a protective film as described in (6) above, wherein the temperature T2 is equal to or higher than the temperature T1.

（8）一種附有保護膜之晶片之製造方法，其具備：積層步驟，係使如上述（1）至（5）中任一項所記載之保護膜形成用片所具備的前述保護膜形成膜中與面對前述第1支撐片之面為相反側之面露出，將前述面貼附於工件之一面上，且將前述保護膜形成用片之前述第1支撐片自前述保護膜形成膜剝離，而獲得具備前述工件與前述保護膜形成膜之第3積層體；第2硬化步驟，係使前述第3積層體所具備之前述保護膜形成膜硬化，而獲得前述保護膜；第2貼附步驟，係將具備第3基材及積層於前述第3基材之一面側之第3黏著劑層的加工用片之前述第3黏著劑層側之面，與經過前述第2硬化步驟之前述第3積層體之前述保護膜側的面貼合，而獲得具備前述加工用片與前述第3積層體之第4積層體；第2分割步驟，係於將前述第4積層體所具備之前述保護膜之溫度T3保持在40℃至70℃之範圍內的狀態下，使前述第4積層體所具備之前述加工用片伸長，將前述保護膜與前述工件一起分割，而獲得第5積層體，該第5積層體係於前述加工用片之一面上配置有將前述工件與前述保護膜之積層體分割而成之複數個附有保護膜之晶片；及第2拾取步驟，係將前述第5積層體所具備之前述複數個附有保護膜之晶片分別自前述加工用片分離，而獲得前述附有保護膜之晶片作為加工物；且進行改質層形成步驟，係於開始前述第2分割步驟之前，以聚焦於設定在前述工件內部之焦點的方式照射紅外線區域之雷射光，而於前述工件內部形成改質層。(8) A method for manufacturing a wafer with a protective film, comprising: a layering step of forming the protective film included in the protective film forming sheet described in any one of (1) to (5) above The surface of the film opposite to the surface facing the first support sheet is exposed, the surface is attached to one surface of the workpiece, and the first support sheet of the protective film forming sheet is formed into a film from the protective film Peel off to obtain a third layered body including the workpiece and the protective film forming film; the second curing step is to cure the protective film forming film of the third layered body to obtain the protective film; The attaching step is to combine the surface on the third adhesive layer side of the processing sheet with the third base material and the third adhesive layer laminated on one surface side of the third base material, and the surface that has undergone the second curing step The surface of the third layered body on the protective film side is bonded to obtain a fourth layered body including the processing sheet and the third layered body; the second dividing step is to combine the fourth layered body with While maintaining the temperature T3 of the protective film in the range of 40°C to 70°C, the processing sheet included in the fourth laminate is extended, and the protective film is divided together with the workpiece to obtain a fifth laminate The fifth layered system is provided with a plurality of protective film-attached wafers formed by dividing the workpiece and the layered body of the protective film on one surface of the processing sheet; and the second pick-up step is to combine the first 5. The plurality of protective film-attached wafers included in the laminate are separated from the processing sheet to obtain the protective film-attached wafer as a processed product; and the step of forming a modified layer is performed at the beginning of the second Before the dividing step, laser light in the infrared region is irradiated to focus on the focal point set inside the workpiece to form a modified layer inside the workpiece.

（9）如上述（8）所記載之附有保護膜之晶片之製造方法，其中前述溫度T3為前述溫度T1以上。(9) The method for manufacturing a wafer with a protective film as described in (8) above, wherein the temperature T3 is higher than the temperature T1.

即，本發明包含以下之態樣。 [1]一種保護膜形成用片，係具備第1支撐片及積層於前述第1支撐片之第1面側之保護膜形成膜，前述保護膜形成膜包含硬化性材料且具有以下之特性：前述保護膜形成膜硬化成為保護膜時，50℃之斷裂應變為20%以下，且損耗正切之峰值溫度T1為25℃至60℃。 [2]如[1]所記載之保護膜形成用片，其中前述保護膜形成膜進一步具有以下特性：前述保護膜之25℃之儲存模數為3.0×109 Pa以上。 [3]如[1]或[2]所記載之保護膜形成用片，其中前述保護膜形成膜進一步具有以下特性：前述保護膜之25℃之損耗正切為0.4以下。 [4]如[1]至[3]中任一項所記載之保護膜形成用片，其中前述保護膜形成膜進一步具有以下特性：前述保護膜之波長為1064 nm之透光率為40%以上。 [5]如[1]至[4]中任一項所記載之保護膜形成用片，其中前述保護膜形成用片進一步具備第2支撐片，係積層於前述保護膜形成膜中與面對前述第1支撐片之面相反之面側。 [6]一種附有保護膜之晶片之製造方法，包括：貼附步驟，係使如[1]至[5]中任一項所記載之保護膜形成用片所具備的前述保護膜形成膜中與面對前述第1支撐片之面為相反側之面露出，將前述露出之面貼附於工件之一面上，而獲得具備前述保護膜形成用片與前述工件之第1積層體；第1硬化步驟，係藉由使前述第1積層體中之前述保護膜形成膜硬化，而獲得前述保護膜；第1分割步驟，係於將經過前述第1硬化步驟之前述第1積層體中之前述保護膜之溫度T2保持在40℃至70℃之範圍內的狀態下，使前述第1支撐片伸長，將前述保護膜與前述工件一起分割，藉此獲得第2積層體，該第2積層體係於前述第1支撐片之一面上配置有將前述工件與前述保護膜之積層體以於厚度方向產生切割面之方式分割而成的複數個附有保護膜之晶片；及第1拾取步驟，係將前述第2積層體所具備之前述複數個附有保護膜之晶片分別自前述第1支撐片分離，而獲得前述附有保護膜之晶片作為加工物；進一步包括改質層形成步驟，係於開始前述第1分割步驟之前，以聚焦於設定在前述工件內部之焦點的方式照射紅外線區域之雷射光，而於前述工件內部形成改質層。 [7]如[6]所記載之附有保護膜之晶片之製造方法，其中前述溫度T2為前述溫度T1以上。 [8]一種附有保護膜之晶片之製造方法，其包括：積層步驟，係使如[1]至[5]中任一項所記載之保護膜形成用片所具備的前述保護膜形成膜中與面對前述第1支撐片之面為相反側之面露出，將前述露出之面貼附於工件之一面上，且將前述保護膜形成用片之前述第1支撐片自前述保護膜形成膜剝離，藉此獲得具備前述工件與前述保護膜形成膜之第3積層體；第2硬化步驟，係藉由使前述第3積層體所具備之前述保護膜形成膜硬化，而獲得前述保護膜；第2貼附步驟，係將具備第3基材及積層於前述第3基材之一面側之第3黏著劑層的加工用片中之積層有前述第3黏著劑層之側之面，與經過前述第2硬化步驟之前述第3積層體中之前述保護膜側之面貼合，而獲得具備前述加工用片與前述第3積層體之第4積層體；第2分割步驟，係於將前述第4積層體所具備之前述保護膜之溫度T3保持在40℃至70℃之範圍內的狀態下，使前述第4積層體所具備之前述加工用片伸長，將前述保護膜與前述工件一起分割，藉此獲得第5積層體，該第5積層體係於前述加工用片之一面上配置有將前述工件與前述保護膜之積層體以於厚度方向產生切割面之方式分割而成的複數個附有保護膜之晶片；及第2拾取步驟，係將前述第5積層體所具備之前述複數個附有保護膜之晶片分別自前述加工用片分離，而獲得前述附有保護膜之晶片作為加工物；進一步包括改質層形成步驟，係於開始前述第2分割步驟之前，以聚焦於設定在前述工件內部之焦點的方式照射紅外線區域之雷射光，而於前述工件內部形成改質層。 [9]如[8]所記載之附有保護膜之晶片之製造方法，其中前述溫度T3為前述溫度T1以上。 [發明功效]That is, the present invention includes the following aspects. [1] A protective film forming sheet comprising a first support sheet and a protective film forming film laminated on the first surface side of the first support sheet, the protective film forming film comprising a curable material and having the following characteristics: When the aforementioned protective film forming film is cured into a protective film, the breaking strain at 50°C is 20% or less, and the peak temperature T1 of the loss tangent is 25°C to 60°C. [2] The protective film forming sheet as described in [1], wherein the protective film forming film further has the following characteristics: the storage modulus of the protective film at 25° C. is 3.0×10 9 Pa or more. [3] The sheet for forming a protective film as described in [1] or [2], wherein the protective film forming film further has the following characteristics: the loss tangent of the protective film at 25° C. is 0.4 or less. [4] The protective film forming sheet as described in any one of [1] to [3], wherein the protective film forming film further has the following characteristics: the protective film has a wavelength of 1064 nm and a light transmittance of 40% the above. [5] The sheet for forming a protective film as described in any one of [1] to [4], wherein the sheet for forming a protective film further includes a second support sheet, which is laminated on the protective film forming film and faces the The surface side opposite to the surface of the first support piece. [6] A method for manufacturing a wafer with a protective film, comprising: an attaching step of forming a film of the protective film included in the protective film forming sheet described in any one of [1] to [5] The surface opposite to the surface facing the first support sheet is exposed, and the exposed surface is attached to one surface of the workpiece to obtain a first laminate including the protective film forming sheet and the workpiece; 1 Curing step, which is to obtain the protective film by curing the protective film forming film in the first laminated body; the first dividing step is to perform the first hardening step in the first laminated body While the temperature T2 of the protective film is maintained in the range of 40°C to 70°C, the first support sheet is extended, and the protective film is divided together with the workpiece, thereby obtaining a second laminate. The second laminate The system is provided with a plurality of protective film-attached wafers formed by dividing the laminate of the workpiece and the protective film in the thickness direction on one surface of the first supporting sheet; and the first picking step, Separating the plurality of protective film-attached wafers provided in the second laminate from the first support sheet to obtain the protective film-attached wafer as a processed product; further including a modified layer forming step, Before starting the first dividing step, laser light in the infrared region is irradiated to focus on the focal point set inside the workpiece to form a modified layer inside the workpiece. [7] The method for manufacturing a wafer with a protective film as described in [6], wherein the temperature T2 is equal to or higher than the temperature T1. [8] A method of manufacturing a wafer with a protective film, comprising: a layering step of forming a film of the protective film included in the protective film forming sheet described in any one of [1] to [5] The surface opposite to the surface facing the first support sheet is exposed, the exposed surface is attached to one surface of the workpiece, and the first support sheet of the protective film forming sheet is formed from the protective film The film is peeled off to obtain a third laminate having the workpiece and the protective film forming film; the second curing step is to harden the protective film forming film of the third laminate to obtain the protective film ; The second attaching step is to laminate a processing sheet with a third base material and a third adhesive layer laminated on one side of the third base material on the side of the third adhesive layer, It is bonded to the surface of the protective film side of the third laminate after the second curing step to obtain a fourth laminate including the processing sheet and the third laminate; the second division step is While maintaining the temperature T3 of the protective film provided in the fourth laminate in the range of 40°C to 70°C, the processing sheet provided in the fourth laminate is extended, and the protective film and the foregoing The workpieces are divided together to obtain a fifth layered body. The fifth layered system is provided with a layered body of the workpiece and the protective film on one side of the processing sheet so as to produce a cut surface in the thickness direction. A plurality of protective film-attached wafers; and the second picking step is to separate the plurality of protective film-attached wafers provided in the fifth laminate from the processing sheet to obtain the protective film attached Wafer as a processed object; further comprising a modified layer forming step, before starting the second dividing step, irradiate the laser light in the infrared region to focus on the focal point set inside the workpiece to form a modified layer inside the workpiece Floor. [9] The method for manufacturing a wafer with a protective film as described in [8], wherein the temperature T3 is higher than the temperature T1. [Invention Effect]

根據本發明之保護膜形成用片，即便由前述保護膜形成膜形成之保護膜為位於黏著片與半導體晶圓等工件之間的構件，也可於隱形切割中使黏著片延伸時恰當地分割保護膜。因此，可穩定地製造附有保護膜之半導體晶片。According to the protective film forming sheet of the present invention, even if the protective film formed of the aforementioned protective film forming film is a member located between the adhesive sheet and a workpiece such as a semiconductor wafer, it can be appropriately divided when the adhesive sheet is extended during stealth dicing Protective film. Therefore, a semiconductor wafer with a protective film can be manufactured stably.

以下說明本發明之實施形態。 圖1係本發明一實施形態之保護膜形成用片之剖面圖。如圖1所示，本實施形態之保護膜形成用片3構成為具備：第1支撐片4；保護膜形成膜1，係積層於第1支撐片4之一面（後述之「第1面」；圖1中為上表面）側；及治具用黏著劑層5，係積層於保護膜形成膜1中與面對第1支撐片4之面為相反側之面的周緣部。治具用黏著劑層5係用於將保護膜形成用片3接著於環狀架（ring frame）等治具之層。而且，本實施形態之保護膜形成用片3於保護膜形成膜1及治具用黏著劑層5上（即與第1支撐片4為相反側）具備剝離片6。該剝離片6係於保護膜形成用片3使用時要剝離去除之片，於保護膜形成用片3中並非必需之構成要件。 即，本發明一實施形態之保護膜形成用片之一個形態包含：第1支撐片4；保護膜形成膜1，積層於第1支撐片4之一面側；治具用黏著劑層5，積層於保護膜形成膜1中與面對第1支撐片4之面為相反側之面的周緣部；及視需要之剝離片6，係積層於保護膜形成膜1及治具用黏著劑層5上。The embodiments of the present invention will be described below. Fig. 1 is a cross-sectional view of a protective film forming sheet according to an embodiment of the present invention. As shown in FIG. 1, the protective film forming sheet 3 of this embodiment is configured to include: a first support sheet 4; a protective film forming film 1, which is laminated on one surface of the first support sheet 4 ("the first surface" described later) 1 is the upper surface) side; and the jig adhesive layer 5, which is laminated in the protective film forming film 1 and the surface facing the first support sheet 4 on the opposite side of the peripheral edge. The adhesive layer 5 for jigs is a layer for adhering the sheet 3 for forming the protective film to jigs such as a ring frame. Furthermore, the protective film formation sheet 3 of this embodiment is equipped with the peeling sheet 6 on the protective film formation film 1 and the adhesive layer 5 for jigs (that is, the side opposite to the 1st support sheet 4). The peeling sheet 6 is a sheet to be peeled and removed when the sheet 3 for forming a protective film is used, and is not an essential component in the sheet 3 for forming a protective film. That is, one form of the protective film forming sheet according to an embodiment of the present invention includes: a first support sheet 4; a protective film forming film 1, laminated on one surface side of the first support sheet 4; and an adhesive layer 5 for jigs, laminated The peripheral portion of the surface of the protective film forming film 1 opposite to the surface facing the first support sheet 4; and the peeling sheet 6 as necessary, which is laminated on the protective film forming film 1 and the adhesive layer 5 for jigs on.

本實施形態之保護膜形成用片3用於在對工件進行加工時貼附於前述工件而保持前述工件，並且於前述工件或對前述工件加工所得之加工物上形成保護膜。該保護膜由硬化之保護膜形成膜1構成。The protective film forming sheet 3 of the present embodiment is used to adhere to the workpiece to hold the workpiece when the workpiece is processed, and to form a protective film on the workpiece or a processed product obtained by processing the workpiece. The protective film is composed of a cured protective film forming film 1.

作為一例，本實施形態之保護膜形成用片3用於在作為工件之半導體晶圓之切割加工時，係保持半導體晶圓，並且於藉由切割所得之半導體晶片上形成保護膜，但並不限定於此。As an example, the protective film forming sheet 3 of this embodiment is used to hold the semiconductor wafer during the dicing process of the semiconductor wafer as a workpiece, and to form a protective film on the semiconductor wafer obtained by dicing, but it is not Limited to this.

本實施形態之保護膜形成用片3通常形成為長條狀並捲繞成輥狀，且以輥對輥（roll to roll）方式使用。The sheet 3 for forming a protective film of the present embodiment is usually formed in a long strip shape and wound in a roll shape, and is used in a roll to roll method.

1.支撐片 與本發明一實施形態之保護膜形成用片3相關之第1支撐片4係具備基材41、及積層於基材41之一面側（即保護膜形成膜1側；圖1中為上側）之黏著劑層42而構成。此處，將第1支撐片4中之要積層保護膜形成膜1側之面稱為「第1面」，將其相反側之面（圖1中為下表面）稱為「第2面」。第1支撐片4中，黏著劑層42積層於第1支撐片4之第1面側，基材41積層於第1支撐片4之第2面側。1. Support sheet The first support sheet 4 related to the protective film forming sheet 3 of one embodiment of the present invention includes a base material 41 and is laminated on one surface side of the base material 41 (that is, the protective film forming film 1 side; the upper side in FIG. 1) The adhesive layer 42 is formed. Here, the surface of the first support sheet 4 on the side of the protective film forming film 1 to be laminated is referred to as the "first surface", and the surface on the opposite side (the lower surface in FIG. 1) is referred to as the "second surface" . In the first support sheet 4, the adhesive layer 42 is laminated on the first surface side of the first support sheet 4, and the base material 41 is laminated on the second surface side of the first support sheet 4.

1-1.基材 與本發明一實施形態之保護膜形成用片3相關之基材41只要為作為用於隱形切割之黏著片之基材而通常使用的基材，則並無特別限定。基材41可具有單層構造，亦可具有積層構造。於保護膜形成膜1為藉由加熱而形成保護膜之膜，在進行用於形成保護膜之保護膜形成膜1之加熱時，基材41亦被加熱的情形下，要求基材41為於該加熱後亦可恰當地使用（例如可列舉能恰當地延伸等）之基材。1-1. Substrate The base material 41 related to the protective film forming sheet 3 of one embodiment of the present invention is not particularly limited as long as it is a base material generally used as a base material of an adhesive sheet for stealth dicing. The base material 41 may have a single-layer structure or a multilayer structure. When the protective film forming film 1 is a film that forms a protective film by heating, when the substrate 41 is also heated when the protective film forming film 1 for forming the protective film is heated, the substrate 41 is required to be After this heating, a base material that can be used appropriately (for example, it can be stretched appropriately).

就該觀點而言，基材41之熔點較佳為90℃～180℃，尤佳為100℃～160℃，進一步較佳為110℃～150℃。From this viewpoint, the melting point of the base material 41 is preferably 90°C to 180°C, more preferably 100°C to 160°C, and further preferably 110°C to 150°C.

對基材41之熔點進行調整之方法並無特別限制，通常主要可利用所使用之樹脂材料之熔點進行調整。另外，亦可藉由混合熔點不同之複數種樹脂材料或使複數種單體共聚合而調整成任意之熔點。The method of adjusting the melting point of the base material 41 is not particularly limited, and usually the melting point of the resin material used can be used for adjustment. In addition, it can also be adjusted to an arbitrary melting point by mixing plural resin materials with different melting points or copolymerizing plural monomers.

基材41之130℃之儲存模數較佳為1 MPa～100 MPa。藉由使130℃之儲存模數為上述範圍，可確保基材41之耐熱性，且降低使第1支撐片4延伸時產生不良情形之可能性。就同時實現提高基材41之耐熱性及使第1支撐片4容易地延伸之觀點而言，基材41之130℃之儲存模數更佳為2 MPa～80 MPa，尤佳為5 MPa～50 MPa。再者，上述儲存模數之測定方法如後述之試驗例所示。The storage modulus of the base material 41 at 130°C is preferably 1 MPa-100 MPa. By setting the storage modulus at 130° C. within the above range, the heat resistance of the base material 41 can be ensured, and the possibility of defects when the first support sheet 4 is stretched is reduced. From the viewpoint of simultaneously improving the heat resistance of the base material 41 and easily extending the first support sheet 4, the storage modulus of the base material 41 at 130°C is more preferably 2 MPa～80 MPa, particularly preferably 5 MPa～ 50 MPa. In addition, the measurement method of the above-mentioned storage modulus is as shown in the test example described later.

對基材41之130℃之儲存模數進行調整之方法並無特別限定，通常主要可利用所使用之樹脂材料之儲存模數進行調整。另外，通常即便為相同化學構造，亦有若分子量高則儲存模數變高之傾向，且有藉由交聯或狹窄之分子量分佈亦使儲存模數變高之傾向。可基於該傾向而調整成任意之儲存模數。The method of adjusting the storage modulus of the base material 41 at 130° C. is not particularly limited. Generally, the storage modulus of the resin material used can be used for adjustment. In addition, even with the same chemical structure, the storage modulus tends to increase when the molecular weight is high, and the storage modulus tends to increase due to crosslinking or narrow molecular weight distribution. It can be adjusted to any storage modulus based on this tendency.

於隱形切割等中使用波長為1064 nm之雷射光時，基材41之加熱後之波長為1064 nm之透光率較佳為40%以上且100%以下，更佳為50%以上且99.9%以下，尤佳為60%以上且99.5%以下。藉由使基材41之加熱後之波長為1064 nm之透光率處於上述範圍，利用隱形切割之工件之分割性優異。When using laser light with a wavelength of 1064 nm in invisible cutting, etc., the light transmittance of the substrate 41 after heating at a wavelength of 1064 nm is preferably 40% or more and 100% or less, more preferably 50% or more and 99.9% Below, more preferably 60% or more and 99.5% or less. By making the light transmittance of the substrate 41 at a wavelength of 1064 nm after heating in the above-mentioned range, the partability of the workpiece by stealth cutting is excellent.

另外，於對保護膜進行雷射標記等時，使用波長為532 nm之雷射光之情形下，基材41之加熱後之波長為532 nm之透光率較佳為0.1%以上且40%以下，更佳為0.3%以上且35%以下，尤佳為0.5%以上且30%以下。藉由使基材41之加熱後之波長為532 nm之透光率處於上述範圍，雷射列印性優異。In addition, in the case of using laser light with a wavelength of 532 nm when performing laser marking on the protective film, the light transmittance of the substrate 41 at a wavelength of 532 nm after heating is preferably 0.1% or more and 40% or less , More preferably 0.3% or more and 35% or less, particularly preferably 0.5% or more and 30% or less. By setting the light transmittance of the substrate 41 with a wavelength of 532 nm after heating in the above range, the laser printability is excellent.

作為構成基材41之樹脂膜之具體例，可列舉：低密度聚乙烯（Low-Density Polyethylene，LDPE）膜、直鏈低密度聚乙烯（Linear Low-Density Polyethylene，LLDPE）膜、高密度聚乙烯（High-Density Polyethylene，HDPE）膜等聚乙烯膜、聚丙烯膜、乙烯/丙烯共聚物膜、聚丁烯膜、聚丁二烯膜、聚甲基戊烯膜、乙烯/降莰烯共聚物膜、降莰烯樹脂膜等聚烯烴系膜；乙烯/乙酸乙烯酯共聚物膜、乙烯/（甲基）丙烯酸共聚物膜、乙烯/（甲基）丙烯酸酯共聚物膜等乙烯系共聚合膜；聚氯乙烯膜、氯乙烯共聚物膜等聚氯乙烯系膜；聚對苯二甲酸乙二酯膜、聚對苯二甲酸丁二酯膜等聚酯系膜；聚胺基甲酸酯膜；聚醯亞胺膜；聚苯乙烯膜；聚碳酸酯膜；氟樹脂膜等。而且，亦可使用該等之交聯膜、離子聚合物膜之類的改質膜。進一步，亦可為積層複數層上述膜而成之積層膜。另外，本說明書中之「（甲基）丙烯酸」表示丙烯酸及甲基丙烯酸兩者。其他類似用語亦相同。Specific examples of the resin film constituting the base material 41 include: Low-Density Polyethylene (LDPE) film, Linear Low-Density Polyethylene (LLDPE) film, High-density polyethylene (High-Density Polyethylene, HDPE) films such as polyethylene film, polypropylene film, ethylene/propylene copolymer film, polybutene film, polybutadiene film, polymethylpentene film, ethylene/norbornene copolymer Films, norbornene resin films and other polyolefin films; ethylene/vinyl acetate copolymer films, ethylene/(meth)acrylic acid copolymer films, ethylene/(meth)acrylate copolymer films, and other ethylene copolymer films ; Polyvinyl chloride film such as polyvinyl chloride film and vinyl chloride copolymer film; polyester film such as polyethylene terephthalate film and polybutylene terephthalate film; polyurethane film ; Polyimide film; polystyrene film; polycarbonate film; fluororesin film, etc. Furthermore, modified membranes such as crosslinked membranes and ionomer membranes can also be used. Furthermore, it may be a laminated film formed by laminating a plurality of the above-mentioned films. In addition, "(meth)acrylic acid" in this specification means both acrylic acid and methacrylic acid. Other similar terms are also the same.

上述中較佳為聚烯烴系膜，更佳為聚乙烯膜、聚丙烯膜及乙烯/丙烯共聚物膜，更佳為乙烯/丙烯共聚物膜。藉由該等樹脂膜，則易於滿足前述物性，尤其於乙烯/丙烯共聚物膜時，藉由調整乙烯單體與丙烯單體之共聚合比，而易於滿足前述物性。另外，就工件貼附性或晶片剝離性之觀點而言亦較佳為該等樹脂膜。Among the above, polyolefin-based films are preferred, polyethylene films, polypropylene films, and ethylene/propylene copolymer films are more preferred, and ethylene/propylene copolymer films are more preferred. With these resin films, it is easy to satisfy the aforementioned physical properties. Especially in the case of an ethylene/propylene copolymer film, the aforementioned physical properties can be easily satisfied by adjusting the copolymerization ratio of ethylene monomer and propylene monomer. In addition, these resin films are also preferable from the viewpoint of work attachment property or wafer peelability.

上述樹脂膜為了使與積層於其表面之黏著劑層42之密接性提高，可視需要對單面或兩面實施利用氧化法或凹凸化法等之表面處理、或底塗處理。作為上述氧化法，例如可列舉：電暈放電處理、電漿放電處理、鉻氧化處理（濕式）、火焰處理、熱風處理、臭氧、紫外線照射處理等。另外，作為凹凸化法，例如可列舉：噴砂法、熔射處理法等。In order to improve the adhesiveness of the above-mentioned resin film with the adhesive layer 42 laminated on the surface, surface treatment by oxidation or unevenness or primer treatment may be performed on one or both surfaces as necessary. Examples of the above-mentioned oxidation method include corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet), flame treatment, hot air treatment, ozone, ultraviolet irradiation treatment, and the like. In addition, as the roughening method, for example, a sandblasting method, a spraying method, etc. can be cited.

再者，基材41亦可於上述樹脂膜中含有著色劑、阻燃劑、塑化劑、抗靜電劑、潤滑劑、填料等各種添加劑。Furthermore, the base material 41 may contain various additives such as a colorant, a flame retardant, a plasticizer, an antistatic agent, a lubricant, and a filler in the above-mentioned resin film.

基材41之厚度只要可於使用保護膜形成用片3之各步驟中恰當地發揮功能，則並無特別限定，較佳為20 μm～450 μm，更佳為25 μm～400 μm，尤佳為50 μm～350 μm。 再者，所謂「厚度」係指於任意5個部位利用接觸式厚度計測定出厚度並以平均表示之值。The thickness of the substrate 41 is not particularly limited as long as it can properly function in each step of using the protective film forming sheet 3, and is preferably 20 μm to 450 μm, more preferably 25 μm to 400 μm, and particularly It is 50 μm～350 μm. In addition, the so-called "thickness" refers to the average value of the thickness measured by a contact thickness meter at any 5 locations.

1-2.黏著劑層 與本發明一實施形態之保護膜形成用片3相關之第1支撐片4所具備的黏著劑層42可由能量線非硬化性黏著劑構成，亦可由能量線硬化性黏著劑構成。作為能量線非硬化性黏著劑，較佳為具有所需之黏著力及再剝離性，例如可使用丙烯酸系黏著劑、橡膠系黏著劑、聚矽氧系黏著劑、胺基甲酸酯系黏著劑、聚酯系黏著劑、聚乙烯醚系黏著劑等。該等中，較佳為與保護膜形成膜1之密接性高之丙烯酸系黏著劑。1-2. Adhesive layer The adhesive layer 42 provided in the first support sheet 4 related to the protective film forming sheet 3 of one embodiment of the present invention may be composed of an energy ray non-curable adhesive or may be composed of an energy ray curable adhesive. As an energy-ray non-curable adhesive, it is preferable to have the required adhesive strength and releasability. For example, acrylic adhesives, rubber adhesives, silicone adhesives, urethane adhesives can be used Adhesives, polyester adhesives, polyvinyl ether adhesives, etc. Among these, an acrylic adhesive with high adhesion to the protective film forming film 1 is preferable.

另一方面，能量線硬化性黏著劑藉由能量線照射而黏著力下降。因此，若使用能量線硬化性黏著劑，則當欲使工件或加工物與第1支撐片4分離時，可藉由照射能量線而容易地分離。 作為能量線，通常使用紫外線、電子束等。能量線之照射量根據能量線之種類而不同，例如於紫外線時，以光量計較佳為50 mJ/cm2 ～1000 mJ/cm2 ，更佳為100 mJ/cm2 ～500 mJ/cm2 。另外，於電子束時，較佳為10 krad～1000 krad左右。On the other hand, the energy-ray curable adhesive decreases its adhesive force by the energy-ray irradiation. Therefore, if an energy ray curable adhesive is used, when a workpiece or a processed object is to be separated from the first support sheet 4, it can be easily separated by irradiating energy ray. As energy rays, ultraviolet rays, electron beams, etc. are generally used. The irradiation amount of the energy ray varies according to the type of the energy ray. For example, in the case of ultraviolet rays, the light quantity is preferably 50 mJ/cm 2 ～1000 mJ/cm 2 , more preferably 100 mJ/cm 2 ～500 mJ/cm 2 . In addition, in the case of an electron beam, it is preferably about 10 krad to 1000 krad.

於黏著劑層42包含能量線硬化性黏著劑時，保護膜形成用片3中之黏著劑層42較佳為已硬化。使能量線硬化性黏著劑硬化而成之材料通常彈性模數高，且表面之平滑性高，因此，若使與包含該材料之硬化部分接觸之保護膜形成膜1硬化而形成保護膜，則與前述黏著劑層42之硬化部分接觸之前述保護膜表面的平滑性（巨觀）變高，作為晶片之保護膜而言係美觀性優異。另外，若對表面平滑性高之保護膜實施雷射列印，則該列印之視覺辨認性提高。When the adhesive layer 42 contains an energy-ray curable adhesive, the adhesive layer 42 in the protective film forming sheet 3 is preferably hardened. The material formed by curing the energy-ray curable adhesive usually has a high elastic modulus and a high surface smoothness. Therefore, if the protective film forming film 1 in contact with the hardened portion containing the material is cured to form a protective film, The smoothness (macro) of the surface of the protective film in contact with the hardened portion of the adhesive layer 42 becomes higher, and it is excellent in aesthetics as a protective film for a chip. In addition, if laser printing is performed on a protective film with high surface smoothness, the visibility of the printing improves.

構成黏著劑層42之能量線硬化性黏著劑可為以具有能量線硬化性之聚合物為主成分者；亦可為以不具有能量線硬化性之聚合物、與選自能量線硬化性之多官能單體及低聚物所組成之群中之至少一種成分的混合物為主成分之黏著劑。The energy-ray curable adhesive constituting the adhesive layer 42 may be a polymer with energy-ray curability as the main component; it may also be a polymer that does not have energy-ray curability, and a polymer selected from energy-ray curability. A mixture of at least one component in the group consisting of multifunctional monomers and oligomers is an adhesive as the main component.

以下說明能量線硬化性黏著劑以具有能量線硬化性之聚合物為主成分之情形。 再者，此處所謂之「主成分」係指相對於能量線硬化性黏著劑之總質量而含有60質量%以上。The following describes the case where the energy ray curable adhesive is mainly composed of a polymer having energy ray curability. In addition, the "main component" referred to here refers to the content of 60% by mass or more with respect to the total mass of the energy ray curable adhesive.

具有能量線硬化性之聚合物較佳為於側鏈導入有具有能量線硬化性之官能基（即能量線硬化性基）之（甲基）丙烯酸酯（共）聚合物（A）（以下有時稱為「能量線硬化型聚合物（A）」）。該能量線硬化型聚合物（A）較佳為使具有含官能基之單體單元之（甲基）丙烯酸系共聚物（a1）、與具有會和該官能基鍵結之取代基的含不飽和基之化合物（a2）反應而獲得之聚合物。The energy-ray-curable polymer is preferably a (meth)acrylate (co)polymer (A) having energy-ray-curable functional groups (ie, energy-ray-curable groups) introduced into the side chain It is called "energy ray hardening polymer (A)"). The energy ray-curable polymer (A) is preferably a (meth)acrylic copolymer (a1) having a functional group-containing monomer unit, and a non-containing polymer having a substituent that binds to the functional group Saturated compound (a2) is a polymer obtained by reaction.

丙烯酸系共聚物（a1）至少包含自含官能基之單體導出之結構單元、與自（甲基）丙烯酸酯單體或其衍生物導出之結構單元。The acrylic copolymer (a1) contains at least a structural unit derived from a monomer containing a functional group and a structural unit derived from a (meth)acrylate monomer or its derivative.

作為自上述含官能基之單體導出之結構單元中的含官能基之單體，較佳為於分子內具有聚合性之雙鍵，與羥基、胺基、經取代之胺基、環氧基等官能基之單體。As the functional group-containing monomer in the structural unit derived from the above-mentioned functional group-containing monomer, it is preferable to have a polymerizable double bond in the molecule, and a hydroxyl group, an amino group, a substituted amino group, and an epoxy group. Monomers with functional groups.

作為上述含官能基之單體之更具體之例，可列舉（甲基）丙烯酸2-羥基乙酯、（甲基）丙烯酸2-羥基丙酯、（甲基）丙烯酸3-羥基丙酯、（甲基）丙烯酸4-羥基丁酯等，該等可單獨使用或組合2種以上而使用。More specific examples of the above-mentioned functional group-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, ( Meth) acrylate 4-hydroxybutyl etc., these can be used individually or in combination of 2 or more types.

作為上述（甲基）丙烯酸酯單體，可使用烷基之碳數為1～20之（甲基）丙烯酸烷酯、烷基之碳數為3～11之（甲基）丙烯酸環烷酯、（甲基）丙烯酸苄酯等。該等中，較佳為烷基之碳數為1～18之（甲基）丙烯酸烷酯，例如可列舉（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基）丙烯酸正丁酯、（甲基）丙烯酸2-乙基己酯等。As the above-mentioned (meth)acrylate monomers, alkyl (meth)acrylates with 1-20 carbon atoms in the alkyl group, cycloalkyl (meth)acrylates with 3-11 carbon atoms in the alkyl group, Benzyl (meth)acrylate, etc. Among these, alkyl (meth)acrylates having an alkyl group of 1 to 18 carbon atoms are preferred, and examples include methyl (meth)acrylate, ethyl (meth)acrylate, and propylene (meth)acrylate. Ester, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc.

丙烯酸系共聚物（a1）係相對於丙烯酸系共聚物（a1）之總質量，以通常為3質量%～100質量%、較佳為5質量%～40質量%之比率含有自上述含官能基之單體導出之結構單元，且以通常為0質量%～97質量%、較佳為60質量%～95質量%之比率含有自（甲基）丙烯酸酯單體或其衍生物導出之結構單元而成。 即，丙烯酸系共聚物（a1）較佳為相對於丙烯酸系共聚物（a1）之總質量，以3質量%～100質量%之比率含有自上述含官能基之單體導出之結構單元，且以通常為0質量%～97質量%之比率含有自（甲基）丙烯酸酯單體或其衍生物導出之結構單元；更佳為以5質量%～40質量%之比率含有自上述含官能基之單體導出之結構單元，且以通常為60質量%～95質量%之比率含有自（甲基）丙烯酸酯單體或其衍生物導出之結構單元。 再者，自上述含官能基之單體導出之結構單元與自（甲基）丙烯酸酯單體或其衍生物導出之結構單元之合計質量不超過100質量%。The acrylic copolymer (a1) is based on the total mass of the acrylic copolymer (a1) and contains the functional group at a ratio of usually 3% to 100% by mass, preferably 5% to 40% by mass. The structural unit derived from the monomer, and contains the structural unit derived from the (meth)acrylate monomer or its derivative at a ratio of usually 0% to 97% by mass, preferably 60% to 95% by mass Become. That is, the acrylic copolymer (a1) preferably contains the structural unit derived from the functional group-containing monomer at a ratio of 3% to 100% by mass relative to the total mass of the acrylic copolymer (a1), and The structural unit derived from the (meth)acrylate monomer or its derivative is usually contained at a ratio of 0% to 97% by mass; more preferably, it contains a functional group derived from the above-mentioned functional group at a ratio of 5% to 40% by mass The structural unit derived from the monomer, and usually contains the structural unit derived from the (meth)acrylate monomer or its derivative at a ratio of 60% to 95% by mass. Furthermore, the total mass of the structural unit derived from the above-mentioned functional group-containing monomer and the structural unit derived from the (meth)acrylate monomer or its derivative does not exceed 100% by mass.

丙烯酸系共聚物（a1）可藉由利用常用方法使如上所述之含官能基之單體與（甲基）丙烯酸酯單體或其衍生物共聚合而獲得，除該等單體以外亦可共聚合二甲基丙烯醯胺、甲酸乙烯酯、乙酸乙烯酯、苯乙烯等。The acrylic copolymer (a1) can be obtained by copolymerizing the above-mentioned functional group-containing monomers with (meth)acrylate monomers or derivatives thereof by a common method, in addition to these monomers Copolymerization of dimethyl acrylamide, vinyl formate, vinyl acetate, styrene, etc.

藉由使具有上述含官能基之單體單元（即自含官能基之單體導出之結構單元）之丙烯酸系共聚物（a1），與具有會和該官能基鍵結之取代基的含不飽和基之化合物（a2）反應，而獲得能量線硬化型聚合物（A）。By making the acrylic copolymer (a1) having the above-mentioned functional group-containing monomer unit (that is, the structural unit derived from the functional group-containing monomer), and the acrylic copolymer (a1) having a substituent that binds to the functional group The saturated compound (a2) reacts to obtain an energy ray hardening polymer (A).

含不飽和基之化合物（a2）所具有之取代基可根據丙烯酸系共聚物（a1）所具有之含官能基之單體單元之官能基的種類而適當選擇。例如，於官能基為羥基、胺基或經取代之胺基時，作為取代基，較佳為異氰酸酯基或環氧基，於官能基為環氧基時，作為取代基，較佳為胺基、羧基或氮丙啶基（aziridinyl）。The substituent of the unsaturated group-containing compound (a2) can be appropriately selected according to the type of the functional group of the functional group-containing monomer unit of the acrylic copolymer (a1). For example, when the functional group is a hydroxyl group, an amino group or a substituted amino group, the substituent is preferably an isocyanate group or an epoxy group, and when the functional group is an epoxy group, the substituent is preferably an amino group , Carboxyl or aziridinyl (aziridinyl).

另外，含不飽和基之化合物（a2）中每一分子含有1個～5個、較佳為1個～2個能量線聚合性之碳-碳雙鍵。作為此種含不飽和基之化合物（a2）之具體例，例如可列舉：異氰酸2-甲基丙烯醯氧基乙酯、異氰酸間異丙烯基-α,α-二甲基苄酯、甲基丙烯醯基異氰酸酯、異氰酸烯丙酯、異氰酸1,1-（雙丙烯醯氧基甲基）乙酯；藉由二異氰酸酯化合物或多異氰酸酯化合物與（甲基）丙烯酸羥基乙酯之反應而獲得之丙烯醯基單異氰酸酯化合物；藉由二異氰酸酯化合物或多異氰酸酯化合物與多元醇化合物與（甲基）丙烯酸羥基乙酯之反應而獲得之丙烯醯基單異氰酸酯化合物；（甲基）丙烯酸縮水甘油酯；（甲基）丙烯酸、（甲基）丙烯酸2-（1-氮丙啶基）乙酯；或2-乙烯基-2-噁唑啉；2-異丙烯基-2-噁唑啉等烯基噁唑啉化合物等。 上述中，較佳為異氰酸2-甲基丙烯醯氧基乙酯。In addition, the unsaturated group-containing compound (a2) contains 1 to 5, preferably 1 to 2 energy-ray polymerizable carbon-carbon double bonds per molecule. As specific examples of such unsaturated group-containing compound (a2), for example, 2-methacryloxyethyl isocyanate, m-isopropenyl isocyanate-α,α-dimethylbenzyl Ester, methacrylic isocyanate, allyl isocyanate, 1,1-(bisacryloxymethyl)ethyl isocyanate; by diisocyanate compound or polyisocyanate compound and (meth)acrylic acid Acrylic monoisocyanate compound obtained by the reaction of hydroxyethyl; Acrylic monoisocyanate compound obtained by the reaction of a diisocyanate compound or polyisocyanate compound and a polyol compound with hydroxyethyl (meth)acrylate; ( Glycidyl meth)acrylate; (meth)acrylic acid, 2-(1-aziridinyl)ethyl (meth)acrylate; or 2-vinyl-2-oxazoline; 2-isopropenyl- Alkenyl oxazoline compounds such as 2-oxazoline. Among the above, 2-methacryloxyethyl isocyanate is preferred.

含不飽和基之化合物（a2）係以相對於上述丙烯酸系共聚物（a1）之含官能基之單體每100當量而通常為10當量～100當量、較佳為20當量～95當量之比率使用。The unsaturated group-containing compound (a2) is usually 10 to 100 equivalents, preferably 20 to 95 equivalents per 100 equivalents of the functional group-containing monomer of the acrylic copolymer (a1). use.

丙烯酸系共聚物（a1）與含不飽和基之化合物（a2）之反應中，可根據官能基與取代基之組合而適當選擇反應之溫度、壓力、溶劑、時間、觸媒之有無、觸媒之種類。藉此使丙烯酸系共聚物（a1）中存在之官能基與含不飽和基之化合物（a2）中之取代基反應，將不飽和基導入至丙烯酸系共聚物（a1）中之側鏈，而獲得能量線硬化型聚合物（A）。In the reaction of the acrylic copolymer (a1) and the unsaturated group-containing compound (a2), the temperature, pressure, solvent, time, presence or absence of catalysts, catalysts can be appropriately selected according to the combination of functional groups and substituents The kind. Thereby, the functional groups in the acrylic copolymer (a1) are reacted with the substituents in the unsaturated group-containing compound (a2) to introduce the unsaturated groups into the side chains of the acrylic copolymer (a1), and Obtain energy ray hardening polymer (A).

如此獲得之能量線硬化型聚合物（A）之重量平均分子量較佳為1萬以上，更佳為15萬～150萬，尤佳為20萬～100萬。再者，本說明書中之重量平均分子量（Mw）係藉由凝膠滲透層析法（GPC法）測定出之聚苯乙烯換算之值。The weight average molecular weight of the energy ray hardening polymer (A) thus obtained is preferably 10,000 or more, more preferably 150,000 to 1.5 million, and particularly preferably 200,000 to 1 million. In addition, the weight average molecular weight (Mw) in this specification is a polystyrene conversion value measured by gel permeation chromatography (GPC method).

即便於能量線硬化性黏著劑以具有能量線硬化性之聚合物為主成分時，能量線硬化性黏著劑亦可進一步含有選自能量線硬化性之單體及低聚物所組成之群中之至少一種成分（B）。Even when the energy ray curable adhesive is mainly composed of a polymer having energy ray curability, the energy ray curable adhesive may further contain energy ray curable monomers and oligomers. At least one component (B).

作為選自能量線硬化性之單體及低聚物所組成之群中之至少一種成分（B），例如可使用多元醇與（甲基）丙烯酸之酯等。As at least one component (B) selected from the group consisting of energy-ray curable monomers and oligomers, for example, esters of polyols and (meth)acrylic acid can be used.

作為該選自能量線硬化性之單體及低聚物所組成之群中之至少一種成分（B），例如可列舉：（甲基）丙烯酸環己酯、（甲基）丙烯酸異莰酯等單官能性丙烯酸酯類；三羥甲基丙烷三（甲基）丙烯酸酯、新戊四醇三（甲基）丙烯酸酯、新戊四醇四（甲基）丙烯酸酯、二新戊四醇六（甲基）丙烯酸酯、1,4-丁二醇二（甲基）丙烯酸酯、1,6-己二醇二（甲基）丙烯酸酯、聚乙二醇二（甲基）丙烯酸酯、二羥甲基三環癸烷二（甲基）丙烯酸酯等多官能性丙烯酸酯類；聚酯低聚（甲基）丙烯酸酯、聚胺基甲酸酯低聚（甲基）丙烯酸酯等。 上述中，較佳為多官能性丙烯酸酯類、聚胺基甲酸酯低聚（甲基）丙烯酸酯。As the at least one component (B) selected from the group consisting of energy-ray curable monomers and oligomers, for example, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, etc. Monofunctional acrylic esters; trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, neopentylerythritol tetra(meth)acrylate, dineopentaerythritol hexa (Meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, two Multifunctional acrylates such as methylol tricyclodecane di(meth)acrylate; polyester oligo(meth)acrylate, polyurethane oligo(meth)acrylate, etc. Among the above, polyfunctional acrylates and polyurethane oligo(meth)acrylates are preferred.

於調配選自能量線硬化性之單體及低聚物所組成之群中之至少一種成分（B）時，能量線硬化性黏著劑中的選自能量線硬化性之單體及低聚物所組成之群中之至少一種成分（B）之含量相對於前述能量線硬化性黏著劑之總質量，較佳為5質量%～80質量%，更佳為20質量%～60質量%。When at least one component (B) selected from the group consisting of energy-ray-curable monomers and oligomers is formulated, the energy-ray-curable adhesive is selected from energy-ray-curable monomers and oligomers The content of at least one component (B) in the group is preferably 5 mass% to 80 mass%, and more preferably 20 mass% to 60 mass% relative to the total mass of the aforementioned energy ray curable adhesive.

此處，於使用紫外線作為用於使能量線硬化性樹脂組成物硬化之能量線時，較佳為進一步添加光聚合起始劑（C），藉由使用該光聚合起始劑（C），可減少聚合硬化時間及光線照射量。Here, when ultraviolet rays are used as the energy ray for curing the energy ray curable resin composition, it is preferable to further add a photopolymerization initiator (C), and by using the photopolymerization initiator (C), Can reduce polymerization hardening time and light exposure.

作為光聚合起始劑（C），具體而言可列舉：二苯甲酮、苯乙酮、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、2,4-二乙基噻吨酮（2,4-diethylthioxanthone）、1-羥基環己基苯基酮、苄基二苯硫醚、一硫化四甲基秋蘭姆、偶氮二異丁腈、苯偶醯、二苯偶醯、二乙醯、β-氯蒽醌、（2,4,6-三甲基苄基二苯基）氧化膦、2-苯并噻唑-N,N-二乙基二硫胺甲酸酯、低聚{2-羥基-2-甲基-1-[4-（1-丙烯基）苯基]丙酮}、2,2-二甲氧基-1,2-二苯基乙烷-1-酮等。 該等可單獨使用，亦可併用2種以上。Specific examples of the photopolymerization initiator (C) include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, and benzoin benzene Methyl formate, benzoin dimethyl ketal, 2,4-diethylthioxanthone (2,4-diethylthioxanthone), 1-hydroxycyclohexyl phenyl ketone, benzyl diphenyl sulfide, tetramethyl monosulfide Thiuram, azobisisobutyronitrile, benzil, dibenzyl, diacetyl, β-chloroanthraquinone, (2,4,6-trimethylbenzyldiphenyl) phosphine oxide, 2 -Benzothiazole-N,N-diethyldithiocarbamate, oligomeric {2-hydroxy-2-methyl-1-[4-(1-propenyl)phenyl]acetone}, 2, 2-Dimethoxy-1,2-diphenylethane-1-one, etc. These can be used individually or in combination of 2 or more types.

當將能量線硬化型共聚物（A）（於調配選自能量線硬化性之單體及低聚物所組成之群中之至少一種成分（B）的情形時，將能量線硬化型共聚物（A）、及選自能量線硬化性之單體及低聚物所組成之群中之至少一種成分（B）之合計量設為100質量份）設為100質量份時，光聚合起始劑（C）較佳為以0.1質量份～10質量份、尤其是0.5質量份～6質量份之範圍之量使用。When the energy-ray curable copolymer (A) (in the case of blending at least one component (B) selected from the group consisting of energy-ray curable monomers and oligomers, the energy-ray curable copolymer (A) and at least one component selected from the group consisting of energy-ray curable monomers and oligomers (B) The total amount is set to 100 parts by mass) When 100 parts by mass, photopolymerization starts The agent (C) is preferably used in an amount in the range of 0.1 parts by mass to 10 parts by mass, especially 0.5 parts by mass to 6 parts by mass.

能量線硬化性黏著劑中，除上述成分以外亦可調配適當其他成分。作為其他成分，例如可列舉不具有能量線硬化性之聚合物成分或低聚物成分（D）、交聯劑（E）等。 即，能量線硬化性黏著劑之一個形態係包含能量線硬化型共聚物（A）、以及視需要之從選自能量線硬化性之單體及低聚物所組成之群中之至少一種成分（B）、光聚合起始劑（C）、不具有能量線硬化性之聚合物成分或低聚物成分（D）、及交聯劑（E）所組成之群中選擇的至少一種成分。In the energy ray curable adhesive, other components may be appropriately formulated in addition to the above-mentioned components. As other components, for example, a polymer component or an oligomer component (D) that does not have energy ray curability, a crosslinking agent (E), and the like can be cited. That is, one form of the energy ray curable adhesive includes an energy ray curable copolymer (A), and optionally at least one component selected from the group consisting of energy ray curable monomers and oligomers At least one component selected from the group consisting of (B), photopolymerization initiator (C), polymer component or oligomer component (D) without energy ray curability, and crosslinking agent (E).

作為不具有能量線硬化性之聚合物成分或低聚物成分（D），例如可列舉聚丙烯酸酯、聚酯、聚胺基甲酸酯、聚碳酸酯、聚烯烴等，較佳為重量平均分子量（Mw）為3000～250萬之聚合物或低聚物。Examples of the polymer component or oligomer component (D) that does not have energy ray curability include polyacrylate, polyester, polyurethane, polycarbonate, polyolefin, etc., and weight average A polymer or oligomer with a molecular weight (Mw) of 3,000 to 2.5 million.

作為交聯劑（E），可使用與能量線硬化型共聚物（A）等所具有之官能基具有反應性的多官能性化合物。作為此種多官能性化合物之例，可列舉：異氰酸酯化合物、環氧化合物、胺化合物、三聚氰胺化合物、氮丙啶化合物、肼化合物、醛化合物、噁唑啉化合物、金屬烷氧化物、金屬螯合物、金屬鹽、銨鹽、反應性酚樹脂等。As the crosslinking agent (E), a polyfunctional compound having reactivity with the functional group possessed by the energy ray curable copolymer (A) or the like can be used. Examples of such polyfunctional compounds include: isocyanate compounds, epoxy compounds, amine compounds, melamine compounds, aziridine compounds, hydrazine compounds, aldehyde compounds, oxazoline compounds, metal alkoxides, metal chelate Compounds, metal salts, ammonium salts, reactive phenol resins, etc.

藉由將該等其他成分（D）、（E）調配至能量線硬化性黏著劑，而可改善硬化前之黏著性及剝離性、硬化後之強度、與其他層之接著性、保存穩定性等。該等其他成分之調配量並無特別限定，可在相對於能量線硬化型共聚物（A）100質量份而為0質量份～40質量份之範圍內適當決定。By blending these other components (D) and (E) into the energy ray curable adhesive, the adhesiveness and peelability before curing, the strength after curing, the adhesion to other layers, and the storage stability can be improved Wait. The blending amount of these other components is not particularly limited, and can be appropriately determined in the range of 0 to 40 parts by mass relative to 100 parts by mass of the energy ray curable copolymer (A).

接著，以下說明能量線硬化性黏著劑係以不具有能量線硬化性之聚合物成分、與選自能量線硬化性之多官能單體及低聚物所組成之群中之至少一種的混合物為主成分之情形。Next, it is explained below that the energy-ray curable adhesive is a mixture of a polymer component that does not have energy-ray curability and at least one selected from the group consisting of energy-ray curable polyfunctional monomers and oligomers. The main component of the situation.

作為不具有能量線硬化性之聚合物成分，例如可使用與前述丙烯酸系共聚物（a1）相同之成分。能量線硬化性樹脂組成物中之不具有能量線硬化性之聚合物成分之含量，相對於前述能量線硬化性樹脂組成物之總質量，較佳為20質量%～99.9質量%，尤佳為30質量%～80質量%。As a polymer component that does not have energy ray curability, for example, the same component as the aforementioned acrylic copolymer (a1) can be used. The content of the polymer component that does not have energy ray curability in the energy ray curable resin composition is preferably 20% by mass to 99.9% by mass relative to the total mass of the aforementioned energy ray curable resin composition, and more preferably 30% to 80% by mass.

作為選自能量線硬化性之多官能單體及低聚物所組成之群中之至少一種成分，可選擇與前述成分（B）相同者。不具有能量線硬化性之聚合物成分、與選自能量線硬化性之多官能單體及低聚物所組成之群中之至少一種成分的調配比，將不具有能量線硬化性之聚合物成分設為100質量份時，選自多官能單體及低聚物所組成之群中之至少一種成分較佳為10質量份～150質量份，更佳為25質量份～100質量份。As at least one component selected from the group consisting of energy-ray curable polyfunctional monomers and oligomers, the same as the aforementioned component (B) can be selected. The blending ratio of a polymer component that does not have energy ray hardenability and at least one component selected from the group consisting of energy ray hardenable polyfunctional monomers and oligomers will be a polymer that does not have energy ray hardenability When the component is 100 parts by mass, at least one component selected from the group consisting of polyfunctional monomers and oligomers is preferably 10 parts by mass to 150 parts by mass, more preferably 25 parts by mass to 100 parts by mass.

於此情形時，亦可與上述同樣地適當調配光聚合起始劑（C）及交聯劑（E）。 即，能量線硬化性黏著劑之一個形態係包含不具有能量線硬化性之聚合物成分、選自能量線硬化性之多官能單體及低聚物所組成之群中之至少一種成分、以及視需要之選自光聚合起始劑（C）及交聯劑（E）所組成之群中之至少一種成分。In this case, the photopolymerization initiator (C) and the crosslinking agent (E) can also be appropriately prepared in the same manner as described above. That is, one form of the energy ray curable adhesive includes at least one component selected from the group consisting of a polymer component that does not have energy ray curability, a polyfunctional monomer and oligomer with energy ray curability, and Optionally, at least one component selected from the group consisting of a photopolymerization initiator (C) and a crosslinking agent (E).

黏著劑層42之厚度只要可於使用保護膜形成用片3之各步驟中恰當地發揮功能，則並無特別限定。具體而言，較佳為1 μm～50 μm，更佳為2 μm～30 μm，又更佳為3 μm～20 μm。The thickness of the adhesive layer 42 is not particularly limited as long as it can function appropriately in each step of using the protective film forming sheet 3. Specifically, it is preferably 1 μm to 50 μm, more preferably 2 μm to 30 μm, and still more preferably 3 μm to 20 μm.

2.保護膜形成膜 保護膜形成膜1係用於在工件或對前述工件加工所得之加工物形成保護膜之膜。該保護膜由硬化之保護膜形成膜1所構成。作為工件，例如可列舉半導體晶圓等，作為對前述工件加工所得之加工物，例如可列舉半導體晶片，但本發明並不限定於該等。再者，於工件為半導體晶圓時，保護膜係形成於半導體晶圓之背面側（未形成有凸塊等電極之側）。2. Protective film forming film The protective film forming film 1 is a film for forming a protective film on a workpiece or a processed product obtained by processing the aforementioned workpiece. The protective film is composed of a cured protective film forming film 1. Examples of the workpiece include semiconductor wafers, and examples of the processed products obtained by processing the aforementioned workpiece include semiconductor wafers, but the present invention is not limited to these. Furthermore, when the workpiece is a semiconductor wafer, the protective film is formed on the back side of the semiconductor wafer (the side where the bumps and other electrodes are not formed).

保護膜形成膜1可為包含單層之膜，亦可為包含複數層之膜，就透光率之控制容易性及製造成本之方面而言，較佳為包含單層。The protective film forming film 1 may be a film including a single layer or a film including a plurality of layers. In terms of the ease of control of light transmittance and the manufacturing cost, it is preferable to include a single layer.

保護膜形成膜1較佳為包含硬化性材料，作為此種材料之具體例，可列舉未硬化之硬化性接著劑。於此情形時，在保護膜形成膜1上重疊半導體晶圓等工件之後，使保護膜形成膜1硬化，藉此，可使由硬化之保護膜形成膜1構成之保護膜牢固地接著於工件，且可將具有耐久性之保護膜形成於晶片等。 即，本發明一實施形態之保護膜形成用片之一個形態，係包含由未硬化之硬化性材料形成之保護膜形成膜。The protective film forming film 1 preferably contains a curable material, and as a specific example of such a material, an uncured curable adhesive can be cited. In this case, after stacking a work such as a semiconductor wafer on the protective film forming film 1, the protective film forming film 1 is hardened, whereby the protective film composed of the hardened protective film forming film 1 can be firmly attached to the work , And can form durable protective films on wafers. That is, one aspect of the protective film forming sheet according to an embodiment of the present invention includes a protective film forming film formed of an uncured curable material.

保護膜形成膜1較佳為於常溫下具有黏著性，或藉由加熱而發揮黏著性。藉此，可於如上所述般在保護膜形成膜1重疊半導體晶圓等工件時使兩者貼合。因此，可於使保護膜形成膜1硬化前確實地進行定位。The protective film forming film 1 preferably has adhesiveness at normal temperature, or exhibits adhesiveness by heating. Thereby, when the protective film formation film 1 overlaps with the workpiece|work, such as a semiconductor wafer, as mentioned above, both can be bonded together. Therefore, it is possible to reliably perform positioning before curing the protective film forming film 1.

構成具有此種特性之保護膜形成膜1之硬化性接著劑較佳為含有硬化性成分與黏合劑聚合物成分。作為硬化性成分，可使用熱硬化性成分、能量線硬化性成分、或該等之混合物，尤佳為使用熱硬化性成分。即，保護膜形成膜1較佳為由熱硬化性接著劑構成。The curable adhesive constituting the protective film forming film 1 having such characteristics preferably contains a curable component and a binder polymer component. As the curable component, a thermosetting component, an energy ray curable component, or a mixture of these can be used, and it is particularly preferable to use a thermosetting component. That is, the protective film forming film 1 is preferably composed of a thermosetting adhesive.

作為熱硬化性成分，例如可列舉：環氧樹脂、酚樹脂、三聚氰胺樹脂、尿素樹脂、聚酯樹脂、胺基甲酸酯樹脂、丙烯酸樹脂、聚醯亞胺樹脂、苯并噁嗪（benzoxazine）樹脂等及該等之混合物。該等中，可較佳地使用環氧樹脂、酚樹脂及該等之混合物。Examples of thermosetting components include epoxy resins, phenol resins, melamine resins, urea resins, polyester resins, urethane resins, acrylic resins, polyimide resins, and benzoxazines. Resins, etc. and their mixtures. Among them, epoxy resins, phenol resins, and mixtures of these can be preferably used.

環氧樹脂具有受到加熱而三維網狀化而形成牢固之覆膜的性質。作為此種環氧樹脂，可使用以往公知之各種環氧樹脂，通常分子量（式量）較佳為300～2000左右，分子量更佳為300～500。更佳為將分子量為330～400之常溫下為液狀之環氧樹脂、與分子量為400～2500、尤其是分子量為500～2000之常溫下為固體之環氧樹脂摻和而使用。另外，環氧樹脂之環氧當量較佳為50 g/eq～5000 g/eq。Epoxy resin has the property of being heated to form a three-dimensional network to form a strong film. As such an epoxy resin, conventionally known various epoxy resins can be used, and generally the molecular weight (formula weight) is preferably about 300 to 2000, and the molecular weight is more preferably 300 to 500. It is more preferable to blend and use an epoxy resin having a molecular weight of 330-400 that is liquid at room temperature and a molecular weight of 400-2500, especially an epoxy resin that is solid at room temperature with a molecular weight of 500-2000. In addition, the epoxy equivalent of the epoxy resin is preferably 50 g/eq to 5000 g/eq.

作為此種環氧樹脂，具體而言，可列舉：雙酚A、雙酚F、間苯二酚、苯基酚醛清漆、甲酚酚醛清漆等酚類之縮水甘油醚；丁二醇、聚乙二醇、聚丙二醇等醇類之縮水甘油醚；鄰苯二甲酸、間苯二甲酸、四氫鄰苯二甲酸等羧酸之縮水甘油醚；苯胺異氰尿酸酯等與氮原子鍵結之活性氫被縮水甘油基取代之縮水甘油型或烷基縮水甘油型之環氧樹脂；乙烯基環己烷二環氧化物、3,4-環氧環己基甲基-3,4-二環己烷羧酸酯、2-（3,4-環氧基）環己基-5,5-螺（3,4-環氧基）環己烷-間二噁烷等藉由使分子內之碳-碳雙鍵進行例如氧化而導入有環氧基之所謂的脂環型環氧化物。此外，亦可使用具有聯苯骨架、二環己二烯骨架、萘骨架等之環氧樹脂。As such epoxy resins, specifically, glycidyl ethers of phenols such as bisphenol A, bisphenol F, resorcinol, phenyl novolac, and cresol novolac; butylene glycol, polyethylene Glycidyl ethers of alcohols such as glycols and polypropylene glycols; glycidyl ethers of carboxylic acids such as phthalic acid, isophthalic acid and tetrahydrophthalic acid; aniline isocyanurate, etc. bonded to nitrogen atoms Glycidyl or alkyl glycidyl epoxy resin with active hydrogen substituted by glycidyl; vinyl cyclohexane diepoxide, 3,4-epoxycyclohexylmethyl-3,4-dicyclohexyl Alkyl carboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, etc. By making the carbon in the molecule- The carbon double bond is oxidized, for example, to introduce a so-called alicyclic epoxide with an epoxy group. In addition, epoxy resins having a biphenyl skeleton, a dicyclohexadiene skeleton, a naphthalene skeleton, etc. may also be used.

該等中，可較佳地使用雙酚系縮水甘油型環氧樹脂、鄰甲酚酚醛清漆型環氧樹脂及苯酚酚醛清漆型環氧樹脂。該等環氧樹脂可單獨使用1種，或者亦可組合2種以上而使用。Among these, bisphenol-based glycidyl-type epoxy resins, ortho-cresol novolac-type epoxy resins, and phenol novolac-type epoxy resins can be preferably used. These epoxy resins may be used individually by 1 type, or may be used in combination of 2 or more types.

於使用環氧樹脂時，較佳為併用熱活性型潛伏性環氧樹脂硬化劑作為助劑。所謂「熱活性型潛伏性環氧樹脂硬化劑」係在室溫不會與環氧樹脂反應，藉由特定溫度以上之加熱而活化並與環氧樹脂反應之類型之硬化劑。熱活性型潛伏性環氧樹脂硬化劑之活化方法係有：藉由利用加熱之化學反應生成活性物質（陰離子、陽離子）之方法；於室溫附近穩定地分散於環氧樹脂中，於高溫下與環氧樹脂相溶、溶解，而開始硬化反應之方法；利用分子篩封入型之硬化劑於高溫溶出而開始硬化反應之方法；利用微膠囊之方法等。When an epoxy resin is used, it is preferable to use a thermoactive latent epoxy resin hardener as an auxiliary agent. The so-called "thermally active latent epoxy resin hardener" is a type of hardener that does not react with epoxy resin at room temperature, but is activated by heating above a certain temperature and reacts with epoxy resin. The activation method of the thermally active latent epoxy resin hardener is: the method of generating active substances (anions, cations) by the chemical reaction of heating; stably dispersed in the epoxy resin near room temperature, at high temperature The method of dissolving and dissolving with epoxy resin to start the hardening reaction; the method of using molecular sieve-enclosed hardener to dissolve at high temperature to start the hardening reaction; the method of using microcapsules, etc.

作為熱活性型潛伏性環氧樹脂硬化劑之具體例，可列舉：各種鎓鹽、或二元酸二醯肼化合物、二氰二胺、胺加成物硬化劑、咪唑化合物等高熔點活性氫化合物等。該等熱活性型潛伏性環氧樹脂硬化劑可單獨使用1種，或者組合2種以上而使用。此種熱活性型潛伏性環氧樹脂硬化劑以相對於環氧樹脂100重量份而較佳為0.1重量份～20重量份、更佳為0.2重量份～10重量份、又更佳為0.3重量份～5重量份之比率使用。Specific examples of thermally active latent epoxy resin hardeners include various onium salts, or dibasic acid dihydrazine compounds, dicyandiamine, amine adduct hardeners, imidazole compounds and other high melting point active hydrogens. Compound etc. These thermally active latent epoxy resin hardeners may be used alone or in combination of two or more kinds. The thermally active latent epoxy resin hardener is preferably 0.1 part by weight to 20 parts by weight, more preferably 0.2 part by weight to 10 parts by weight, and still more preferably 0.3 part by weight relative to 100 parts by weight of epoxy resin Used in the ratio of parts to 5 parts by weight.

作為酚系樹脂，可無特別限制地使用烷基酚、多酚、萘酚等酚類與醛類之縮合物等。具體而言，可使用苯酚酚醛清漆樹脂、鄰甲酚酚醛清漆樹脂、對甲酚酚醛清漆樹脂、第三丁基苯酚酚醛清漆樹脂、二環戊二烯甲酚樹脂、聚對乙烯基苯酚樹脂、雙酚A型酚醛清漆樹脂、或該等之改質物等。As the phenol resin, condensation products of phenols and aldehydes, such as alkylphenols, polyphenols, and naphthols, can be used without particular limitation. Specifically, phenol novolak resin, ortho-cresol novolak resin, p-cresol novolak resin, tertiary butylphenol novolak resin, dicyclopentadiene cresol resin, poly(p-vinylphenol) resin, Bisphenol A-type novolac resins, or these modified products, etc.

該等酚系樹脂中所含之酚性羥基係藉由加熱而容易與上述環氧樹脂之環氧基發生加成反應，可形成耐衝擊性高之硬化物。因此，亦可併用環氧樹脂與酚系樹脂。The phenolic hydroxyl group contained in these phenolic resins easily undergo an addition reaction with the epoxy group of the epoxy resin by heating, and can form a cured product with high impact resistance. Therefore, an epoxy resin and a phenol resin can also be used together.

作為能量線硬化性成分，可列舉黏著劑層42中之具有能量線硬化性之聚合物、或選自能量線硬化性之單體及低聚物所組成之群中之至少一種成分所列舉的成分。Examples of the energy-ray curable component include at least one component selected from the group consisting of energy-ray-curable polymers in the adhesive layer 42 or energy-ray-curable monomers and oligomers. ingredient.

黏合劑聚合物成分會對保護膜形成膜1賦予適度之黏性，而可提高保護膜形成用片3之操作性。黏合劑聚合物之重量平均分子量處於通常為5萬～200萬、較佳為10萬～150萬、尤佳為20萬～100萬之範圍。若重量平均分子量過低，則保護膜形成膜1之膜形成變得不充分，若過高，則與其他成分之相溶性變差，結果會阻礙均勻之膜形成。即，若重量平均分子量為上述下限值以上，則保護膜形成膜1之膜形成充分，若為上述上限值以下，則與其他成分之相溶性良好，結果為可形成均勻之膜。作為此種黏合劑聚合物，例如可使用丙烯酸系聚合物、聚酯樹脂、苯氧基樹脂、胺基甲酸酯樹脂、聚矽氧樹脂、橡膠系聚合物等，可尤佳地使用丙烯酸系聚合物。The binder polymer component imparts moderate viscosity to the protective film forming film 1 and can improve the handling of the protective film forming sheet 3. The weight average molecular weight of the binder polymer is usually in the range of 50,000 to 2 million, preferably 100,000 to 1.5 million, and particularly preferably 200,000 to 1 million. If the weight average molecular weight is too low, the film formation of the protective film forming film 1 will become insufficient, and if it is too high, the compatibility with other components will deteriorate, and as a result, uniform film formation will be hindered. That is, if the weight average molecular weight is more than the above lower limit, the film formation of the protective film forming film 1 is sufficient, and if it is less than the above upper limit, the compatibility with other components is good, and as a result, a uniform film can be formed. As such a binder polymer, for example, acrylic polymers, polyester resins, phenoxy resins, urethane resins, silicone resins, rubber polymers, etc. can be used, and acrylic polymers can be used particularly preferably. polymer.

作為丙烯酸系聚合物，例如可列舉包含（甲基）丙烯酸酯單體與自（甲基）丙烯酸衍生物導出之結構單元的（甲基）丙烯酸酯共聚物。此處，作為（甲基）丙烯酸酯單體，可較佳地列舉烷基之碳數為1～18之（甲基）丙烯酸烷酯，具體而言，可列舉（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基）丙烯酸丁酯等。另外，作為（甲基）丙烯酸衍生物，例如可列舉（甲基）丙烯酸、（甲基）丙烯酸縮水甘油酯、（甲基）丙烯酸羥基乙酯等。Examples of acrylic polymers include (meth)acrylate copolymers containing (meth)acrylate monomers and structural units derived from (meth)acrylic acid derivatives. Here, as the (meth)acrylate monomers, alkyl (meth)acrylates having 1 to 18 carbon atoms in the alkyl group are preferably cited. Specifically, methyl (meth)acrylate, Ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, etc. In addition, examples of (meth)acrylic acid derivatives include (meth)acrylic acid, glycidyl (meth)acrylate, and hydroxyethyl (meth)acrylate.

上述中，若使用甲基丙烯酸縮水甘油酯等作為結構單元而於丙烯酸系聚合物中導入縮水甘油基，則與作為前述熱硬化性成分之環氧樹脂之相溶性提高，保護膜形成膜1之硬化後之玻璃轉移溫度（Tg）變高，而耐熱性提高。另外，上述中，若使用丙烯酸羥基乙酯等作為結構單元而於丙烯酸系聚合物導入羥基，則可控制對工件之密接性或黏著物性。Among the above, if glycidyl methacrylate or the like is used as a structural unit and a glycidyl group is introduced into an acrylic polymer, the compatibility with the epoxy resin as the thermosetting component is improved, and the protective film forming film 1 The glass transition temperature (Tg) after hardening becomes higher and the heat resistance improves. In addition, in the above, if hydroxyethyl acrylate or the like is used as a structural unit and a hydroxyl group is introduced into the acrylic polymer, it is possible to control the adhesion to the workpiece or the adhesion properties.

使用丙烯酸系聚合物作為黏合劑聚合物時，前述聚合物之重量平均分子量較佳為10萬以上，尤佳為15萬～100萬。丙烯酸系聚合物之玻璃轉移溫度通常為20℃以下，較佳為-70℃～0℃左右，於常溫（23℃）下具有黏著性。When an acrylic polymer is used as the binder polymer, the weight average molecular weight of the aforementioned polymer is preferably 100,000 or more, particularly preferably 150,000 to 1,000,000. The glass transition temperature of acrylic polymer is usually below 20°C, preferably around -70°C to 0°C, and has adhesiveness at normal temperature (23°C).

關於熱硬化性成分與黏合劑聚合物成分之調配比率，當將黏合劑聚合物成分設為100重量份時，熱硬化性成分之調配量較佳為50重量份～1500重量份，更佳為70重量份～1000重量份，尤佳為80重量份～800重量份。若以此種比率調配熱硬化性成分與黏合劑聚合物成分，則於硬化前顯示出適度之黏性，可穩定地進行貼附作業，且於硬化後獲得覆膜強度優異之保護膜。Regarding the blending ratio of the thermosetting component and the adhesive polymer component, when the adhesive polymer component is 100 parts by weight, the blending amount of the thermosetting component is preferably 50 parts by weight to 1500 parts by weight, more preferably 70 parts by weight to 1000 parts by weight, particularly preferably 80 parts by weight to 800 parts by weight. If the thermosetting component and the adhesive polymer component are blended at such a ratio, it will show a moderate viscosity before curing, can stably perform the sticking operation, and obtain a protective film with excellent film strength after curing.

保護膜形成膜1亦可進一步含有選自著色劑及填料所組成之群中之至少一種成分。The protective film forming film 1 may further contain at least one component selected from the group consisting of a colorant and a filler.

作為著色劑，例如可使用無機系顏料、有機系顏料、有機系染料等公知之著色劑，就提高透光率之控制性之觀點而言，著色劑較佳為含有有機系之著色劑。就提高著色劑之化學穩定性（具體而言可例示難溶出、難發生移色、經時變化少之性質）之觀點而言，著色劑較佳為包含顏料之著色劑。As the coloring agent, for example, well-known coloring agents such as inorganic pigments, organic pigments, and organic dyes can be used. From the viewpoint of improving the controllability of light transmittance, the coloring agent preferably contains an organic coloring agent. From the viewpoint of improving the chemical stability of the colorant (specifically, it can exemplify the properties of being hard to dissolve, hard to change color, and less change over time), the coloring agent is preferably a coloring agent containing a pigment.

作為填料，可列舉結晶二氧化矽、熔融二氧化矽、合成二氧化矽等二氧化矽、或氧化鋁、玻璃球等無機填料。其中，較佳為二氧化矽，更佳為合成二氧化矽，尤佳為將成為半導體裝置之誤動作之主要原因的α線之線源盡可能去除之類型之合成二氧化矽。作為填料之形狀，可列舉球形、針狀、不定形等，較佳為球形，尤佳為圓球形。若填料為球形或圓球形，則不易產生光線之漫反射，而易於控制保護膜形成膜1之透光率之光譜圖譜。 作為選自著色劑及填料所組成之群中之至少一種成分之含量，相對於保護膜形成膜整體之質量，較佳為5質量%～75質量%。 填料之平均粒徑較佳為0.005 μm～20 μm。Examples of the filler include silica such as crystalline silica, fused silica, and synthetic silica, or inorganic fillers such as alumina and glass balls. Among them, silicon dioxide is preferable, and synthetic silicon dioxide is more preferable, and particularly preferable is a type of synthetic silicon dioxide that removes as much as possible the line source of the alpha line that is the main cause of the malfunction of the semiconductor device. As the shape of the filler, spherical, needle-like, amorphous, etc. can be cited, and spherical is preferred, and spherical is particularly preferred. If the filler is spherical or spherical, it is not easy to produce diffuse reflection of light, and it is easy to control the light transmittance spectrum of the protective film forming film 1. The content of at least one component selected from the group consisting of colorants and fillers is preferably 5% by mass to 75% by mass relative to the mass of the entire protective film forming film. The average particle size of the filler is preferably 0.005 μm to 20 μm.

另外，保護膜形成膜1亦可含有偶合劑。藉由含有偶合劑，於保護膜形成膜1之硬化後，不會損害保護膜之耐熱性，且可使前述保護膜與工件之接著性及密接性提高，並且進一步亦可使耐水性（耐濕熱性）提高。作為偶合劑，就其通用性及成本優勢等而言，較佳為矽烷偶合劑。In addition, the protective film forming film 1 may contain a coupling agent. By containing the coupling agent, after the curing of the protective film forming film 1, the heat resistance of the protective film will not be impaired, and the adhesion and adhesion between the protective film and the workpiece can be improved, and the water resistance (resistant Humidity) improved. As the coupling agent, a silane coupling agent is preferred in terms of its versatility and cost advantage.

作為矽烷偶合劑，例如可列舉：γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基甲基二乙氧基矽烷、β-（3,4-環氧環己基）乙基三甲氧基矽烷、γ-（甲基丙烯醯氧基丙基）三甲氧基矽烷、γ-胺基丙基三甲氧基矽烷、N-6-（胺基乙基）-γ-胺基丙基三甲氧基矽烷、N-6-（胺基乙基）-γ-胺基丙基甲基二乙氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷、γ-脲基丙基三乙氧基矽烷、γ-巰基丙基三甲氧基矽烷、γ-巰基丙基甲基二甲氧基矽烷、雙（3-三乙氧基矽基丙基）四硫化物、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、咪唑矽烷等。該等中，較佳為γ-縮水甘油氧基丙基三甲氧基矽烷。該等可單獨使用1種，或者混合2種以上而使用。 於保護膜形成膜1含有黏合劑聚合物成分及硬化性成分之情形，當將黏合劑聚合物成分及硬化性成分之質量份之合計設為100質量份時，偶合劑之含量較佳為0.1質量份～5質量份。As the silane coupling agent, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl) Ethyl trimethoxysilane, γ-(methacryloxypropyl) trimethoxysilane, γ-aminopropyl trimethoxysilane, N-6-(aminoethyl)-γ-amino Propyl trimethoxysilane, N-6-(aminoethyl)-γ-aminopropylmethyl diethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ- Ureapropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl) tetrasulfide, Methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, imidazolesilane, etc. Among them, γ-glycidoxypropyltrimethoxysilane is preferred. These can be used individually by 1 type, or in mixture of 2 or more types. In the case where the protective film forming film 1 contains a binder polymer component and a curable component, when the total mass parts of the binder polymer component and the curable component is 100 parts by mass, the content of the coupling agent is preferably 0.1 Parts by mass ~ 5 parts by mass.

為了調節硬化前之凝聚力，保護膜形成膜1亦可含有有機多元異氰酸酯化合物、有機多元亞胺化合物、有機金屬螯合物等交聯劑。另外，為了抑制靜電並使晶片之可靠性提高，保護膜形成膜1亦可含有抗靜電劑。又，為了提高保護膜之阻燃性能，使作為封裝之可靠性提高，保護膜形成膜1亦可含有磷酸化合物、溴化合物、磷系化合物等阻燃劑。 即，保護膜形成膜1之一個形態係包含硬化性成分、黏合劑聚合物成分、以及視需要之從選自著色劑及填料所組成之群中之至少一種成分、偶合劑、交聯劑、抗靜電劑、及阻燃劑所組成之群中選擇的至少一種成分。In order to adjust the cohesive force before curing, the protective film forming film 1 may also contain a crosslinking agent such as an organic polyisocyanate compound, an organic polyimine compound, and an organic metal chelate compound. In addition, in order to suppress static electricity and improve the reliability of the wafer, the protective film forming film 1 may contain an antistatic agent. In addition, in order to improve the flame retardancy of the protective film and improve the reliability as a package, the protective film forming film 1 may also contain flame retardants such as phosphoric acid compounds, bromine compounds, and phosphorus compounds. That is, one form of the protective film forming film 1 includes a curable component, a binder polymer component, and optionally at least one component selected from the group consisting of a colorant and a filler, a coupling agent, a crosslinking agent, At least one component selected from the group consisting of antistatic agents and flame retardants.

為了使作為保護膜之功能有效地發揮，保護膜形成膜1之厚度較佳為3 μm～300 μm，更佳為5 μm～200 μm，尤佳為7 μm～100 μm。In order to effectively perform the function as a protective film, the thickness of the protective film forming film 1 is preferably 3 μm to 300 μm, more preferably 5 μm to 200 μm, and particularly preferably 7 μm to 100 μm.

3.保護膜 由本發明一實施形態之保護膜形成膜1形成之保護膜具備以下特性。3. Protective film The protective film formed from the protective film forming film 1 of one embodiment of the present invention has the following characteristics.

保護膜於50℃之斷裂應變為0.1%以上且20%以下。藉由使該斷裂應變為20%以下，於在後述之條件下使第1支撐片4伸長（延伸）時，可恰當地分割第1支撐片4所具備之保護膜。若50℃之斷裂應變超過20%，則保護膜之分割容易變得不恰當，具體而言，於分割部分中容易產生形成保護膜之材料局部成為絲狀而未分割之現象（本說明書中稱為「拉絲現象」）。就更穩定地達成保護膜之恰當分割之觀點而言，保護膜之50℃之斷裂應變較佳為0.2%以上且15%以下，更佳為0.3%以上且13%以下，尤佳為0.5%以上且10%以下。 再者，保護膜之「50℃之斷裂應變」可藉由後述試驗例所記載之方法進行測定。The breaking strain of the protective film at 50°C is 0.1% or more and 20% or less. By setting the breaking strain to 20% or less, when the first support sheet 4 is stretched (stretched) under the conditions described below, the protective film included in the first support sheet 4 can be appropriately divided. If the breaking strain at 50°C exceeds 20%, the division of the protective film is likely to become inappropriate. Specifically, the material forming the protective film is likely to become filamentous in the divided part without being divided (referred to in this manual) Is the "drawing phenomenon"). From the viewpoint of achieving proper division of the protective film more stably, the breaking strain at 50°C of the protective film is preferably 0.2% or more and 15% or less, more preferably 0.3% or more and 13% or less, and particularly preferably 0.5% Above and below 10%. In addition, the "breaking strain at 50°C" of the protective film can be measured by the method described in the test example described later.

保護膜之損耗正切之峰值溫度T1處於25℃至60℃之範圍內。藉由使損耗正切之峰值溫度T1處於上述範圍內，於後述條件（具體而言為第1分割步驟中之使第1支撐片4伸長時之保護膜的溫度T2保持在40℃至70℃之範圍內）下使第1支撐片4伸長（延伸）時，可恰當地分割第1支撐片4所具備之保護膜。於溫度T1過低時，保護膜會軟質化，保護膜之50℃之斷裂應變容易超過20%。於溫度T1過高時，保護膜會硬質化，在使第1支撐片4延伸時難以恰當地進行保護膜之分割。就更穩定地達成保護膜之恰當分割之觀點而言，溫度T2較佳為損耗正切之峰值溫度T1以上。 再者，保護膜之「損耗正切之峰值溫度」可藉由後述試驗例所記載之方法進行測定。The peak temperature T1 of the loss tangent of the protective film is in the range of 25°C to 60°C. By keeping the peak temperature T1 of the loss tangent within the above-mentioned range, the temperature T2 of the protective film when the first support sheet 4 is stretched in the first division step is maintained at 40°C to 70°C under the conditions described later When the first support sheet 4 is stretched (extended) in the range), the protective film provided in the first support sheet 4 can be appropriately divided. When the temperature T1 is too low, the protective film will soften, and the breaking strain of the protective film at 50°C will easily exceed 20%. When the temperature T1 is too high, the protective film hardens, and it is difficult to properly divide the protective film when the first support sheet 4 is stretched. From the viewpoint of more stably achieving proper division of the protective film, the temperature T2 is preferably higher than the peak temperature T1 of the loss tangent. Furthermore, the "peak temperature of loss tangent" of the protective film can be measured by the method described in the test example described later.

保護膜於25℃之儲存模數較佳為3.0×109 Pa以上且5.0×1011 Pa以下，更佳為5.0×109 Pa以上且1.0×1011 Pa以下。藉由使保護膜之25℃之儲存模數為3.0×109 Pa以上，於使附有保護膜之半導體晶片自第1支撐片4分離時，不易產生保護膜附有瑕疵之不良情形。The storage modulus of the protective film at 25°C is preferably 3.0×10 9 Pa or more and 5.0×10 11 Pa or less, and more preferably 5.0×10 9 Pa or more and 1.0×10 11 Pa or less. By making the storage modulus of the protective film at 25°C of 3.0×10 9 Pa or more, when the semiconductor chip with the protective film is separated from the first support sheet 4, it is unlikely that the protective film is defective.

保護膜於25℃之損耗正切較佳為0.01以上且0.4以下。藉由使保護膜之25℃之損耗正切為0.4以下，於使附有保護膜之半導體晶片自第1支撐片4分離時，不易產生保護膜有瑕疵之不良情形。保護膜之25℃之損耗正切更佳為0.03以上且0.3以下，尤佳為0.05以上且0.2以下。 再者，保護膜之「25℃之儲存模數」及「25℃之損耗正切」可藉由後述試驗例所記載之方法進行測定。The loss tangent of the protective film at 25°C is preferably 0.01 or more and 0.4 or less. By setting the loss tangent of the protective film at 25°C to 0.4 or less, when the semiconductor chip with the protective film is separated from the first support sheet 4, the defect of the protective film is less likely to occur. The loss tangent of the protective film at 25°C is more preferably 0.03 or more and 0.3 or less, and particularly preferably 0.05 or more and 0.2 or less. Furthermore, the "storage modulus at 25°C" and the "loss tangent at 25°C" of the protective film can be measured by the method described in the test example described later.

保護膜之波長為1064 nm之透光率較佳為40%以上且100%以下。藉由使保護膜之波長為1064 nm之透光率為40%以上，可讓用於隱形切割之雷射光有效率地到達半導體晶圓等工件內。就穩定地使雷射光有效率地到達半導體晶圓的觀點而言，保護膜之波長為1064 nm之透光率較佳為50%以上且99.9%以下，更佳為60%以上且99.5%以下。The light transmittance of the protective film with a wavelength of 1064 nm is preferably 40% or more and 100% or less. By making the protective film with a wavelength of 1064 nm and a light transmittance of more than 40%, the laser light used for invisible cutting can efficiently reach the semiconductor wafer and other workpieces. From the viewpoint of stably allowing the laser light to reach the semiconductor wafer efficiently, the transmittance of the protective film with a wavelength of 1064 nm is preferably 50% or more and 99.9% or less, more preferably 60% or more and 99.5% or less .

保護膜於50℃之斷裂應力較佳為1.0×103 Pa以上且2.0×107 Pa以下。藉由使該斷裂應力為2.0×107 Pa以下，於後述條件下使第1支撐片4伸長（延伸）時，可恰當地分割第1支撐片4所具備之保護膜。就更穩定地達成保護膜之恰當分割之觀點而言，保護膜之50℃之斷裂應力更佳為5.0×103 Pa以上且1.9×107 Pa以下，更佳為5.0×103 Pa以上且1.8×107 Pa以下，又更佳為8.0×103 Pa以上且1.7×107 Pa以下。 再者，保護膜之「50℃之斷裂應力」可藉由後述試驗例所記載之方法進行測定。The breaking stress of the protective film at 50°C is preferably 1.0×10 3 Pa or more and 2.0×10 7 Pa or less. By setting the breaking stress to 2.0×10 7 Pa or less, when the first support sheet 4 is stretched (stretched) under the conditions described later, the protective film included in the first support sheet 4 can be appropriately divided. From the viewpoint of achieving proper division of the protective film more stably, the breaking stress at 50°C of the protective film is more preferably 5.0×10 3 Pa or more and 1.9×10 7 Pa or less, and more preferably 5.0×10 3 Pa or more and 1.8×10 7 Pa or less, and more preferably 8.0×10 3 Pa or more and 1.7×10 7 Pa or less. In addition, the "breaking stress at 50°C" of the protective film can be measured by the method described in the test example described later.

即，本發明之保護膜形成用片之一個形態係具有前述保護膜形成膜，且前述保護膜形成膜具有以下特性：50℃之斷裂應變為0.1%以上且20%以下，且損耗正切之峰值溫度T1處於25℃至60℃之範圍內。 前述保護膜形成膜可進一步具有以下之至少一種特性：25℃之儲存模數為3.0×109 Pa以上且5.0×1011 Pa以下；25℃之損耗正切為0.01以上且0.4以下；波長為1064 nm之透光率為40%以上且100%以下；50℃之斷裂應力為1.0×103 Pa以上且2.0×107 Pa以下。 再者，此處所謂之「特性」係指保護膜形成膜之化學特性或物理化學特性。That is, one form of the protective film forming sheet of the present invention has the aforementioned protective film forming film, and the aforementioned protective film forming film has the following characteristics: the breaking strain at 50°C is 0.1% or more and 20% or less, and the peak loss tangent The temperature T1 is in the range of 25°C to 60°C. The aforementioned protective film forming film may further have at least one of the following characteristics: the storage modulus at 25°C is 3.0×10 9 Pa or more and 5.0×10 11 Pa or less; the loss tangent at 25°C is 0.01 or more and 0.4 or less; and the wavelength is 1064 The light transmittance of nm is above 40% and below 100%; the breaking stress at 50°C is above 1.0×10 3 Pa and below 2.0×10 7 Pa. Furthermore, the "characteristics" referred to herein refer to the chemical properties or physicochemical properties of the protective film forming film.

4.治具用黏著劑層 作為構成治具用黏著劑層5之黏著劑，較佳為具有所需之黏著力及再剝離性之黏著劑，例如可使用丙烯酸系黏著劑、橡膠系黏著劑、聚矽氧系黏著劑、胺基甲酸酯系黏著劑、聚酯系黏著劑、聚乙烯醚系黏著劑等。該等中，較佳為與環狀架等治具之密接性高，於切割步驟等中可有效抑制保護膜形成用片3自環狀架等剝落的丙烯酸系黏著劑。再者，亦可於治具用黏著劑層5之厚度方向中介置作為芯材之基材。4. Adhesive layer for jig As the adhesive constituting the adhesive layer 5 for jigs, an adhesive having the required adhesive force and releasability is preferable. For example, acrylic adhesives, rubber-based adhesives, silicone-based adhesives, Urethane-based adhesives, polyester-based adhesives, polyvinyl ether-based adhesives, etc. Among these, it is preferable that the adhesiveness with a jig such as a ring frame is high, and it is an acrylic adhesive that can effectively prevent the protective film forming sheet 3 from peeling off the ring frame or the like in a cutting step or the like. Furthermore, it can also be used as a base material of the core material interposed in the thickness direction of the jig adhesive layer 5.

另一方面，就相對於環狀架等治具之接著性之觀點而言，治具用黏著劑層5之厚度較佳為5 μm～200 μm，更佳為10 μm～100 μm。On the other hand, from the viewpoint of adhesion to jigs such as a ring frame, the thickness of the jig adhesive layer 5 is preferably 5 μm to 200 μm, and more preferably 10 μm to 100 μm.

5.剝離片 本發明一實施形態之保護膜形成用片3的剝離片6，係於至使用保護膜形成用片3之前的期間，對保護膜形成膜1及治具用黏著劑層5進行保護。5. Peel off sheet The peeling sheet 6 of the protective film forming sheet 3 of one embodiment of the present invention protects the protective film forming film 1 and the adhesive layer 5 for jigs until the protective film forming sheet 3 is used.

剝離片6之構成為任意，可例示利用剝離劑等對塑膠膜進行剝離處理而成之片。作為塑膠膜之具體例，可列舉：聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯等聚酯膜；及聚丙烯或聚乙烯等聚烯烴膜。作為剝離劑，可使用聚矽氧系剝離劑、氟系剝離劑、長鏈烷基系剝離劑等，該等中較佳為廉價且可獲得穩定性能之聚矽氧系剝離劑。剝離片6之厚度並無特別限制，通常為20 μm～250 μm左右。The configuration of the release sheet 6 is arbitrary, and a sheet obtained by peeling a plastic film with a release agent or the like can be exemplified. Specific examples of plastic films include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; and polyolefin films such as polypropylene or polyethylene. . As the release agent, a silicone-based release agent, a fluorine-based release agent, a long-chain alkyl-based release agent, etc. can be used. Among these, a silicone-based release agent that is inexpensive and can obtain stable performance is preferred. The thickness of the release sheet 6 is not particularly limited, but is usually about 20 μm to 250 μm.

6.保護膜形成用片之製造方法 保護膜形成用片3較佳為分別製作包含保護膜形成膜1之積層體（本說明書中稱為「積層體I」）及包含第1支撐片4之積層體（本說明書中稱為「積層體II」）之後，使用積層體I及積層體II，將保護膜形成膜1與第1支撐片4積層而製造，但並不限定於此。6. Manufacturing method of protective film forming sheet The sheet 3 for forming a protective film is preferably made of a laminate including the protective film forming film 1 (referred to as "layer I" in this specification) and a laminate including the first support sheet 4 (referred to as "laminated body I" in this specification). After that, the layered body I and the layered body II are used to laminate the protective film forming film 1 and the first support sheet 4 to produce, but it is not limited to this.

製造積層體I時，於第1剝離片之剝離面形成保護膜形成膜1。具體而言，調製含有構成保護膜形成膜1之硬化性接著劑、及視需要進一步含有溶劑之保護膜形成膜用之塗佈劑，利用輥式塗佈機、刀式塗佈機、輥刀式塗佈機、氣刀式塗佈機、模具塗佈機、棒式塗佈機、凹版塗佈機、簾幕式塗佈機等塗佈機，於第1剝離片之剝離面塗佈前述塗佈劑並使其乾燥，而將保護膜形成膜1形成於第1剝離片之剝離面。接著，於保護膜形成膜1之露出面重疊第2剝離片之剝離面並壓接，而獲得由兩片剝離片夾著保護膜形成膜1而成之積層體（積層體I）。When manufacturing the laminated body I, the protective film formation film 1 is formed on the peeling surface of the 1st peeling sheet. Specifically, a coating agent for a protective film forming film containing a curable adhesive constituting the protective film forming film 1 and a solvent further containing a coating agent for the protective film forming film is prepared using a roll coater, a knife coater, and a roll knife Coater, air knife coater, die coater, bar coater, gravure coater, curtain coater and other coating machines, apply the aforementioned on the release surface of the first release sheet The coating agent is applied and dried to form the protective film forming film 1 on the release surface of the first release sheet. Next, the release surface of the second release sheet was superimposed on the exposed surface of the protective film forming film 1 and pressure-bonded to obtain a laminate (laminate I) in which the protective film forming film 1 was sandwiched between two release sheets.

該積層體I可視需要實施半切（half cut），使保護膜形成膜1（及第2剝離片）成為所需之形狀，例如圓形等。於此情形，半切所產生之保護膜形成膜1及第2剝離片之多餘部分適當去除即可。The layered body I may be subjected to a half cut as necessary to make the protective film forming film 1 (and the second release sheet) into a desired shape, such as a circular shape. In this case, the excess parts of the protective film forming film 1 and the second release sheet generated by the half-cutting may be appropriately removed.

另一方面，當製造積層體II時，於第3剝離片之剝離面塗佈含有構成黏著劑層42之黏著劑、及視需要進一步含有溶劑之黏著劑層用之塗佈劑，並使其乾燥，而於第3剝離片之剝離面形成黏著劑層42。之後，於黏著劑層42之露出面壓接基材41，而獲得包括含有基材41及黏著劑層42之第1支撐片4、與第3剝離片之積層體（積層體II）。On the other hand, when the laminated body II is produced, the release surface of the third release sheet is coated with an adhesive that constitutes the adhesive layer 42 and, if necessary, a coating agent for the adhesive layer that further contains a solvent. After drying, the adhesive layer 42 is formed on the release surface of the third release sheet. After that, the substrate 41 is pressure-bonded to the exposed surface of the adhesive layer 42 to obtain a laminate (layered product II) including the first support sheet 4 containing the substrate 41 and the adhesive layer 42 and the third release sheet.

此處，於黏著劑層42包含能量線硬化性黏著劑時，可在該階段對黏著劑層42照射能量線而使黏著劑層42硬化，亦可在積層保護膜形成膜1之後照射能量線而使黏著劑層42硬化。又，於在積層保護膜形成膜1之後使黏著劑層42硬化時，可在切割步驟前使黏著劑層42硬化，亦可在切割步驟後使黏著劑層42硬化。Here, when the adhesive layer 42 contains an energy-ray curable adhesive, the adhesive layer 42 may be irradiated with energy rays at this stage to harden the adhesive layer 42, or the energy ray may be irradiated after the laminated protective film is formed to form the film 1. The adhesive layer 42 is hardened. In addition, when the adhesive layer 42 is hardened after the protective film is laminated to form the film 1, the adhesive layer 42 may be hardened before the cutting step, or the adhesive layer 42 may be hardened after the cutting step.

作為能量線，通常使用紫外線、電子束等。能量線之照射量根據能量線之種類而不同，於例如紫外線時，以光量計較佳為50 mJ/cm2 ～1000 mJ/cm2 ，更佳為100 mJ/cm2 ～500 mJ/cm2 。另外，於電子束時，較佳為10 krad～1000 krad左右。As energy rays, ultraviolet rays, electron beams, etc. are generally used. The irradiation amount of the energy ray differs according to the type of the energy ray. For example, in the case of ultraviolet rays, the light quantity is preferably 50 mJ/cm 2 ～1000 mJ/cm 2 , more preferably 100 mJ/cm 2 ～500 mJ/cm 2 . In addition, in the case of an electron beam, it is preferably about 10 krad to 1000 krad.

如此獲得積層體I及積層體II後，將積層體I中之第2剝離片剝離，並且將積層體II中之第3剝離片剝離，將積層體I露出之保護膜形成膜1與積層體II露出之第1支撐片4之黏著劑層42重疊並壓接。第1支撐片4亦可視需要進行半切，而成為所需之形狀，例如具有較保護膜形成膜1大之直徑之圓形等。於此情形時，藉由半切而產生之第1支撐片4之多餘部分適當去除即可。After the laminate I and the laminate II are obtained in this way, the second release sheet in the laminate I is peeled off, and the third release sheet in the laminate II is peeled, and the protective film forming film 1 and the laminate are exposed from the laminate I The adhesive layer 42 of the first supporting sheet 4 exposed by II is overlapped and crimped. The first supporting sheet 4 can also be half-cut as needed to become a desired shape, such as a circle having a larger diameter than the protective film forming film 1. In this case, the excess part of the first support sheet 4 produced by half-cutting can be appropriately removed.

如此而獲得保護膜形成用片3，其包含：第1支撐片4，係於基材41上積層黏著劑層42而成；保護膜形成膜1，係積層於第1支撐片4中積層有黏著劑層42之側；及第1剝離片，其積層於保護膜形成膜1中與面對第1支撐片4之面為相反側之面。最後，將第1剝離片剝離之後，於保護膜形成膜1中與面對第1支撐片4之面為相反側之面的周緣部，形成治具用黏著劑層5。治具用黏著劑層5亦可藉由與上述黏著劑層42相同之方法進行塗佈而形成。Thus, a protective film forming sheet 3 is obtained, which includes: a first support sheet 4 formed by laminating an adhesive layer 42 on a base material 41; and a protective film forming film 1 formed by laminating an adhesive layer on the first support sheet 4 The side of the adhesive layer 42; and the first release sheet, which is laminated in the protective film forming film 1 and the surface facing the first support sheet 4 is the opposite side. Finally, after peeling the first release sheet, the adhesive layer 5 for jigs is formed on the peripheral edge portion of the surface opposite to the surface facing the first support sheet 4 in the protective film forming film 1. The adhesive layer 5 for jigs can also be formed by applying the same method as the adhesive layer 42 described above.

7.保護膜形成用片之使用方法 以下，作為一例說明使用本發明一實施形態之保護膜形成用片3，而由作為工件之半導體晶圓製造附有保護膜之晶片的方法。7. How to use the protective film forming sheet Hereinafter, as an example, a method of manufacturing a protective film-attached wafer from a semiconductor wafer as a workpiece using the protective film forming sheet 3 according to an embodiment of the present invention will be described.

（1）第1貼附步驟 首先，使上述本發明一實施形態之保護膜形成用片3所具備之保護膜形成膜1中與面對第1支撐片4之面為相反側之面露出。圖1所示之保護膜形成用片3係如圖2所示，將剝離片6剝離即可。(1) The first attachment step First, the surface of the protective film forming film 1 included in the protective film forming sheet 3 of the one embodiment of the present invention that is opposite to the surface facing the first support sheet 4 is exposed. The protective film forming sheet 3 shown in FIG. 1 is as shown in FIG. 2, and the release sheet 6 may be peeled off.

接著，將露出之上述面貼附於作為工件之半導體晶圓7之一面，具體而言係貼附於與電路形成面為相反側之面（背面），而獲得具備保護膜形成用片3與工件1之第1積層體10（圖3）。圖3所示之第1積層體10進一步具備治具用黏著劑層5及環狀架8。如前所述，治具用接著劑層5為保護膜形成用片3之一要件，於第1貼附步驟中，在將保護膜形成用片3之保護膜形成膜1貼附於半導體晶圓7時，將保護膜形成用片3之治具用接著劑層5貼附於環狀架8即可。 即，第1貼附步驟之一個形態包括：使本發明一實施形態之保護膜形成用片所具備之保護膜形成膜中與面對第1支撐片之面為相反側之面露出；及將前述露出之面貼附於工件之一面，而獲得具備前述保護膜形成用片與前述工件之第1積層體。 加熱時間及加熱溫度根據構成膜之材料而不同，較佳為例如於90℃～170℃加熱0.5小時～5小時。Next, the exposed surface is attached to one surface of the semiconductor wafer 7 as a work, specifically attached to the surface (back) opposite to the circuit formation surface, to obtain a protective film forming sheet 3 and The first laminate 10 of the work 1 (Figure 3). The first laminated body 10 shown in FIG. 3 further includes an adhesive layer 5 for jigs and a ring frame 8. As mentioned above, the adhesive layer 5 for jigs is an essential element of the protective film forming sheet 3. In the first attaching step, the protective film forming film 1 of the protective film forming sheet 3 is attached to the semiconductor crystal. In the case of circle 7, the jig adhesive layer 5 of the protective film forming sheet 3 may be attached to the ring frame 8. That is, one aspect of the first attaching step includes exposing the surface of the protective film forming film included in the protective film forming sheet of one embodiment of the present invention that is opposite to the surface facing the first support sheet; and The exposed surface is attached to one surface of the workpiece to obtain a first laminate including the sheet for forming a protective film and the workpiece. The heating time and the heating temperature vary depending on the material constituting the film, but it is preferably, for example, heating at 90°C to 170°C for 0.5 hour to 5 hours.

（2）第1硬化步驟 使藉由第1貼附步驟而獲得之第1積層體10之保護膜形成用片3所具備的保護膜形成膜1硬化，而獲得保護膜。用於獲得保護膜之硬化條件係根據構成保護膜形成膜1之材料而適當設定。於保護膜形成膜1為熱硬化性接著劑時，在特定溫度下將保護膜形成膜1加熱恰當之時間即可。另外，於保護膜形成膜1並非熱硬化性接著劑時，另行實施加熱處理。 即，第1硬化步驟之一個形態係包括藉由使前述第1積層體中之保護膜形成膜硬化，而獲得保護膜。(2) The first hardening step The protective film forming film 1 included in the protective film forming sheet 3 of the first laminate 10 obtained by the first bonding step is cured to obtain a protective film. The curing conditions for obtaining the protective film are appropriately set according to the material constituting the protective film forming film 1. When the protective film forming film 1 is a thermosetting adhesive, the protective film forming film 1 may be heated at a specific temperature for an appropriate time. In addition, when the protective film forming film 1 is not a thermosetting adhesive, heat treatment is separately performed. That is, one aspect of the first curing step includes obtaining a protective film by curing the protective film forming film in the first laminate.

（3）第1分割步驟 於將經過前述第1硬化步驟之第1積層體10之保護膜形成用片3所具備的保護膜之溫度T2保持在40℃至70℃之範圍內之狀態下，使保護膜形成用片3所具備之第1支撐片4伸長（延伸），而將保護膜與半導體晶圓7一起分割。結果如圖4所示般獲得第2積層體20，係於第1支撐片4之一面上，配置有將半導體晶圓7與保護膜之積層體以於厚度方向產生切割面的方式分割而成之複數（例如為2～20,000）個附有保護膜之晶片9。 即，第1分割步驟之一個形態包括：於將經過前述第1硬化步驟之前述第1積層體中前述保護膜之溫度T2保持在40℃至70℃之範圍內的狀態下，使前述第1支撐片伸長，將前述工件與前述保護膜之積層體分割，藉此獲得於前述第1支撐片之一面上配置有複數個附有保護膜之晶片的第2積層體。(3) The first division step The protective film forming sheet 3 is maintained in a state where the temperature T2 of the protective film included in the protective film forming sheet 3 of the first laminate 10 after the first curing step is maintained in the range of 40°C to 70°C The provided first support sheet 4 is extended (stretched), and the protective film is divided together with the semiconductor wafer 7. As a result, as shown in FIG. 4, a second laminated body 20 is obtained, which is formed on one surface of the first support sheet 4, and the laminated body of the semiconductor wafer 7 and the protective film is arranged so as to produce a cut surface in the thickness direction. The plural (for example, 2～20,000) chip 9 with protective film. That is, one aspect of the first dividing step includes: maintaining the temperature T2 of the protective film in the first laminate after the first curing step in the range of 40°C to 70°C, and making the first The support sheet is stretched, and the laminate of the work and the protective film is divided, thereby obtaining a second laminate in which a plurality of wafers with protective films are arranged on one surface of the first support sheet.

使第1支撐片4伸長之方法並無限定。可如圖4所示，自第1支撐片4中之與與面對環狀架8之面相反之面側壓抵環狀之構件R，且使環狀架8與環狀之構件R之鉛垂方向之相對位置變化，藉此使第1支撐片4伸長。即，藉由前述伸長而於支撐片4產生之應力中，係包含與水平方向或半導體晶圓7之背面平行之方向的向量。The method of extending the first support sheet 4 is not limited. As shown in FIG. 4, the ring-shaped member R can be pressed from the side of the first support piece 4 opposite to the surface facing the ring frame 8, and the ring frame 8 and the ring-shaped member R The relative position in the vertical direction changes, thereby extending the first support piece 4. That is, the stress generated in the support sheet 4 by the aforementioned elongation includes a vector in a direction parallel to the horizontal direction or the back surface of the semiconductor wafer 7.

通常，進行第1支撐片4之延伸時，位於第1支撐片4與半導體晶圓7之間的構件為保護膜形成膜1。保護膜形成膜1通常由可藉由硬化而形成保護膜之材料，即硬化性材料構成，其典型例為未硬化之硬化性接著劑。此種材料被賦予拉伸力時，直至斷裂之前的變形量（斷裂應變）大，有使第1支撐片4伸長（延伸）亦無法分割之情形。因此，於第1支撐片4之延伸時，係將保護膜形成膜1冷卻到0℃至-20℃左右（具體而言，通常係藉由將第1積層體10冷卻而達成），而使保護膜形成膜1之斷裂應變降低。然而，通常與加熱相比，進行冷卻需要相對昂貴之冷卻設備，且冷卻所需之能量較加熱所需之能量多。因此，將保護膜形成膜1冷卻，通常為將第1積層體10冷卻，會導致附有保護膜之晶片之製造方法中之初期投資及運轉成本增大。Generally, when the first supporting sheet 4 is extended, the member located between the first supporting sheet 4 and the semiconductor wafer 7 is the protective film forming film 1. The protective film forming film 1 is generally composed of a material that can form a protective film by curing, that is, a curable material, and a typical example thereof is an uncured curable adhesive. When such a material is given a tensile force, the amount of deformation (breaking strain) before breaking is large, and the first support sheet 4 may be stretched (stretched) without being divided. Therefore, when the first support sheet 4 is stretched, the protective film forming film 1 is cooled to about 0°C to -20°C (specifically, it is usually achieved by cooling the first laminated body 10), so that The breaking strain of the protective film forming film 1 is reduced. However, generally compared with heating, cooling requires relatively expensive cooling equipment, and the energy required for cooling is greater than that for heating. Therefore, cooling the protective film forming film 1 usually means cooling the first layered body 10, which increases the initial investment and operating costs in the method of manufacturing a wafer with a protective film.

與此相對，本發明一實施形態之附有保護膜之晶片之製造方法中，進行第1支撐片4之延伸時位於第1支撐片4與半導體晶圓7之間的構件為保護膜。由於保護膜係保護膜形成膜1硬化而獲得，故其斷裂應變較保護膜形成膜1之斷裂應變低。因此，不易產生起因於斷裂應變之分割不良。然而，由於保護膜為已硬化之材料，故有斷裂應力變高之情形，有因斷裂應力高而產生分割不良之可能性。因此，本發明一實施形態之附有保護膜之晶片之製造方法中，於第1支撐片4之延伸時，係設為將保護膜之溫度T2保持在40℃至70℃之範圍內之狀態。In contrast, in the method of manufacturing a chip with a protective film according to an embodiment of the present invention, the member located between the first support sheet 4 and the semiconductor wafer 7 when the first support sheet 4 is extended is a protective film. Since the protective film is obtained by curing the protective film forming film 1, its breaking strain is lower than that of the protective film forming film 1. Therefore, it is not easy to produce segmentation failure due to fracture strain. However, since the protective film is a hardened material, the fracture stress may increase, and there may be a possibility of poor segmentation due to the high fracture stress. Therefore, in the method of manufacturing a chip with a protective film according to an embodiment of the present invention, when the first support sheet 4 is stretched, the temperature T2 of the protective film is maintained in the range of 40°C to 70°C. .

即，與以往之冷延伸相反地進行熱延伸，藉此而使保護膜產生分割不良之可能性降低。若將保護膜之溫度T2升高至40℃左右，則與室溫（23℃）狀態相比斷裂應力之下降變得明顯，可穩定地獲得源於熱延伸之效果（分割不良之降低）。另一方面，若使第1支撐片4之延伸時之保護膜之溫度T2超過70℃，則因保護膜之斷裂應變增大、第1支撐片4之機械特性變化（楊氏模數下降、軟質化等）所引起之作業不良（具體例可列舉延伸量之下降、第1支撐片4對載物台之熔著等）等不良情形明顯化之可能性變高。因此，藉由將第1支撐片4之延伸時之保護膜之溫度T2設為70℃以下，可使附有保護膜之晶片之製造中產生不良情形之可能性穩定地降低。就使此種產生不良情形之可能性更穩定地降低之觀點而言，第1支撐片4之延伸時之保護膜之溫度T2較佳為設為42℃以上且65℃以下，更佳為設為43℃以上且60℃以下，尤佳為設為45℃以上且55℃以下。That is, by performing hot stretching in contrast to the conventional cold stretching, the possibility of defective division of the protective film is reduced. If the temperature T2 of the protective film is increased to about 40°C, the fracture stress decreases significantly compared to the room temperature (23°C) state, and the effect due to thermal extension (reduction of poor segmentation) can be stably obtained. On the other hand, if the temperature T2 of the protective film when the first support sheet 4 is stretched exceeds 70°C, the breaking strain of the protective film increases and the mechanical properties of the first support sheet 4 change (the Young’s modulus decreases, Poor work caused by softening, etc. (specific examples include a decrease in elongation, fusion of the first support sheet 4 to the stage, etc.) and other defects are more likely to become apparent. Therefore, by setting the temperature T2 of the protective film when the first support sheet 4 is stretched to 70° C. or lower, the possibility of defects in the manufacture of a chip with a protective film can be stably reduced. From the viewpoint of stably reducing the possibility of such failures, the temperature T2 of the protective film when the first support sheet 4 is stretched is preferably set to 42°C or higher and 65°C or lower, and more preferably It is 43° C. or higher and 60° C. or lower, particularly preferably 45° C. or higher and 55° C. or lower.

（4）第1拾取步驟 第1拾取步驟中，將藉由實施第1分割步驟而獲得的第2積層體20所具備之複數個附有保護膜之晶片9分別自第1支撐片4分離，而獲得個別之附有保護膜之晶片9作為加工物。該分離方法並無限定。可如圖5所示，使用頂起銷P及真空吸附筒夾C。如此，可獲得附有保護膜之晶片9。即，第1拾取步驟之一個形態係包括藉由將前述第2積層體所具備之前述複數個附有保護膜之晶片分別自前述第1支撐片分離，而獲得前述附有保護膜之晶片作為加工物。(4) The first picking step In the first pick-up step, the plurality of protective film-attached wafers 9 included in the second laminate 20 obtained by performing the first division step are separated from the first support sheet 4 to obtain individual protected wafers. The film wafer 9 is used as a processed object. The separation method is not limited. As shown in Figure 5, the jacking pin P and the vacuum suction collet C can be used. In this way, a chip 9 with a protective film can be obtained. That is, one form of the first pickup step includes obtaining the protective film-attached wafers by separating the plurality of protective film-attached wafers included in the second laminate from the first support sheet, respectively. Processed objects.

（5）改質層形成步驟 於開始第1分割步驟之前係進行改質層形成步驟，係以聚焦於設定在半導體晶圓7（工件）內部之焦點的方式照射紅外線區域（例如為1064 nm）之雷射光，而於半導體晶圓7內部形成改質層。第1分割步驟中，藉由使對經過改質層形成步驟之半導體晶圓7貼合之第1支撐片伸長，而於分割預定線處進行半導體晶圓7之分割。即，改質層形成步驟之一個形態係包括在開始前述第1分割步驟之前，以聚焦於設定在前述工件內部之焦點的方式照射紅外線區域之雷射光，而於前述工件內部形成改質層。(5) Steps for forming modified layer Before starting the first dividing step, a reforming layer forming step is performed. The laser light in the infrared region (for example, 1064 nm) is irradiated to the focal point set in the semiconductor wafer 7 (workpiece). A modified layer is formed inside the circle 7. In the first division step, the semiconductor wafer 7 is divided at the planned division line by extending the first support sheet bonded to the semiconductor wafer 7 after the reforming layer forming step. That is, one aspect of the reforming layer forming step includes irradiating laser light in the infrared region to focus on the focal point set inside the workpiece before starting the first dividing step, and forming the reforming layer inside the workpiece.

8.保護膜形成用片之其他實施形態 （1）第1支撐片不具有治具用黏著劑層之情形 圖6係本發明其他實施形態之一的保護膜形成用片之剖面圖。如圖6所示，本實施形態之保護膜形成用片3A之構成為具備：第1支撐片4，係於基材41之一面積層黏著劑層42而成；保護膜形成膜1，其積層於第1支撐片4中之積層有黏著劑層42之側；及剝離片6，其積層於保護膜形成膜1中與面對第1支撐片4之面為相反側之面。實施形態中之保護膜形成膜1係以於面方向與工件大致相同或較工件稍大之方式形成，且以於面方向上較第1支撐片4小之方式形成。未積層有保護膜形成膜1之部分之黏著劑層42可貼附於環狀架等治具。8. Other embodiments of the protective film forming sheet (1) When the first support sheet does not have an adhesive layer for jigs Fig. 6 is a cross-sectional view of a protective film forming sheet according to another embodiment of the present invention. As shown in FIG. 6, the protective film forming sheet 3A of the present embodiment is configured to include: a first support sheet 4 formed by layering an adhesive layer 42 on one area of a base material 41; The side where the adhesive layer 42 is laminated in the first support sheet 4; and the release sheet 6, which is laminated in the protective film forming film 1 on the opposite side to the surface facing the first support sheet 4. The protective film forming film 1 in the embodiment is formed so as to be substantially the same as or slightly larger than the workpiece in the surface direction, and is formed so as to be smaller than the first support sheet 4 in the surface direction. The adhesive layer 42 in the portion where the protective film forming film 1 is not laminated can be attached to a jig such as a ring frame.

本實施形態之保護膜形成用片3A之各構件之材料及厚度等與前述保護膜形成用片3之各構件之材料及厚度相同。然而，於黏著劑層42包含能量線硬化性黏著劑時，較佳為使黏著劑層42中之要與保護膜形成膜1接觸之部分之能量線硬化性黏著劑硬化，除此以外之部分不使能量線硬化性黏著劑硬化。藉此，可提高使保護膜形成膜1硬化而成之保護膜之平滑性（巨觀），並且可將對環狀架等治具之接著力維持為高。The material and thickness of each member of the protective film forming sheet 3A of this embodiment are the same as the material and thickness of each member of the protective film forming sheet 3 described above. However, when the adhesive layer 42 contains an energy-ray-curable adhesive, it is preferable to harden the energy-ray-curable adhesive in the part of the adhesive layer 42 that is to be in contact with the protective film forming film 1, and other parts Does not harden the energy ray curable adhesive. Thereby, the smoothness (macro) of the protective film formed by curing the protective film forming film 1 can be improved, and the adhesive force to jigs such as a ring frame can be maintained high.

再者，亦可於保護膜形成用片3A之第1支撐片4之黏著劑層42中與基材41為相反側之周緣部，另行設置與前述保護膜形成用片3之治具用黏著劑層5相同之治具用黏著劑層。Furthermore, in the adhesive layer 42 of the first support sheet 4 of the protective film forming sheet 3A, the peripheral edge portion opposite to the base material 41 may be separately provided with an adhesive for jigs with the aforementioned protective film forming sheet 3 Adhesive layer for jigs with the same agent layer 5.

（2）第1支撐片不具有黏著劑層之情形 如圖11所示，本發明其他實施形態之一的保護膜形成用片3B所具備之第1支撐片亦可不具備黏著劑層，而（僅）由基材構成。於此情形時，基材中之保護膜形成膜側之面相當於第1支撐片之第1面。(2) When the first support sheet does not have an adhesive layer As shown in FIG. 11, the 1st support sheet with which the sheet 3B for protective film formation of another embodiment of this invention is equipped may not have an adhesive layer, and may consist of a base material (only). In this case, the surface of the base material on the side where the protective film is formed corresponds to the first surface of the first support sheet.

於第1支撐片由基材構成時，較佳為在保護膜形成膜中與面對基材（第1支撐片）之面為相反側之面的周緣部，設置與圖1所示之治具用黏著劑層5相同之治具用黏著劑層。When the first support sheet is composed of a base material, it is preferable that the peripheral portion of the surface opposite to the surface facing the base material (the first support sheet) in the protective film formation film is provided with the same treatment as shown in FIG. The adhesive layer for jigs is the same as the adhesive layer 5 for jigs.

（3）第1支撐片為剝離片之情形 本發明之其他實施形態之一的保護膜形成用片所具備之第1支撐片可為具有剝離面之剝離片。於此情形時，剝離面相當於第1支撐片之第1面。剝離片之具體構成並無限定。(3) When the first support sheet is a release sheet The first support sheet included in the protective film forming sheet of one of the other embodiments of the present invention may be a peeling sheet having a peeling surface. In this case, the peeling surface corresponds to the first surface of the first support sheet. The specific structure of the release sheet is not limited.

（4）具備第2支撐片之情形 本發明之其他實施形態之一的保護膜形成用片係可具備第2支撐片，係積層於保護膜形成膜之與面對第1支撐片之面為相反之面側。第2支撐片可為剝離片，且以剝離面與保護膜形成膜相向之方式配置。(4) The situation with the second supporting piece The sheet for forming a protective film according to another embodiment of the present invention may include a second supporting sheet, which is laminated on the side of the protective film forming film opposite to the surface facing the first supporting sheet. The second support sheet may be a peeling sheet, and is arranged such that the peeling surface faces the protective film forming film.

（5）將第1支撐片自保護膜形成膜剝離之情形 如圖2至圖5所示，上述本發明一實施形態之附有保護膜之晶片9之製造方法中，於第1硬化步驟中由保護膜形成膜1形成保護膜之後，於第1拾取步驟中自第1支撐片4分離保護膜，具體而言為分離作為附有保護膜之晶片9之一部分的保護膜之分割體。(5) When the first support sheet is peeled from the protective film forming film As shown in FIGS. 2 to 5, in the method for manufacturing a protective film-attached wafer 9 according to an embodiment of the present invention, after the protective film is formed from the protective film forming film 1 in the first curing step, the protective film is formed in the first pickup step The protective film is separated from the first support sheet 4, specifically, a division of the protective film that is a part of the wafer 9 with the protective film.

本發明之其他實施形態之一的附有保護膜之晶片之製造方法中，保護膜形成膜自第1支撐片剝離之後被硬化而成為保護膜。此種製造方法之一例如下。In the manufacturing method of a wafer with a protective film which is one of the other embodiments of the present invention, the protective film forming film is peeled from the first support sheet and then cured to become a protective film. An example of such a manufacturing method is as follows.

即，本實施形態之製造方法之一個形態係如圖7～圖10所示般，包括：積層步驟，係使本發明一實施形態之保護膜形成用片所具備之保護膜形成膜1中與面對第1支撐片之面為相反側之面露出，將前述露出之面貼附於半導體晶圓等工件7之一面，且將前述保護膜形成用片之第1支撐片自保護膜形成膜1剝離，藉此獲得具備前述工件7與前述保護膜形成膜1之第3積層體11；第2硬化步驟，係藉由使前述第3積層體11所具備之前述保護膜形成膜1硬化，而獲得保護膜；第2貼附步驟，係將具備第3基材132及積層於第3基材132之一面側之第3黏著劑層131的加工用片13中之前述第3黏著劑層側131之面，與經過前述第2硬化步驟之前述第3積層體11中之前述保護膜側之面貼合，藉此獲得具備前述加工用片13與前述第3積層體11之第4積層體12；第2分割步驟，係於將前述第4積層體12所具備之前述保護膜之溫度T3保持在40℃至70℃之範圍內的狀態下，使前述第4積層體12所具備之前述加工用片13伸長，將前述保護膜與前述工件7一起分割，藉此獲得第5積層體14，該第5積層體14係於前述加工用片13之一面上配置有將前述工件7與前述保護膜之積層體以於厚度方向產生切割面的方式分割而成之複數個附有保護膜之晶片9；及第2拾取步驟，係將前述第5積層體14所具備之複數個附有保護膜之晶片9分別自前述加工用片13分離，而獲得附有保護膜之晶片9作為加工物；進一步包括改質層形成步驟，該改質層形成步驟係於開始前述第2分割步驟之前，以聚焦於設定在前述工件7內部之焦點的方式照射紅外線區域之雷射光，而於前述工件7內部形成改質層。That is, one mode of the manufacturing method of the present embodiment is shown in FIGS. 7 to 10, and includes a layering step of making the protective film forming film 1 included in the protective film forming sheet of one embodiment of the present invention and The surface facing the first support sheet is exposed on the opposite side. The exposed surface is attached to one surface of the workpiece 7 such as a semiconductor wafer, and the first support sheet of the protective film forming sheet is formed from the protective film. 1. Peel off to obtain a third layered body 11 including the workpiece 7 and the protective film forming film 1; the second curing step is to harden the protective film forming film 1 of the third layered body 11, The protective film is obtained; the second attaching step is to include the third adhesive layer in the processing sheet 13 with the third substrate 132 and the third adhesive layer 131 laminated on one side of the third substrate 132 The surface of the side 131 is bonded to the surface of the protective film side of the third laminate 11 after the second curing step, thereby obtaining the fourth laminate including the processing sheet 13 and the third laminate 11 Body 12; The second dividing step is to maintain the temperature T3 of the protective film provided in the fourth laminate 12 in the range of 40°C to 70°C, so that the fourth laminate 12 has The processing sheet 13 is stretched, and the protective film is divided together with the work 7 to obtain a fifth laminate 14. The fifth laminate 14 is arranged on one surface of the processing sheet 13 to connect the work 7 and A plurality of protective film-attached wafers 9 divided into the laminate of the protective film such that a cut surface is generated in the thickness direction; and the second pick-up step is to attach the plurality of wafers with the fifth laminate 14 to The protective film wafers 9 are separated from the aforementioned processing sheet 13 to obtain the protective film-attached wafer 9 as a processed product; further comprising a modified layer forming step, which is before the start of the second dividing step , The laser light in the infrared region is irradiated to focus on the focal point set inside the workpiece 7 to form a modified layer inside the workpiece 7.

此處，加工用片13所具備之第3基材132具有與支撐片4所具備之基材41相同之特徵即可。又，加工用片13所具備之第3黏著劑層131具有與支撐片4所具備之黏著劑層42相同之特徵即可。另外，第2分割步驟中之溫度T3較佳為上述溫度T1以上。Here, the third base 132 included in the processing sheet 13 may have the same characteristics as the base 41 included in the support sheet 4. In addition, the third adhesive layer 131 included in the processing sheet 13 may have the same characteristics as the adhesive layer 42 included in the support sheet 4. In addition, the temperature T3 in the second dividing step is preferably higher than the above-mentioned temperature T1.

以上說明之實施形態係為了使本發明理解容易而記載，並非限定本發明。因此，上述實施形態所揭示之各要件亦包括屬於本發明技術範圍之所有設計變更或均等物。The embodiments described above are described in order to facilitate the understanding of the present invention, and do not limit the present invention. Therefore, the requirements disclosed in the above-mentioned embodiments also include all design changes or equivalents belonging to the technical scope of the present invention.

例如，亦可於第1支撐片4中之基材41與黏著劑層42之間介置其他層。另外，亦可於包含基材41之第1支撐片4之第1面積層其他層。作為其他層，例如可列舉底塗層等用於調整基材41與黏著劑層42之間之接著性的層、調整支撐片4與保護膜形成膜1之間之接著性的層。 （實施例）For example, another layer may be interposed between the base material 41 and the adhesive layer 42 in the first support sheet 4. In addition, other layers of the first area layer of the first support sheet 4 including the base material 41 may be used. As other layers, for example, a layer for adjusting the adhesiveness between the base material 41 and the adhesive layer 42 such as a primer layer, and a layer for adjusting the adhesiveness between the support sheet 4 and the protective film forming film 1 can be cited. (Example)

以下藉由實施例等更具體地說明本發明，但本發明之範圍並不限定於該等實施例等。Hereinafter, the present invention will be explained in more detail with examples and the like, but the scope of the present invention is not limited to these examples and the like.

〔實施例1〕 將以下之各成分以表1所示之調配比（固體成分換算）進行混合，且以固體成分濃度相對於保護膜形成膜用塗佈劑之總質量而成為50質量%之方式利用甲基乙基酮進行稀釋，而調製保護膜形成膜用塗佈劑。 （A-1）黏合劑聚合物：使丙烯酸正丁酯10質量份、丙烯酸甲酯70質量份、甲基丙烯酸縮水甘油酯5質量份及丙烯酸2-羥基乙酯15質量份共聚而成之（甲基）丙烯酸酯共聚物（重量平均分子量：40萬，玻璃轉移溫度：-1℃） （A-2）黏合劑聚合物：使丙烯酸甲酯85質量份、及丙烯酸2-羥基乙酯15質量份共聚而成之（甲基）丙烯酸酯共聚物（重量平均分子量：40萬，玻璃轉移溫度：-6℃） （A-3）黏合劑聚合物：使丙烯酸正丁酯55質量份、丙烯酸甲酯10質量份、甲基丙烯酸縮水甘油酯20質量份及丙烯酸2-羥基乙酯15質量份共聚而成之（甲基）丙烯酸酯共聚物（重量平均分子量：80萬，玻璃轉移溫度：-28℃） （B-1）雙酚A型環氧樹脂（三菱化學公司製造，jER828，環氧當量為184 g/eq～194 g/eq） （B-2）雙酚A型環氧樹脂（三菱化學公司製造，jER1055，環氧當量為800 g/eq～900 g/eq） （B-3）二環戊二烯型環氧樹脂（DIC公司製造，Epiclon HP-7200HH，環氧當量為255 g/eq～260 g/eq） （B-4）甲酚酚醛清漆型環氧樹脂（日本化藥公司製造，EOCN-104，環氧當量為220 g/eq） （C）熱活性潛伏性環氧樹脂硬化劑：二氰二胺（ADEKA公司製造，Adeka Hardener EH-3636AS，活性氫量為21 g/eq） （D）硬化促進劑：2-苯基-4,5-二羥基甲基咪唑（四國化成工業公司製造，Curezol 2PHZ） （E-1）環氧基改質球狀二氧化矽填料（Admatechs公司製造，SC2050MA，平均粒徑為0.5 μm） （E-2）乙烯基改質球狀二氧化矽填料（Admatechs公司製造，YA050C-MJA，平均粒徑為0.05 μm） （E-3）不定形二氧化矽填料（龍森公司製造，SV-10，平均粒徑為8 μm） （F）矽烷偶合劑：γ-縮水甘油氧基丙基三甲氧基矽烷（信越化學工業公司製造，KBM403，甲氧基當量：12.7 mmol/g，分子量：236.3）[Example 1] The following components are mixed at the blending ratio (in terms of solid content) shown in Table 1, and methyl ethyl is used so that the solid content concentration is 50% by mass relative to the total mass of the coating agent for forming a protective film. The base ketone is diluted to prepare a coating agent for forming a protective film. (A-1) Binder polymer: copolymerized with 10 parts by mass of n-butyl acrylate, 70 parts by mass of methyl acrylate, 5 parts by mass of glycidyl methacrylate and 15 parts by mass of 2-hydroxyethyl acrylate ( Meth) acrylate copolymer (weight average molecular weight: 400,000, glass transition temperature: -1°C) (A-2) Adhesive polymer: (meth)acrylate copolymer copolymerized by 85 parts by mass of methyl acrylate and 15 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight: 400,000, glass transfer Temperature: -6℃) (A-3) Binder polymer: copolymerized by 55 parts by mass of n-butyl acrylate, 10 parts by mass of methyl acrylate, 20 parts by mass of glycidyl methacrylate, and 15 parts by mass of 2-hydroxyethyl acrylate ( Meth) acrylate copolymer (weight average molecular weight: 800,000, glass transition temperature: -28°C) (B-1) Bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER828, epoxy equivalent is 184 g/eq～194 g/eq) (B-2) Bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER1055, epoxy equivalent is 800 g/eq～900 g/eq) (B-3) Dicyclopentadiene epoxy resin (manufactured by DIC, Epiclon HP-7200HH, epoxy equivalent 255 g/eq～260 g/eq) (B-4) Cresol novolac epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104, epoxy equivalent 220 g/eq) (C) Thermally active latent epoxy resin hardener: dicyandiamine (manufactured by ADEKA, Adeka Hardener EH-3636AS, active hydrogen content is 21 g/eq) (D) Hardening accelerator: 2-phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd., Curezol 2PHZ) (E-1) Epoxy modified spherical silica filler (manufactured by Admatechs, SC2050MA, with an average particle size of 0.5 μm) (E-2) Vinyl modified spherical silica filler (manufactured by Admatechs, YA050C-MJA, average particle size is 0.05 μm) (E-3) Unshaped silica filler (manufactured by Ronson, SV-10, average particle size 8 μm) (F) Silane coupling agent: γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., KBM403, methoxy equivalent: 12.7 mmol/g, molecular weight: 236.3)

[表1]

Figure 02_image001
[Table 1]
Figure 02_image001

於在聚對苯二甲酸乙二酯（PET）膜之單面形成聚矽氧系之剝離劑層而成之剝離片（LINTEC公司製造，SP-PET381031）上，利用刀式塗佈機，以最終獲得之保護膜形成膜之厚度成為25 μm之方式塗佈前述保護膜形成膜用塗佈劑之後，利用烘箱於120℃乾燥2分鐘，而形成保護膜形成膜。然後於保護膜形成膜上，重疊在PET膜之單面形成聚矽氧系之剝離劑層而成之剝離片（LINTEC公司製造，SP-PET251130）之剝離面，並使兩者貼合，而獲得保護膜形成用片。On a release sheet (made by LINTEC, SP-PET381031) formed by forming a silicone release agent layer on one side of a polyethylene terephthalate (PET) film, use a knife coater to The protective film forming film finally obtained was coated with the aforementioned coating agent for protective film forming film so that the thickness of the protective film forming film became 25 μm, and then dried in an oven at 120° C. for 2 minutes to form a protective film forming film. Then, on the protective film forming film, overlap the peeling surface of the peeling sheet (manufactured by LINTEC Corporation, SP-PET251130) formed by forming a polysiloxane release agent layer on one side of the PET film, and attach the two together. A sheet for forming a protective film was obtained.

〔實施例2〕 調製如下之保護膜形成膜用塗佈劑，即，將構成保護膜形成膜之各成分之種類及調配量設為表1之實施例2之列所示之組成，且以固體成分濃度成為50%之方式利用甲基乙基酮進行稀釋，除此以外，以與實施例1相同之方式製造保護膜形成用片。[Example 2] The following coating agent for protective film forming film was prepared by setting the type and blending amount of each component constituting the protective film forming film to the composition shown in Example 2 of Table 1, and the solid content concentration was 50 The protective film formation sheet was produced in the same manner as in Example 1 except for diluting with methyl ethyl ketone as %.

〔比較例1〕 調製如下之保護膜形成膜用塗佈劑，即，將構成保護膜形成膜之各成分之種類及調配量設為表1之比較例1之列所示之組成，且以固體成分濃度成為50%之方式利用甲基乙基酮進行稀釋，除此以外，以與實施例1相同之方式製造保護膜形成用片。[Comparative Example 1] The coating agent for the protective film forming film was prepared by setting the types and blending amounts of the components constituting the protective film forming film to the composition shown in the column of Comparative Example 1 in Table 1, and the solid content concentration was 50 The protective film formation sheet was produced in the same manner as in Example 1 except for diluting with methyl ethyl ketone as %.

〔比較例2〕 調製如下之保護膜形成膜用塗佈劑，即，將構成保護膜形成膜之各成分之種類及調配量設為表1之比較例2之列所示之組成，且以固體成分濃度成為50%之方式利用甲基乙基酮進行稀釋，除此以外，以與實施例1相同之方式製造保護膜形成用片。再者，（E-3）不定形二氧化矽填料（SV-10）使用預先利用珠磨機於甲基乙基酮中分散24小時而成者。[Comparative Example 2] The coating agent for protective film forming film was prepared by setting the type and blending amount of each component constituting the protective film forming film to the composition shown in the column of Comparative Example 2 in Table 1, and the solid content concentration was 50 The protective film formation sheet was produced in the same manner as in Example 1 except for diluting with methyl ethyl ketone as %. In addition, (E-3) Unshaped silica filler (SV-10) is prepared by pre-dispersing in methyl ethyl ketone with a bead mill for 24 hours.

〔試驗例1〕＜黏彈性之測定＞ （1）硬化物樣品之製作 將實施例及比較例中所製作之保護膜形成用片之兩片剝離片剝離，且以厚度成為200 μm之方式積層所獲得之保護膜形成膜。將所獲得之保護膜形成層在烘箱內（大氣環境下）於130℃加熱2小時，而獲得厚度為200 μm之保護膜作為硬化物樣品。 （2）硬化後之50℃之斷裂應變之測定 切割所獲得之硬化物樣品，準備寬度5 mm×長度20 mm×厚度200 μm之試驗片。使用動態機械分析裝置（TA Instruments公司製造，DMA Q800），進行試驗片之拉伸試驗（夾盤間距：5 mm）。於溫度為50℃之環境下保持1分鐘之後，一面以1 N/分鐘之固定增加率增加負重一面進行拉伸試驗。自其結果獲得斷裂應變。將結果示於表2。 （3）硬化物樣品之損耗正切之峰值溫度之測定 切割硬化物樣品，準備寬度4.5 mm×長度20 mm×厚度200 μm之試驗片。使用動態機械分析裝置（TA Instruments公司製造，DMA Q800），於下述條件下進行儲存模數及損耗模數之測定。 測定模式：拉伸模式 測定開始溫度：0℃ 測定結束溫度：300℃ 升溫速度：3℃/分鐘 頻率：11 Hz 測定環境：大氣 根據所獲得之儲存模數及損耗模數算出損耗正切（tanδ），將該值成為最大之溫度設為損耗正切之峰值溫度。將結果示於表2。 （4）硬化物樣品之25℃之儲存模數及損耗正切之測定 根據上述儲存模數及損耗模數之測定資料，求出25℃之儲存模數及25℃之損耗正切。將結果示於表2。 （5）硬化後之50℃之斷裂應力之測定 切割所獲得之硬化物樣品，準備寬度5 mm×長度20 mm×厚度200 μm之試驗片。使用動態機械分析裝置（TA Instruments公司製造，DMA Q800），進行試驗片之拉伸試驗（夾盤間距：5 mm）。於溫度為50℃之環境下保持1分鐘之後，一面以1 N/分鐘之固定之增加率增加負重，一面進行拉伸試驗。自其結果獲得斷裂應力。其結果為，實施例1中為1.71×107 Pa，實施例2中為1.02×107 Pa、比較例1中為8.90×106 Pa，比較例2中為2.27×107 Pa。[Test example 1] <Measurement of viscoelasticity> (1) Preparation of cured product sample The two release sheets of the protective film forming sheet produced in the examples and comparative examples were peeled off and laminated so that the thickness became 200 μm The obtained protective film forms a film. The obtained protective film forming layer was heated at 130°C for 2 hours in an oven (under the atmospheric environment) to obtain a protective film with a thickness of 200 μm as a cured product sample. (2) Measurement of breaking strain at 50℃ after hardening. The hardened sample obtained by cutting, prepare a test piece with a width of 5 mm × a length of 20 mm × a thickness of 200 μm. A dynamic mechanical analysis device (manufactured by TA Instruments, DMA Q800) was used to perform a tensile test of the test piece (chuck distance: 5 mm). After maintaining for 1 minute in an environment with a temperature of 50°C, a tensile test was performed while increasing the load at a constant rate of increase of 1 N/min. From the result, the fracture strain is obtained. The results are shown in Table 2. (3) Measurement of the peak temperature of the loss tangent of the hardened sample. Cut the hardened sample and prepare a test piece with a width of 4.5 mm × a length of 20 mm × a thickness of 200 μm. Using a dynamic mechanical analysis device (manufactured by TA Instruments, DMA Q800), the storage modulus and loss modulus were measured under the following conditions. Measurement mode: Tensile mode Measurement start temperature: 0°C Measurement end temperature: 300°C Heating rate: 3°C/min Frequency: 11 Hz Measurement environment: Atmosphere calculates the loss tangent (tanδ) based on the obtained storage modulus and loss modulus , The temperature at which this value becomes the maximum is the peak temperature of the loss tangent. The results are shown in Table 2. (4) Measurement of the storage modulus and loss tangent at 25°C of the cured product sample. According to the measurement data of the storage modulus and loss modulus mentioned above, calculate the storage modulus at 25°C and the loss tangent at 25°C. The results are shown in Table 2. (5) Measurement of fracture stress at 50°C after curing. The cured product sample obtained by cutting, prepare a test piece with a width of 5 mm × a length of 20 mm × a thickness of 200 μm. A dynamic mechanical analysis device (manufactured by TA Instruments, DMA Q800) was used to perform a tensile test of the test piece (chuck distance: 5 mm). After keeping it at a temperature of 50°C for 1 minute, while increasing the load at a fixed rate of increase of 1 N/min, a tensile test was performed. From the result, the fracture stress is obtained. As a result, it was 1.71×10 7 Pa in Example 1, 1.02×10 7 Pa in Example 2, 8.90×10 6 Pa in Comparative Example 1, and 2.27×10 7 Pa in Comparative Example 2.

〔試驗例2〕＜分割性之評價＞ 於厚度100 μm、外徑8吋之矽晶圓所構成之工件上，使用貼附裝置（LINTEC公司製造，RAD-3600F/12）於70℃貼附切割加工成與矽晶圓相同形狀之保護膜形成膜之後，在烘箱內（大氣環境下）於130℃加熱2小時使其硬化，而製作附有保護膜之晶圓。 使用貼附裝置（LINTEC公司製造，RAD-2700F/12），將隱形切割用切割帶（LINTEC公司製造，Adwill D-821HS）貼附於附有保護膜之晶圓之保護膜面。此時，亦進行切割帶對環狀架之貼附。 使用雷射照射裝置，隔著切割帶及保護膜而照射在晶圓內部聚光之雷射（波長：1064 nm）。此時，沿著以形成5 mm×5 mm之晶片體之方式設定之切割預定線一面掃描一面照射。 然後，使用延伸裝置（DISCO公司製造，DDS2300），於溫度為50℃之環境下，以速度100 mm/秒、延伸量10 mm將貼合於附有保護膜之晶圓之切割帶延伸。 其結果，在於所有切割預定線處被分割之晶圓同樣地保護膜亦被分割，時將保護膜分割性設為良好（表2中「A」），將於分割後之保護膜確認到拉絲現象之情形（表2中「B」）、或有保護膜未被分割之部位之情形（表2中「C」）判定為不良。將結果示於表2。[Test Example 2] <Evaluation of severability> Use an attachment device (manufactured by LINTEC, RAD-3600F/12) on a workpiece composed of a silicon wafer with a thickness of 100 μm and an outer diameter of 8 inches at 70°C, which is cut into the same shape as the silicon wafer. After the film is formed into a film, it is heated at 130°C for 2 hours in an oven (atmospheric environment) to harden it to produce a wafer with a protective film. Use the attaching device (manufactured by LINTEC, RAD-2700F/12) to attach the invisible dicing dicing tape (manufactured by LINTEC, Adwill D-821HS) to the protective film surface of the wafer with the protective film. At this time, the cutting tape is attached to the ring frame. A laser irradiation device is used to irradiate the laser (wavelength: 1064 nm) condensed inside the wafer through the dicing tape and the protective film. At this time, scan and irradiate along the planned cutting line set to form a 5 mm×5 mm wafer body. Then, using an extension device (manufactured by DISCO, DDS2300) at a temperature of 50°C, the dicing tape attached to the wafer with the protective film is extended at a speed of 100 mm/sec and an extension of 10 mm. As a result, the protective film of all wafers that are divided at the planned dicing line is also divided. When the protective film is divided into good ("A" in Table 2), the protective film after division is confirmed to be drawn Phenomenon (“B” in Table 2), or where the protective film is not divided (“C” in Table 2) is judged as defective. The results are shown in Table 2.

〔試驗例3〕＜保護膜之強度之評價＞ 於試驗例2中進行之分割性評價後，使用上述延伸裝置，且使用將熱源設定為550℃之IR（Infrared，紅外線）爐，將具備被分割之晶圓及保護膜（即複數個附有保護膜之晶片）以及切割帶之積層體（第4積層體）加熱5分鐘，藉此矯正切割帶延伸時產生之切割帶之鬆弛。然後，使用固晶機（Canon Machinery公司製造，Bestem-D02），於進行過3 mm之延伸之狀態下，自切割帶之與面對被分割晶圓及保護膜之面為相反的面側壓抵頂起銷，且利用真空吸附筒夾將被頂出之附有保護膜之晶片拉起，藉此拾取附有保護膜之晶片。 對所拾取之附有保護膜之晶片進行觀察，將未確認到壓抵於保護膜之銷之痕跡之情形判定為良好（表2中「A」），將確認到無問題程度之銷之痕跡的情形判定為合格（表2中「B」），將確認到銷之痕跡之情形判定為不良（表2中「C」）。將結果示於表2。再者，關於本評價，由於比較例2之保護膜在試驗例2中未恰當地被分割，故而僅對具備實施例1及2以及比較例1（評價對象設為被割斷之一部分）之保護膜之第4積層體進行本評價。[Test Example 3] <Evaluation of the strength of the protective film> After the evaluation of the severability in Test Example 2, using the above-mentioned extension device and using an IR (Infrared) furnace with the heat source set to 550°C, the wafer to be divided and the protective film (that is, a plurality of The laminate of the protective film) and the laminate of the dicing tape (the fourth laminate) are heated for 5 minutes to correct the slack of the dicing tape when the dicing tape is stretched. Then, using a die bonder (manufactured by Canon Machinery, Bestem-D02), in a state of 3 mm extension, the side of the dicing tape and the side facing the divided wafer and the protective film are pressed side by side. Press the jacking pin, and use the vacuum suction collet to pull up the chip with the protective film that has been ejected, thereby picking up the chip with the protective film. Observe the picked-up chip with protective film, and judge that the trace of the pin pressed against the protective film is not confirmed as good ("A" in Table 2), and the pin with no problem level will be confirmed The situation is judged as pass ("B" in Table 2), and the situation where the traces of sales are confirmed is judged as bad ("C" in Table 2). The results are shown in Table 2. In addition, regarding this evaluation, since the protective film of Comparative Example 2 was not properly divided in Test Example 2, only the protective film provided with Examples 1 and 2 and Comparative Example 1 (the evaluation object is set to be part of the cut) The fourth laminate of the film was subjected to this evaluation.

[表2]

Figure 108128902-A0304-0001
[Table 2]
Figure 108128902-A0304-0001

根據表2可知，具備50℃之斷裂應變為20%以下且損耗正切之峰值溫度T1處於25℃至60℃之範圍內之保護膜之實施例之保護膜形成用片的分割性優異，並且保護膜之強度亦優異。 [產業上之可利用性]According to Table 2, it can be seen that the protective film forming sheet of the embodiment having a protective film with a breaking strain of 50°C of 20% or less and a loss tangent peak temperature T1 in the range of 25°C to 60°C has excellent partitioning properties and protects The strength of the film is also excellent. [Industrial availability]

本發明之保護膜形成用片適合用於包括將保護膜一面加熱一面分割之步驟之情形，因此於產業上極其有用。The sheet for forming a protective film of the present invention is suitable for use in a case including a step of heating and dividing the protective film, and therefore is extremely useful in industry.

1‧‧‧保護膜形成膜 3、3A、3B‧‧‧保護膜形成用片 4‧‧‧支撐片 41‧‧‧基材 42‧‧‧黏著劑層 5‧‧‧治具用黏著劑層 6‧‧‧剝離片 7‧‧‧半導體晶圓 8‧‧‧環狀架 9‧‧‧附有保護膜之晶片 10‧‧‧第1積層體 11、20‧‧‧第2積層體 12‧‧‧第3積層體 13‧‧‧加工用片 131‧‧‧第3黏著劑層 132‧‧‧第3基材 14‧‧‧第4積層體 R‧‧‧環狀構件 P‧‧‧頂起銷 C‧‧‧真空吸附筒夾 1‧‧‧Protection film forming film 3, 3A, 3B‧‧‧Protection film forming sheet 4‧‧‧Support sheet 41‧‧‧Substrate 42‧‧‧Adhesive layer 5‧‧‧Adhesive layer for fixture 6‧‧‧Release sheet 7‧‧‧Semiconductor wafer 8‧‧‧Ring frame 9‧‧‧Chip with protective film 10‧‧‧Layer 1 11, 20‧‧‧Layer 2 12‧‧‧Layer 3 13‧‧‧Processing film 131‧‧‧The third adhesive layer 132‧‧‧The third substrate 14‧‧‧Layer 4 R‧‧‧Ring member P‧‧‧ jacking pin C‧‧‧Vacuum suction collet

圖1係概念性地表示本發明一實施形態之保護膜形成用片的剖面圖。 圖2係概念性地表示自本發明一實施形態之保護膜形成用片使剝離片剝離後之狀態的剖面圖。 圖3係概念性地表示經過本發明一實施形態之附有保護膜之晶片之製造方法所具備的第1貼附步驟而獲得之第1積層體之剖面圖。 圖4係概念性地表示經過本發明一實施形態之附有保護膜之晶片之製造方法所具備的第1分割步驟而獲得之第2積層體之剖面圖。 圖5係概念性地表示正實施本發明一實施形態之附有保護膜之晶片之製造方法所具備的第1拾取步驟之狀態之剖面圖。 圖6係概念性地表示本發明之其他實施形態之一的保護膜形成用片之剖面圖。 圖7係概念性地表示經過本發明之另一實施形態之附有保護膜之晶片之製造方法所具備的積層步驟而獲得之第3積層體之剖面圖。 圖8係概念性地表示經過本發明之另一實施形態之附有保護膜之晶片之製造方法所具備的第2貼附步驟而獲得之第4積層體之剖面圖。 圖9係概念性地表示經過本發明之另一實施形態之附有保護膜之晶片之製造方法所具備的第2分割步驟而獲得之第5積層體之剖面圖。 圖10係概念性地表示正實施本發明之另一實施形態之附有保護膜之晶片之製造方法所具備的第2拾取步驟之狀態之剖面圖。 圖11係概念性地表示本發明之其他實施形態之一的保護膜形成用片之剖面圖。Fig. 1 is a cross-sectional view conceptually showing a sheet for forming a protective film according to an embodiment of the present invention. Fig. 2 is a cross-sectional view conceptually showing a state in which a release sheet is peeled from the protective film forming sheet according to an embodiment of the present invention. 3 is a cross-sectional view conceptually showing the first laminate obtained through the first attaching step included in the method of manufacturing a chip with a protective film according to an embodiment of the present invention. 4 is a cross-sectional view conceptually showing a second laminate obtained through the first dividing step included in the method for manufacturing a wafer with a protective film according to an embodiment of the present invention. FIG. 5 is a cross-sectional view conceptually showing a state in which the first pick-up step included in the method of manufacturing a chip with a protective film according to an embodiment of the present invention is implemented. Fig. 6 is a cross-sectional view conceptually showing a sheet for forming a protective film according to another embodiment of the present invention. FIG. 7 is a cross-sectional view conceptually showing a third laminate obtained through the lamination steps included in the method of manufacturing a wafer with a protective film according to another embodiment of the present invention. FIG. 8 is a cross-sectional view conceptually showing a fourth laminate obtained through the second attaching step included in the method for manufacturing a chip with a protective film according to another embodiment of the present invention. 9 is a cross-sectional view conceptually showing a fifth laminate obtained through the second division step included in the method of manufacturing a wafer with a protective film according to another embodiment of the present invention. 10 is a cross-sectional view conceptually showing a state in which the second pick-up step included in the method for manufacturing a chip with a protective film according to another embodiment of the present invention is being implemented. Fig. 11 is a cross-sectional view conceptually showing a sheet for forming a protective film according to another embodiment of the present invention.

1‧‧‧保護膜形成膜 1‧‧‧Protection film forming film

3‧‧‧保護膜形成用片 3‧‧‧Sheet for forming protective film

4‧‧‧支撐片 4‧‧‧Support sheet

41‧‧‧基材 41‧‧‧Substrate

42‧‧‧黏著劑層 42‧‧‧Adhesive layer

5‧‧‧治具用黏著劑層 5‧‧‧Adhesive layer for fixture

6‧‧‧剝離片 6‧‧‧Release sheet

Claims (8)

一種保護膜形成用片，係具備第1支撐片及積層於前述第1支撐片之第1面側之保護膜形成膜； 前述保護膜形成膜係由硬化性材料所構成； 前述保護膜形成膜具有以下特性： 前述保護膜形成膜硬化成為保護膜時，前述保護膜之50℃之斷裂應變為20%以下； 損耗正切之峰值溫度T1為25℃至60℃； 且前述保護膜在波長為1064 nm之透光率為40%以上。A sheet for forming a protective film, comprising a first supporting sheet and a protective film forming film laminated on the first surface side of the first supporting sheet; The aforementioned protective film forming film is composed of a curable material; The aforementioned protective film forming film has the following characteristics: When the protective film forming film hardens to become a protective film, the breaking strain at 50°C of the protective film is 20% or less; The peak temperature of loss tangent T1 is 25℃ to 60℃; And the light transmittance of the aforementioned protective film at a wavelength of 1064 nm is more than 40%. 一種保護膜形成用片，係具備第1支撐片及積層於前述第1支撐片之第1面側之保護膜形成膜； 前述保護膜形成膜係由硬化性材料所構成； 前述保護膜形成膜具有以下特性： 前述保護膜形成膜硬化成為保護膜時，前述保護膜之50℃之斷裂應變為20%以下； 且損耗正切之峰值溫度T1為25℃至52℃。A sheet for forming a protective film, comprising a first supporting sheet and a protective film forming film laminated on the first surface side of the first supporting sheet; The aforementioned protective film forming film is composed of a curable material; The aforementioned protective film forming film has the following characteristics: When the protective film forming film hardens to become a protective film, the breaking strain at 50°C of the protective film is 20% or less; And the peak temperature T1 of the loss tangent is 25°C to 52°C. 如請求項2所記載之保護膜形成用片，其中前述保護膜形成膜進而具有以下特性： 前述保護膜在波長為1064 nm之透光率為40%以上。The protective film forming sheet according to claim 2, wherein the protective film forming film further has the following characteristics: The light transmittance of the aforementioned protective film at a wavelength of 1064 nm is more than 40%. 如請求項1至3中任一項所記載之保護膜形成用片，其中前述硬化性材料係含有硬化性成分與黏合劑聚合物成分； 前述硬化性成分係選自由熱硬化性成分與能量線硬化性成分所構成群組中至少1種； 前述熱硬化性成分係選自由環氧樹脂、酚樹脂、三聚氰胺樹脂、尿素樹脂、聚酯樹脂、胺基甲酸酯樹脂、丙烯酸樹脂、聚醯亞胺樹脂、以及苯并噁嗪樹脂所構成群組中至少1種； 前述能量線硬化性成分係於側鏈導入有具有能量線硬化性之官能基之（甲基）丙烯酸酯（共）聚合物（A）； 前述黏合劑聚合物成分係選自丙烯酸系聚合物、聚酯樹脂、苯氧基樹脂、胺基甲酸酯樹脂、聚矽氧樹脂、以及橡膠系聚合物中至少1種。The sheet for forming a protective film according to any one of claims 1 to 3, wherein the curable material contains a curable component and a binder polymer component; The aforementioned sclerosing component is at least one selected from the group consisting of thermosetting components and energy ray sclerosing components; The aforementioned thermosetting component is selected from the group consisting of epoxy resin, phenol resin, melamine resin, urea resin, polyester resin, urethane resin, acrylic resin, polyimide resin, and benzoxazine resin At least 1 in the group; The aforementioned energy-ray-curable component is a (meth)acrylate (co)polymer (A) with energy-ray-curable functional groups introduced into the side chain; The aforementioned binder polymer component is selected from at least one of acrylic polymers, polyester resins, phenoxy resins, urethane resins, silicone resins, and rubber polymers. 一種附有保護膜之晶片之製造方法，係包括： 貼附步驟，係使如請求項1至4中任一項所記載之保護膜形成用片所具備之前述保護膜形成膜中與面對前述第1支撐片之面為相反側之面露出，將前述露出之面貼附於工件之一面，而獲得具備前述保護膜形成用片與前述工件之第1積層體； 第1硬化步驟，係藉由使前述第1積層體中之前述保護膜形成膜硬化，而獲得前述保護膜； 第1分割步驟，係於將經過前述第1硬化步驟之前述第1積層體中之前述保護膜溫度T2保持在40℃至70℃之範圍內的狀態下，使前述第1支撐片伸長，將前述保護膜與前述工件一起分割，藉此獲得第2積層體，該第2積層體係於前述第1支撐片之一面上配置有將前述工件與前述保護膜之積層體以於厚度方向產生切割面的方式分割而成之複數個附有保護膜之晶片；及 第1拾取步驟，係將前述第2積層體所具備之前述複數個附有保護膜之晶片分別自前述第1支撐片分離，而獲得前述附有保護膜之晶片作為加工物； 進一步包括改質層形成步驟，係於開始前述第1分割步驟之前，以聚焦於設定在前述工件內部之焦點的方式照射紅外線區域之雷射光，而於前述工件內部形成改質層。A manufacturing method of a chip with a protective film includes: The attaching step is to expose the surface of the protective film forming film included in the protective film forming sheet described in any one of claims 1 to 4 that is opposite to the surface facing the first support sheet, Attach the exposed surface to one surface of the workpiece to obtain a first laminate having the sheet for forming a protective film and the workpiece; In the first curing step, the protective film is obtained by curing the protective film forming film in the first laminate; The first dividing step is to extend the first support sheet while maintaining the temperature T2 of the protective film in the first laminate after the first curing step in the range of 40°C to 70°C. The protective film is divided together with the workpiece to obtain a second laminate. The second laminate system is provided with a laminate of the workpiece and the protective film on one surface of the first support sheet to create a cut surface in the thickness direction A plurality of chips with protective film divided by the method; and The first pick-up step is to separate the plurality of protective film-attached wafers provided in the second laminate from the first support sheet to obtain the protective film-attached wafers as a processed product; It further includes a modified layer forming step, which is to irradiate the laser light in the infrared region to focus on the focal point set inside the workpiece before starting the first dividing step to form the modified layer inside the workpiece. 如請求項5所記載之附有保護膜之晶片之製造方法，其中前述溫度T2為前述溫度T1以上。The method for manufacturing a wafer with a protective film described in claim 5, wherein the temperature T2 is higher than the temperature T1. 一種附有保護膜之晶片之製造方法，其包括： 積層步驟，係使如請求項1至4中任一項所記載之保護膜形成用片所具備之前述保護膜形成膜中與面對前述第1支撐片之面為相反側之面露出，將前述露出之面貼附於工件之一面，且將前述保護膜形成用片之前述第1支撐片自前述保護膜形成膜剝離，而獲得具備前述工件與前述保護膜形成膜之第3積層體； 第2硬化步驟，係藉由使前述第3積層體所具備之前述保護膜形成膜硬化，而獲得前述保護膜； 第2貼附步驟，係將具備第3基材及積層於前述第3基材之一面側之第3黏著劑層的加工用片中之積層有前述第3黏著劑層之側之面，與經過前述第2硬化步驟之前述第3積層體中之前述保護膜側之面貼合，而獲得具備前述加工用片與前述第3積層體之第4積層體； 第2分割步驟，係於將前述第4積層體所具備之前述保護膜之溫度T3保持在40℃至70℃之範圍內的狀態下，使前述第4積層體所具備之前述加工用片伸長，將前述保護膜與前述工件一起分割，藉此獲得第5積層體，該第5積層體係於前述加工用片之一面上配置有將前述工件與前述保護膜之積層體以於厚度方向產生切割面的方式分割而成之複數個附有保護膜之晶片；及 第2拾取步驟，係將前述第5積層體所具備之前述複數個附有保護膜之晶片分別自前述加工用片分離，而獲得前述附有保護膜之晶片作為加工物； 進一步包括改質層形成步驟，係於開始前述第2分割步驟之前，以聚焦於設定在前述工件內部之焦點的方式照射紅外線區域之雷射光，而於前述工件內部形成改質層。A method for manufacturing a chip with a protective film, which includes: The lamination step is to expose the surface of the protective film forming film included in the protective film forming sheet described in any one of claims 1 to 4 that is opposite to the surface facing the first support sheet, and The exposed surface is attached to one surface of the workpiece, and the first support sheet of the protective film forming sheet is peeled from the protective film forming film to obtain a third laminate having the workpiece and the protective film forming film; In the second curing step, the protective film is obtained by curing the protective film forming film included in the third laminate; In the second attaching step, a processing sheet having a third base material and a third adhesive layer laminated on one side of the third base material is laminated on the surface on the side of the third adhesive layer, and After the second curing step, the surface of the protective film side of the third laminate is attached to obtain a fourth laminate including the processing sheet and the third laminate; The second dividing step is to extend the processing sheet included in the fourth laminate while maintaining the temperature T3 of the protective film included in the fourth laminate in the range of 40°C to 70°C , The protective film and the workpiece are divided together to obtain a fifth layered body. The fifth layered system is provided with a layered body of the workpiece and the protective film on one side of the processing sheet to produce cuts in the thickness direction A plurality of chips with protective film divided by the surface; and The second pick-up step is to separate the plurality of protective film-attached wafers included in the fifth laminate from the processing sheet to obtain the protective film-attached wafer as a processed product; The method further includes a modified layer forming step, which is to irradiate laser light in the infrared region to focus on a focal point set inside the workpiece before starting the second dividing step, thereby forming a modified layer inside the workpiece. 如請求項7所記載之附有保護膜之晶片之製造方法，其中前述溫度T3為前述溫度T1以上。The method for manufacturing a wafer with a protective film described in claim 7, wherein the temperature T3 is higher than the temperature T1.
TW108128902A 2014-08-22 2015-08-21 Sheet for forming protective film and method of manufacturing tip having protective film TWI712670B (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2014-169266 2014-08-22
JP2014-169267 2014-08-22
JP2014169266 2014-08-22
JP2014169267 2014-08-22

Publications (2)

Publication Number Publication Date
TW201940622A TW201940622A (en) 2019-10-16
TWI712670B true TWI712670B (en) 2020-12-11

Family

ID=55350823

Family Applications (4)

Application Number Title Priority Date Filing Date
TW104127314A TWI668290B (en) 2014-08-22 2015-08-21 Sheet for forming protective film and method of manufacturing semiconductor tip having protective film
TW108128902A TWI712670B (en) 2014-08-22 2015-08-21 Sheet for forming protective film and method of manufacturing tip having protective film
TW108122914A TWI706023B (en) 2014-08-22 2015-08-21 Sheet for forming protective film and method of manufacturing tip having protective film
TW104127316A TWI672354B (en) 2014-08-22 2015-08-21 Sheet for forming protective film and method of manufacturing semiconductor tip having protective film

Family Applications Before (1)

Application Number Title Priority Date Filing Date
TW104127314A TWI668290B (en) 2014-08-22 2015-08-21 Sheet for forming protective film and method of manufacturing semiconductor tip having protective film

Family Applications After (2)

Application Number Title Priority Date Filing Date
TW108122914A TWI706023B (en) 2014-08-22 2015-08-21 Sheet for forming protective film and method of manufacturing tip having protective film
TW104127316A TWI672354B (en) 2014-08-22 2015-08-21 Sheet for forming protective film and method of manufacturing semiconductor tip having protective film

Country Status (8)

Country Link
JP (2) JP6589209B2 (en)
KR (2) KR102368140B1 (en)
CN (2) CN106660333B (en)
MY (2) MY182846A (en)
PH (2) PH12017500285B1 (en)
SG (2) SG11201701270QA (en)
TW (4) TWI668290B (en)
WO (2) WO2016027883A1 (en)

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108350108B (en) * 2015-10-29 2021-04-20 琳得科株式会社 Protective film-forming film and composite sheet for forming protective film
WO2017149890A1 (en) * 2016-03-04 2017-09-08 リンテック株式会社 Protective film-forming composite sheet
CN108243616B (en) * 2016-03-04 2022-10-28 琳得科株式会社 Semiconductor processing sheet
SG11201807528RA (en) * 2016-03-04 2018-09-27 Lintec Corp Protective film-forming composite sheet
JP6617056B2 (en) * 2016-03-04 2019-12-04 リンテック株式会社 Semiconductor processing sheet, winding body thereof, and method for manufacturing the winding body
JP7042211B2 (en) * 2016-03-04 2022-03-25 リンテック株式会社 Sheet for semiconductor processing
JP6573841B2 (en) * 2016-03-04 2019-09-11 リンテック株式会社 Semiconductor processing sheet
KR102407322B1 (en) * 2016-04-28 2022-06-10 린텍 가부시키가이샤 A film for forming a protective film and a composite sheet for forming a protective film
TWI731964B (en) * 2016-04-28 2021-07-01 日商琳得科股份有限公司 Complex sheet for forming protective film
TWI778960B (en) * 2016-04-28 2022-10-01 日商琳得科股份有限公司 Film for forming protective film, composite sheet for forming protective film, and method of manufacturing semiconductor chip having protective film
TWI796297B (en) * 2016-04-28 2023-03-21 日商琳得科股份有限公司 Composite sheet for forming protective film
TWI721158B (en) * 2016-04-28 2021-03-11 日商琳得科股份有限公司 Protective film forming film and composite sheet for forming protective film
WO2017195711A1 (en) * 2016-05-12 2017-11-16 住友ベークライト株式会社 Adhesive tape for processing semiconductor substrates
JP6776081B2 (en) * 2016-09-28 2020-10-28 リンテック株式会社 Manufacturing method of semiconductor chip with protective film and manufacturing method of semiconductor device
CN110622302B (en) * 2017-05-17 2022-11-22 琳得科株式会社 Semiconductor device and method for manufacturing the same
WO2019044046A1 (en) * 2017-08-28 2019-03-07 リンテック株式会社 Film-like transparent adhesive and infrared sensor module
WO2019146607A1 (en) * 2018-01-24 2019-08-01 リンテック株式会社 Long laminated sheet, and winding body thereof
KR102487552B1 (en) 2018-02-05 2023-01-11 삼성전자주식회사 Composition for protective film against sawing process and method of manufacturing semiconductor package using the composition
WO2019182001A1 (en) * 2018-03-23 2019-09-26 リンテック株式会社 Film-like adhesive and sheet for semiconductor processing
KR102467148B1 (en) * 2018-03-30 2022-11-14 린텍 가부시키가이샤 Composite sheet for forming support sheet and protective film
WO2019187010A1 (en) * 2018-03-30 2019-10-03 リンテック株式会社 Composite sheet for protective film formation and method for producing same
WO2020218519A1 (en) * 2019-04-26 2020-10-29 リンテック株式会社 Method for producing three-layer body, method for producing four-layer body, method for producing semiconductor device equipped with rear surface protective film, and three-layer body
JP7453879B2 (en) 2020-08-12 2024-03-21 リンテック株式会社 Protective film forming sheet roll and protective film forming sheet roll manufacturing method
JP7084972B2 (en) * 2020-10-06 2022-06-15 リンテック株式会社 Composite sheet for forming a protective film

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200507193A (en) * 2003-07-08 2005-02-16 Lintec Corp Adhesive sheet for dicing and die bonding and method of manufacturing semiconductor device
JP3857953B2 (en) * 2002-05-16 2006-12-13 株式会社巴川製紙所 Adhesive sheet for semiconductor device manufacturing
US20090053518A1 (en) * 2006-03-28 2009-02-26 Lintec Corporation Sheet for Forming a Protective Film for Chips
CN101817250A (en) * 2009-02-27 2010-09-01 琳得科株式会社 Optics diaphragm and manufacture method and polaroid and manufacture method thereof

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2377521T3 (en) 2002-03-12 2012-03-28 Hamamatsu Photonics K.K. Method to divide a substrate
KR100633849B1 (en) * 2002-04-03 2006-10-13 가부시키가이샤 도모에가와 세이시쇼 Adhesive sheet for producing semiconductor devices
JP4364508B2 (en) * 2002-12-27 2009-11-18 リンテック株式会社 Protective film forming sheet for chip back surface and manufacturing method of chip with protective film
KR101169182B1 (en) * 2003-06-06 2012-07-30 히다치 가세고교 가부시끼가이샤 Semiconductor device producing method
EP2360013A4 (en) * 2008-11-27 2013-01-16 Mitsui Du Pont Polychemical Protective film for electronic component, manufacturing method therefor, and use thereof
JP5603757B2 (en) * 2009-12-04 2014-10-08 リンテック株式会社 Laser dicing adhesive sheet and method for manufacturing semiconductor device
JP2011151362A (en) 2009-12-24 2011-08-04 Nitto Denko Corp Dicing tape-integrated film for semiconductor back surface
JP2012033637A (en) 2010-07-29 2012-02-16 Nitto Denko Corp Dicing tape integrated semiconductor rear face film, and method of manufacturing semiconductor device
JP5580701B2 (en) * 2010-09-13 2014-08-27 日東電工株式会社 Dicing die bond film
JP5449622B2 (en) * 2011-07-01 2014-03-19 古河電気工業株式会社 Adhesive film, dicing die bonding film, and semiconductor processing method using the same
JP5865045B2 (en) * 2011-12-07 2016-02-17 リンテック株式会社 Dicing sheet with protective film forming layer and chip manufacturing method
JP6001273B2 (en) * 2012-02-13 2016-10-05 信越化学工業株式会社 Protective film for semiconductor wafer and method for manufacturing semiconductor chip
CN104271694B (en) * 2012-05-14 2017-03-22 琳得科株式会社 Sheet having adhesive resin layer attached thereto, and method for producing semiconductor device
WO2014083872A1 (en) * 2012-11-30 2014-06-05 リンテック株式会社 Sheet for forming resin film for chips and method for manufacturing semiconductor device
CN106104760B (en) * 2014-03-24 2019-11-01 琳得科株式会社 Protective film forms film and piece is used in protective film formation
WO2015145807A1 (en) * 2014-03-24 2015-10-01 リンテック株式会社 Protective film forming film, protective film forming sheet and work product manufacturing method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3857953B2 (en) * 2002-05-16 2006-12-13 株式会社巴川製紙所 Adhesive sheet for semiconductor device manufacturing
TW200507193A (en) * 2003-07-08 2005-02-16 Lintec Corp Adhesive sheet for dicing and die bonding and method of manufacturing semiconductor device
US20090053518A1 (en) * 2006-03-28 2009-02-26 Lintec Corporation Sheet for Forming a Protective Film for Chips
CN101817250A (en) * 2009-02-27 2010-09-01 琳得科株式会社 Optics diaphragm and manufacture method and polaroid and manufacture method thereof

Also Published As

Publication number Publication date
KR102368140B1 (en) 2022-02-25
PH12017500284B1 (en) 2017-07-03
WO2016027888A1 (en) 2016-02-25
CN106660333A (en) 2017-05-10
TWI706023B (en) 2020-10-01
MY182846A (en) 2021-02-05
CN106660333B (en) 2018-11-06
WO2016027883A1 (en) 2016-02-25
KR20170044652A (en) 2017-04-25
TW201940622A (en) 2019-10-16
JPWO2016027888A1 (en) 2017-06-01
CN106660332A (en) 2017-05-10
PH12017500284A1 (en) 2017-07-03
TW201938728A (en) 2019-10-01
MY186759A (en) 2021-08-18
TWI672354B (en) 2019-09-21
TW201614023A (en) 2016-04-16
SG11201701272UA (en) 2017-04-27
TW201614024A (en) 2016-04-16
CN106660332B (en) 2020-08-07
KR20170044108A (en) 2017-04-24
KR102376017B1 (en) 2022-03-17
SG11201701270QA (en) 2017-03-30
JP6589209B2 (en) 2019-10-16
JPWO2016027883A1 (en) 2017-06-01
TWI668290B (en) 2019-08-11
PH12017500285A1 (en) 2017-06-28
PH12017500285B1 (en) 2017-06-28

Similar Documents

Publication Publication Date Title
TWI712670B (en) Sheet for forming protective film and method of manufacturing tip having protective film
JP6319433B2 (en) Composite sheet for protective film formation
JP6324438B2 (en) Protective film forming film and protective film forming sheet
WO2015105002A1 (en) Composite sheet for protective-film formation
JPWO2015146936A1 (en) Protective film-forming film, protective film-forming sheet, workpiece or workpiece manufacturing method, inspection method, workpiece judged to be non-defective, and workpiece judged to be non-defective
JP7008620B2 (en) Sheet for semiconductor processing
JP6464196B2 (en) Resin film forming sheet, resin film forming composite sheet, and silicon wafer recycling method
JP6423458B2 (en) Composite sheet for forming resin film and method for manufacturing chip with resin film
JP2019096913A (en) Sheet for resin film formation and composite sheet for resin film formation
KR102330885B1 (en) Protective membrane forming film
TWI747869B (en) Plates for semiconductor processing
WO2016136774A1 (en) Film-like adhesive agent, adhesive sheet, and method for manufacturing semiconductor device
WO2016098697A1 (en) Sheet laminate for forming resin film
JP6838018B2 (en) Protective film forming film, protective film forming sheet and inspection method
TW202145323A (en) Sheet for manufacturing semiconductor device, and method to manufacture the sheet for manufacturing semiconductor device by sequentially laminating the first adhesive layer, the film-like adhesive, the release film, the second adhesive layer, and the support substrate on a substrate
TW202348756A (en) Protective film-forming film, composite sheet for forming protective film, method of manufacturing semiconductor device, and use of protective film-forming film having desirable storage elastic modulus for a test piece formed by multiple pieces of the protective films
TW202142647A (en) Film-like adhesive and film-like adhesive composite sheet having a fracture strength is 30 MPa or less and a percentage elongation at break is more than 11%
KR20230085855A (en) Film for protective film formation, sheet for protective film formation, composite sheet for protective film formation and device manufacturing method