TWI774672B - Method of manufacturing semiconductor chip having protective film and method of manufacturing semiconductor device - Google Patents

Method of manufacturing semiconductor chip having protective film and method of manufacturing semiconductor device Download PDF

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TWI774672B
TWI774672B TW106113972A TW106113972A TWI774672B TW I774672 B TWI774672 B TW I774672B TW 106113972 A TW106113972 A TW 106113972A TW 106113972 A TW106113972 A TW 106113972A TW I774672 B TWI774672 B TW I774672B
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protective film
forming
film
meth
acrylate
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TW201811971A (en
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稻男洋一
佐藤明德
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日商琳得科股份有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H—ELECTRICITY
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    • H01L23/00—Details of semiconductor or other solid state devices
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    • 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
    • B32B27/08—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 of synthetic resin
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    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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    • H01L21/67703—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 conveying, e.g. between different workstations between different workstations
    • H01L21/67721—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 conveying, e.g. between different workstations between different workstations the substrates to be conveyed not being semiconductor wafers or large planar substrates, e.g. chips, lead frames
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
    • H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/72—Cured, e.g. vulcanised, cross-linked
    • 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
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    • B32B2310/0831—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation using UV radiation
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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Abstract

The present invention relates to a method of manufacturing a semiconductor chip (19) having a protective film in which a semiconductor wafer (18) of a laminated body that has a support sheet (10), an energy beam-curable film for forming a protective film (13), and a semiconductor wafer (18) in this order, is diced, and the film for forming the protective film (13) is irradiated with an enegy beam and thereby cured. Also, the present invention relates to a method of manufacturing the semiconductor device in which the semiconductor chip (19) having the protective film is picked up and the semiconductor chip (19) is connected to a substrate.

Description

附有保護膜的半導體晶片的製造方法以及半導體裝置的製造方法 Manufacturing method of semiconductor wafer with protective film and manufacturing method of semiconductor device

本發明係關於一種附有保護膜的半導體晶片的製造方法以及半導體裝置的製造方法。 The present invention relates to a method of manufacturing a semiconductor wafer with a protective film and a method of manufacturing a semiconductor device.

本申請案主張基於2016年4月28日在日本提出申請之日本特願2016-92033號的優先權，並將該申請案的內容引用至本文中。 This application claims priority based on Japanese Patent Application No. 2016-92033 for which it applied in Japan on April 28, 2016, and the content of this application is incorporated herein by reference.

近年來，業界使用稱為所謂倒裝(face down)方式之安裝方法製造半導體裝置。倒裝方式中，使用於電路面上具有凸塊(bump)等電極之半導體晶片，將前述電極與基板接合。因此，會有半導體晶片中的與電路面為相反側的背面裸露之情形。 In recent years, the industry has used a mounting method called a so-called face down method to manufacture semiconductor devices. In the flip-chip method, a semiconductor wafer having electrodes such as bumps on a circuit surface is used, and the electrodes are bonded to a substrate. Therefore, the back surface of the semiconductor wafer on the opposite side to the circuit surface may be exposed.

會有於該裸露之半導體晶片的背面形成含有有機材 料之樹脂膜作為保護膜從而以附有保護膜的半導體晶片之形式組入至半導體裝置中之情形。 There will be formation of organic material on the backside of the bare semiconductor wafer The resin film of the material is used as a protective film to be incorporated into a semiconductor device in the form of a semiconductor wafer with a protective film.

保護膜係用以防止在切割步驟或封裝之後半導體晶片產生龜裂。 The protective film is used to prevent cracking of the semiconductor wafer after the dicing step or packaging.

為了形成此種保護膜，例如使用於支持片上具備用以形成保護膜之保護膜形成用膜而成之保護膜形成用複合片。保護膜形成用複合片中，可使保護膜形成用膜藉由硬化而形成保護膜，進而可利用支持片作為切割片(dicing sheet)，從而可製成保護膜形成用膜與切割片形成為一體之保護膜形成用複合片。 In order to form such a protective film, for example, the composite sheet for protective film formation which is provided with the film for protective film formation for forming a protective film on a support sheet is used. In the composite sheet for forming a protective film, the film for forming a protective film can be hardened to form a protective film, and a support sheet can be used as a dicing sheet, so that the film for forming a protective film and the dicing sheet can be formed as A composite sheet for forming an integrated protective film.

作為此種保護膜形成用複合片，例如至今主要利用具備熱硬化性之保護膜形成用膜而成之保護膜形成用複合片，前述熱硬化性之保護膜形成用膜係藉由加熱而硬化，藉此形成保護膜。該情形時，例如於半導體晶圓的背面(與電極形成面為相反側的面)藉由熱硬化性之保護膜形成用膜貼附保護膜形成用複合片後，藉由加熱使保護膜形成用膜硬化而成為保護膜，藉由切割將半導體晶圓連同保護膜一起分割而製成半導體晶片。然後，將半導體晶片在保持貼附有該保護膜之狀態下直接自支持片拉離而進行拾取。再者，亦存在保護膜形成用膜之硬化及切割以與此相反之順序進行之情形。 As such a composite sheet for forming a protective film, for example, conventionally, a composite sheet for forming a protective film mainly using a film for forming a protective film having thermosetting properties, which is cured by heating , thereby forming a protective film. In this case, for example, after attaching the composite sheet for forming a protective film to the back surface of the semiconductor wafer (the surface opposite to the electrode forming surface) with a thermosetting film for forming a protective film, the protective film is formed by heating. The film is cured to be a protective film, and the semiconductor wafer is divided together with the protective film by dicing to obtain a semiconductor wafer. Then, the semiconductor wafer is directly pulled away from the support sheet in a state where the protective film is kept attached, and is picked up. In addition, there is a case where hardening and dicing of the film for protective film formation are performed in the reverse order.

但是，熱硬化性之保護膜形成用膜之加熱硬化通常需要數小時左右之長時間，因此期望縮短硬化時間。針對上述情形，業界正研究將可藉由照射紫外線等能量線而硬化之保護膜形成用膜用於形成保護膜。例如揭示有：形成於剝離膜上之能量線硬化型保護膜(參照專利文獻1)；可形成高硬度且對半導體晶片之密接性優異之保護膜之能量線硬化型晶片保護用膜(參照專利文獻2)。 However, heat curing of a thermosetting protective film-forming film usually requires a long time of about several hours, and therefore it is desired to shorten the curing time. In view of the above situation, the industry is studying the use of a film for forming a protective film that can be cured by irradiation with energy rays such as ultraviolet rays for forming a protective film. For example, there are disclosed: an energy ray hardening type protective film formed on a peeling film (refer to Patent Document 1); Reference 2).

[先前技術文獻] [Prior Art Literature] [專利文獻] [Patent Literature]

專利文獻1：日本特許第5144433號公報。 Patent Document 1: Japanese Patent No. 5144433.

專利文獻2：日本特開2010-031183號公報。 Patent Document 2: Japanese Patent Laid-Open No. 2010-031183.

但是，使用專利文獻1及專利文獻2中所揭示之能量線硬化型晶片保護用膜製造半導體晶片、半導體裝置之過程中，切割半導體晶圓時，有如下之虞：因晶片飛濺導致不良，或者因切削水向保護膜形成用膜或保護膜與支持片之間浸入而污染保護膜的表面。 However, in the process of manufacturing semiconductor wafers and semiconductor devices using the energy-beam-curable wafer protection films disclosed in Patent Document 1 and Patent Document 2, when the semiconductor wafer is diced, there is a risk of causing defects due to wafer spatter, or The surface of the protective film is contaminated by the infiltration of cutting water into the film for protective film formation or between the protective film and the support sheet.

因此，本發明之目的在於提供一種附有保護膜的半導體晶片的製造方法以及半導體裝置的製造方法，前述附有保護膜的半導體晶片的製造方法中，於切割半導體晶圓 時，無晶片飛濺，或者切削水向保護膜形成用膜或保護膜與支持片之間浸入之虞，可於半導體晶片的背面形成良好的保護膜。 Therefore, an object of the present invention is to provide a method of manufacturing a semiconductor wafer with a protective film and a method of manufacturing a semiconductor device, in which the method of manufacturing the semiconductor wafer with a protective film includes dicing the semiconductor wafer. In this case, there is no risk of wafer splashing or intrusion of cutting water into the protective film forming film or between the protective film and the support sheet, and a good protective film can be formed on the back surface of the semiconductor wafer.

為了解決上述課題，本發明提供一種附有保護膜的半導體晶片的製造方法，對依序具備有支持片、能量線硬化性之保護膜形成用膜及半導體晶圓之積層體中的前述半導體晶圓進行切割，接著對前述保護膜形成用膜照射能量線而使前述保護膜形成用膜硬化。 In order to solve the above-mentioned problems, the present invention provides a method for producing a semiconductor wafer with a protective film, wherein the semiconductor wafer is sequentially provided with a support sheet, a film for forming a protective film with energy ray curability, and a laminate of the semiconductor wafer. The circle is cut, and then the film for forming a protective film is irradiated with energy rays to cure the film for forming a protective film.

本發明之附有保護膜的半導體晶片的製造方法中，較佳為前述積層體中的支持片與前述保護膜形成用膜之間的黏著力為100mN/25mm以上。 In the manufacturing method of the semiconductor wafer with a protective film of this invention, it is preferable that the adhesive force between the support sheet in the said laminated body and the said film for protective film formation is 100 mN/25mm or more.

本發明之附有保護膜的半導體晶片的製造方法中，前述積層體可於前述半導體晶圓貼附前述保護膜形成用膜後，於前述保護膜形成用膜貼附前述支持片而成。 In the manufacturing method of the semiconductor wafer with a protective film of this invention, the said laminated body can attach the said support sheet to the said film for protective film formation after attaching the said film for protection film to the said semiconductor wafer.

本發明之附有保護膜的半導體晶片的製造方法中，前述積層體可將於支持片上具備前述保護膜形成用膜而成之保護膜形成用複合片的前述保護膜形成用膜側貼附於前述半導體晶圓而成。 In the method for producing a semiconductor wafer with a protective film of the present invention, the layered body may be attached to the protective film-forming film side of the composite sheet for forming a protective film comprising the film for forming a protective film on a support sheet. The aforementioned semiconductor wafer is formed.

本發明之半導體裝置的製造方法係拾取藉由上述任一項所記載之附有保護膜的半導體晶片的製造方法所獲得之附有保護膜的半導體晶片，將前述半導體晶片連接於基板。 The manufacturing method of the semiconductor device of this invention picks up the semiconductor wafer with a protective film obtained by the manufacturing method of the semiconductor wafer with a protective film as described in any one of the above, and connects the said semiconductor wafer to a board|substrate.

根據本發明，提供一種附有保護膜的半導體晶片的製造方法以及半導體裝置的製造方法，前述附有保護膜的半導體晶片的製造方法中，切割半導體晶圓時，無晶片飛濺，或者切削水向保護膜形成用膜或保護膜與支持片之間浸入之虞，可於半導體晶片形成保護膜。 According to the present invention, there is provided a method of manufacturing a semiconductor wafer with a protective film, and a method of manufacturing a semiconductor device. In the method of manufacturing a semiconductor wafer with a protective film, when the semiconductor wafer is cut, there is no wafer spatter or cutting water. A protective film can be formed on a semiconductor wafer because there is a risk of intrusion between the film for protective film formation or the protective film and the support sheet.

1A、1B、1C、1D、1E:保護膜形成用複合片 1A, 1B, 1C, 1D, 1E: Composite sheet for forming protective film

2F:保護膜形成用片 2F: Sheet for forming protective film

10:支持片 10: Support Sheet

10a:(支持片的)表面 10a: Surface (of the supporting sheet)

11:基材 11: Substrate

11a:(基材的)表面 11a: Surface (of the substrate)

12:黏著劑層 12: Adhesive layer

12a:(黏著劑層的)表面 12a: Surface (of the adhesive layer)

13、23:保護膜形成用膜 13, 23: Film for forming protective film

13'、23':保護膜 13', 23': protective film

13a、23a:(保護膜形成用膜的一方的)表面 13a, 23a: (one side of the film for protective film formation) surface

13b:(保護膜形成用膜的另一方的)表面 13b: (the other side of the protective film-forming film) surface

15:剝離膜 15: Peel off film

15':第1剝離膜 15': 1st release film

15":第2剝離膜 15": 2nd release film

16:治具用接著劑層 16: Adhesive layer for jig

16a:(治具用接著劑層的)表面 16a: (the surface of the adhesive layer for the jig)

17:環狀框 17: Ring box

18:半導體晶圓 18: Semiconductor Wafers

19:半導體晶片 19: Semiconductor wafer

20:切割刀片 20: Cutting Blade

21:能量線照射裝置 21: Energy ray irradiation device

圖1係顯示本發明之附有保護膜的半導體晶片的製造方法之概略圖。 FIG. 1 is a schematic view showing a method of manufacturing a semiconductor wafer with a protective film of the present invention.

圖2係以示意方式顯示可用於本發明之保護膜形成用複合片的一實施形態之剖視圖。 FIG. 2 is a cross-sectional view schematically showing an embodiment of the composite sheet for forming a protective film that can be used in the present invention.

圖3係以示意方式顯示可用於本發明之保護膜形成用複合片的另一實施形態之剖視圖。 3 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film that can be used in the present invention.

圖4係以示意方式顯示可用於本發明之保護膜形成用複合片的又一實施形態之剖視圖。 FIG. 4 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film that can be used in the present invention.

圖5係以示意方式顯示可用於本發明之保護膜形成用複合片的又一實施形態之剖視圖。 FIG. 5 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film that can be used in the present invention.

圖6係以示意方式顯示可用於本發明之保護膜形成用複合片的又一實施形態之剖視圖。 FIG. 6 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film that can be used in the present invention.

圖7係以示意方式顯示可用於本發明之保護膜形成用片的實施形態之剖視圖。 FIG. 7 is a cross-sectional view schematically showing an embodiment of the sheet for forming a protective film that can be used in the present invention.

◇附有保護膜的半導體晶片以及半導體裝置的製造方法 ◇Semiconductor wafer with protective film and manufacturing method of semiconductor device

圖1係顯示本發明之附有保護膜的半導體晶片的製造方法之概略圖。 FIG. 1 is a schematic view showing a method of manufacturing a semiconductor wafer with a protective film of the present invention.

本發明之附有保護膜的半導體晶片19的製造方法係對依序具備有支持片10、能量線硬化性之保護膜形成用膜13及半導體晶圓18之積層體中的前述半導體晶圓18進行切割，接著對前述保護膜形成用膜13照射能量線而使前述保護膜形成用膜13硬化。 The manufacturing method of the semiconductor wafer 19 with a protective film of the present invention is performed on the semiconductor wafer 18 including the support sheet 10 , the film for forming a protective film 13 having energy ray curability, and the laminate of the semiconductor wafer 18 in this order. Dicing is performed, and then the film 13 for forming a protective film is irradiated with energy rays to cure the film 13 for forming a protective film.

再者，自圖1可知，前述半導體晶圓18係貼附於前述保護膜形成用膜13之表面的一部分。 Furthermore, as is clear from FIG. 1 , the semiconductor wafer 18 is attached to a part of the surface of the protective film forming film 13 .

由於在切割後對保護膜形成用膜13照射能量線而使保護膜形成用膜13硬化，故而切割時的保護膜形成用膜13相對較柔軟，因此切割半導體晶圓18時，無切削水向保護膜形成用膜13或保護膜13'與支持片10之間浸入之虞，從而可於半導體晶片19的背面形成良好的保護膜13'。 After dicing, the protective film forming film 13 is hardened by irradiating energy rays to the protective film forming film 13 . Therefore, the protective film forming film 13 during dicing is relatively soft. Therefore, when the semiconductor wafer 18 is diced, no cutting water flows. The protective film 13 ′ for forming a protective film or the protective film 13 ′ and the support sheet 10 may be infiltrated, so that a favorable protective film 13 ′ can be formed on the back surface of the semiconductor wafer 19 .

本說明書中，所謂「切割」可列舉以下情形為例：一邊使埋入有金剛石研磨粒之切割刀片以高速旋轉一邊切削半導體晶圓；藉由使用雷射光之雷射切割法切削半導體晶圓。 In this specification, the term "dicing" can be exemplified in the following cases: cutting a semiconductor wafer while rotating a dicing blade embedded with diamond abrasive grains at a high speed; cutting a semiconductor wafer by a laser dicing method using laser light.

前述積層體可於半導體晶圓貼附前述保護膜形成用膜後，貼附於前述支持片而成，此時，可分別適宜選擇適於半導體晶圓之製品、製造之保護膜形成用膜及支持片使 用。 The laminated body can be formed by attaching the film for forming a protective film to a semiconductor wafer, and then attaching it to the supporting sheet. In this case, a product suitable for a semiconductor wafer, a film for forming a protective film and a film suitable for manufacturing can be appropriately selected. support chip use.

該情形之本發明之附有保護膜的半導體晶片的製造方法係能如下所示。 In this case, the manufacturing method of the semiconductor wafer with a protective film of this invention can be as follows.

亦即，於半導體晶圓的背面(與電極形成面為相反側的面)貼附保護膜形成用膜後，於保護膜形成用膜貼附支持片而製成積層體。接著，藉由切割將半導體晶圓連同保護膜形成用膜一起分割而製成半導體晶片。接著，對已分割之保護膜形成用膜照射能量線，使保護膜形成用膜硬化，製成附有保護膜的半導體晶片。 That is, after affixing the film for protective film formation to the back surface (surface on the opposite side to the electrode formation surface) of the semiconductor wafer, a support sheet is affixed to the film for protective film formation to form a laminate. Next, a semiconductor wafer is divided|segmented together with the film for protective film formation by dicing, and a semiconductor wafer is produced. Next, the divided film for protective film formation is irradiated with energy rays, the film for protective film formation is cured, and a semiconductor wafer with a protective film is produced.

前述積層體可將於支持片上具備前述保護膜形成用膜而成之保護膜形成用複合片的前述保護膜形成用膜側貼附於前述半導體晶圓而成，藉此，可將貼附步驟簡化。 The above-mentioned layered body can be formed by attaching the film side for the protective film forming of the composite sheet for forming a protective film including the film for forming the protective film on the support sheet to the semiconductor wafer, and thereby the attaching step can be performed. simplify.

該情形之本發明之附有保護膜的半導體晶片的製造方法係能如下所示。 In this case, the manufacturing method of the semiconductor wafer with a protective film of this invention can be as follows.

亦即，將保護膜形成用複合片，藉由該保護膜形成用複合片之保護膜形成用膜貼附於半導體晶圓的背面(與電極形成面為相反側的面)。接著，藉由切割將半導體晶圓連同保護膜形成用膜一起分割而製成半導體晶片。接著，對已分割之保護膜形成用膜照射能量線，使保護膜形成用膜硬化，製成附有保護膜的半導體晶片。 That is, the composite sheet for protective film formation and the film for protective film formation of the composite sheet for protective film formation are attached to the back surface (surface opposite to the electrode formation surface) of the semiconductor wafer. Next, a semiconductor wafer is divided|segmented together with the film for protective film formation by dicing, and a semiconductor wafer is produced. Next, the divided film for protective film formation is irradiated with energy rays, the film for protective film formation is cured, and a semiconductor wafer with a protective film is produced.

以下，利用與先前法相同的方法，將附有保護膜的半導體晶片在保持貼附有該保護膜之狀態下直接自支持片 拉離而進行拾取，將所獲得之附有保護膜的半導體晶片的半導體晶片倒裝晶片連接於基板的電路面後，製成半導體封裝。然後，使用該半導體封裝，製作目標半導體裝置即可。 Next, using the same method as the previous method, the semiconductor wafer with the protective film is directly self-supporting in the state where the protective film is attached. It pulls out and picks up, and after connecting the semiconductor wafer of the obtained semiconductor wafer with a protective film to the circuit surface of a board|substrate by flip-chip, it is set as a semiconductor package. Then, using this semiconductor package, a target semiconductor device may be fabricated.

◇保護膜形成用複合片 ◇Composite sheet for protective film formation

可用於本發明之保護膜形成用複合片於支持片上具備能量線硬化性之保護膜形成用膜。 The composite sheet for protective film formation which can be used for this invention has the film for protective film formation which has energy ray curability on the support sheet.

本說明書中，所謂「保護膜形成用膜」意指硬化前之保護膜形成用膜，所謂「保護膜」意指保護膜形成用膜硬化後之膜。 In this specification, "the film for protective film formation" means the film for protective film formation before hardening, and the "protective film" means the film after hardening of the film for protective film formation.

本發明中，所謂「能量線」意指具有能量量子的電磁波或帶電粒子束，作為前述能量線的示例，可列舉紫外線、放射線、電子束等。 In the present invention, the term "energy rays" means electromagnetic waves or charged particle beams having energy quanta, and examples of the energy rays include ultraviolet rays, radiation, and electron beams.

紫外線例如可藉由使用高壓水銀燈、融合(Fusion)H型燈、氙氣燈、黑光燈或LED(Light-Emitting Diode；發光二極體)燈等作為紫外線源進行照射。電子束可照射藉由電子束加速器等所產生之電子束。 Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H-type lamp, a xenon lamp, a black light lamp, or an LED (Light-Emitting Diode; light-emitting diode) lamp or the like as an ultraviolet source. The electron beam may be irradiated with an electron beam generated by an electron beam accelerator or the like.

本發明中，所謂「能量線硬化性」意指藉由照射能量線而硬化之性質，所謂「非能量線硬化性」意指即便照射能量線亦不硬化之性質。 In the present invention, the term "energy-beam curability" means the property of being cured by irradiation with energy rays, and the term "non-energy-beam curability" means the property of not being cured even when irradiated with energy rays.

前述積層體中的支持片與前述保護膜形成用膜之間 的黏著力並無特別限定，例如可為80mN/25mm以上，亦可為100mN/25mm以上，亦可為150mN/25mm以上，亦可為200mN/25mm以上，另外，上限值並無特別限定，可為10000mN/25mm以下，可為8000mN/25mm以下，亦可為7000mN/25mm以下。藉由調整為前述下限值以上，切割時矽晶片之飛散得到抑制，亦可防止切削水向保護膜形成用膜與支持片之間浸入。藉由調整為前述上限值以下，隨後藉由照射能量線使之硬化而成為保護膜時，可容易適當地調整前述保護膜與前述支持片之間的黏著力。 Between the support sheet in the above-mentioned laminate and the film for forming a protective film The adhesive force of the adhesive is not particularly limited, for example, it can be 80mN/25mm or more, 100mN/25mm or more, 150mN/25mm or more, and 200mN/25mm or more. In addition, the upper limit is not particularly limited. It can be 10000mN/25mm or less, 8000mN/25mm or less, and 7000mN/25mm or less. By adjusting to be more than the aforementioned lower limit value, the scattering of the silicon wafer during dicing is suppressed, and the infiltration of cutting water between the film for forming a protective film and the support sheet can also be prevented. The adhesive force between the said protective film and the said support sheet can be easily and suitably adjusted, when it becomes a protective film by adjusting to be below the said upper limit and hardening by irradiating an energy ray subsequently.

作為本發明之另一態樣，前述積層體中的支持片與前述保護膜形成用膜之間的黏著力為10mN/25mm至30000mN/25mm，較佳為100mN/25mm至20000mN/25mm，更佳為150mN/25mm至10000mN/25mm，進而較佳為200mN/25mm至8000mN/25mm。 As another aspect of the present invention, the adhesive force between the support sheet in the laminate and the film for forming the protective film is 10mN/25mm to 30000mN/25mm, preferably 100mN/25mm to 20000mN/25mm, more preferably It is 150mN/25mm to 10000mN/25mm, and more preferably 200mN/25mm to 8000mN/25mm.

本說明書中，前述支持片與前述保護膜形成用膜之間的黏著力可藉由後述之測定方法進行測定。 In this specification, the adhesive force between the said support sheet and the said film for protective film formation can be measured by the measurement method mentioned later.

前述保護膜形成用膜藉由照射能量線而硬化，成為保護膜。該保護膜保護半導體晶圓或半導體晶片的背面(與電極形成面為相反側的面)。保護膜形成用膜為軟質，可容易地貼附於貼附對象物。對前述保護膜形成用膜照射能量線而成為保護膜時，前述保護膜與前述支持片之間的黏著力較佳為50mN/25mm至1500mN/25mm，更佳為52mN/25mm至1450mN/25mm，尤佳為53mN/25mm至 1430mN/25mm。藉由前述黏著力為前述下限值以上，拾取附有保護膜的半導體晶片時，目標外的附有保護膜的半導體晶片之拾取得到抑制，從而可高選擇性地拾取目標之附有保護膜的半導體晶片。藉由前述黏著力為前述上限值以下，拾取附有保護膜的半導體晶片時，半導體晶片之破裂及缺損得到抑制。如此，藉由前述黏著力為特定範圍內，保護膜形成用複合片具有良好的拾取適性。 The said film for protective film formation is hardened by irradiating an energy ray, and becomes a protective film. This protective film protects the semiconductor wafer or the back surface of the semiconductor wafer (the surface on the opposite side to the electrode formation surface). The film for protective film formation is soft and can be easily attached to the object to be attached. When the above-mentioned protective film is formed by irradiating energy rays to the protective film, the adhesive force between the above-mentioned protective film and the above-mentioned supporting sheet is preferably 50mN/25mm to 1500mN/25mm, more preferably 52mN/25mm to 1450mN/25mm, 53mN/25mm to 1430mN/25mm. When the above-mentioned adhesive force is equal to or more than the above-mentioned lower limit value, when picking up a semiconductor wafer with a protective film, the pickup of a semiconductor wafer with a protective film other than the target is suppressed, and the target with a protective film can be picked up with high selectivity. semiconductor wafers. When the said adhesive force is below the said upper limit value, when picking up the semiconductor wafer with a protective film, the cracking and the defect of a semiconductor wafer are suppressed. Thus, since the said adhesive force exists in a specific range, the composite sheet for protective film formation has favorable pick-up property.

本說明書中，前述保護膜與前述支持片之間的黏著力可藉由後述之測定方法進行測定。 In this specification, the adhesive force between the said protective film and the said support sheet can be measured by the measurement method mentioned later.

可用於本發明之保護膜形成用複合片中，前述保護膜形成用膜為能量線硬化性，藉此相較於具備熱硬化性之保護膜形成用膜之以往之保護膜形成用複合片之情形而言，可藉由短時間內之硬化而形成保護膜。 It can be used in the composite sheet for forming a protective film of the present invention, wherein the film for forming a protective film is energy ray curable, thereby comparing with the conventional composite sheet for forming a protective film having a thermosetting film for forming a protective film. In this case, the protective film can be formed by hardening in a short time.

本發明中，可不使用保護膜形成用複合片，而於半導體晶圓的背面貼附保護膜形成用膜後，於前述保護膜形成用膜貼附支持片，此時的保護膜形成用膜及支持片可適宜使用上述之保護膜形成用複合片之說明中所說明之保護膜形成用膜及支持片。 In the present invention, without using the composite sheet for forming a protective film, after the film for forming a protective film is pasted on the back surface of the semiconductor wafer, a support sheet can be pasted on the film for forming a protective film, and the film for forming a protective film and As a support sheet, the film for protective film formation and the support sheet demonstrated in the description of the composite sheet for protective film formation mentioned above can be used suitably.

本發明中，作為保護膜形成用複合片之使用對象之半導體晶圓或半導體晶片的厚度並無特別限定，就獲得更顯著的本發明之功效而言，較佳為30μm至1000μm，更佳為100μm至300μm。 In the present invention, the thickness of the semiconductor wafer or the semiconductor wafer used as the protective film-forming composite sheet is not particularly limited, and in terms of obtaining more significant effects of the present invention, it is preferably 30 μm to 1000 μm, more preferably 100μm to 300μm.

以下，對本發明之構成進行詳細的說明。 Hereinafter, the configuration of the present invention will be described in detail.

◎支持片 ◎Support film

前述支持片可由1層(單層)構成，亦可由2層以上之複數層構成。於支持片由複數層構成之情形時，這些複數層的構成材料及厚度相互可相同亦可不同，只要無損本發明之功效，則這些複數層之組合並無特別限定。 The aforementioned support sheet may be constituted by one layer (single layer), or may be constituted by a plurality of layers of two or more layers. When the support sheet is composed of plural layers, the constituent materials and thicknesses of these plural layers may be the same or different from each other, and the combination of these plural layers is not particularly limited as long as the effect of the present invention is not impaired.

本說明書中，並不限於支持片之情形，所謂「複數層相互可相同亦可不同」意指「可全部層相同，亦可全部層皆不同，還可僅一部分層相同」，進而所謂「複數層相互不同」意指「各層的構成材料及厚度的至少一者相互不同」。 In this specification, not limited to the case of the support sheet, the phrase "a plurality of layers may be the same or different from each other" means "all layers may be the same, all layers may be different, or only a part of the layers may be the same". "The layers are different from each other" means "at least one of the constituent material and the thickness of each layer is different from each other".

作為較佳的支持片，例如可列舉：於基材上以直接接觸之方式積層黏著劑層而成之支持片、於基材上經由中間層積層黏著劑層而成之支持片、僅由基材構成之支持片等。 As a preferable support sheet, for example, a support sheet formed by laminating an adhesive layer on a substrate in a direct contact manner, a supporting sheet formed by laminating an adhesive layer on a substrate through an intermediate layer, and The support sheet composed of materials, etc.

以下，參照圖式並按照上述支持片之每個種類說明可用於本發明之保護膜形成用複合片的示例。對於以下之說明中所使用之圖，為了易於理解本發明之特徵，方便起見，會有將成為主要部分之部分放大顯示之情形，而並不限於各構成要素的尺寸比率等與實際相同。 Hereinafter, examples of the composite sheet for forming a protective film that can be used in the present invention will be described for each type of the above-mentioned support sheet with reference to the drawings. In the drawings used in the following description, in order to facilitate the understanding of the features of the present invention and for convenience, parts that will be the main parts may be shown enlarged, and the dimensional ratios and the like of each constituent element are not limited to be the same as the actual ones.

圖2係以示意方式顯示可用於本發明之保護膜形成用複合片的一實施形態之剖視圖。 FIG. 2 is a cross-sectional view schematically showing an embodiment of the composite sheet for forming a protective film that can be used in the present invention.

此處所示之保護膜形成用複合片1A於基材11上具備黏著劑層12並於黏著劑層12上具備保護膜形成用膜13而成。支持片10為基材11及黏著劑層12之積層體，換言之，保護膜形成用複合片1A具有於支持片10的一方的表面10a上積層有保護膜形成用膜13之構成。保護膜形成用複合片1A進一步於保護膜形成用膜13上具備剝離膜15。 The composite sheet 1A for protective film formation shown here is provided with the adhesive bond layer 12 on the base material 11, and is provided with the film 13 for protective film formation on the adhesive bond layer 12. The support sheet 10 is a laminate of the base material 11 and the adhesive layer 12 , in other words, the protective film-forming composite sheet 1A has a structure in which the protective film-forming film 13 is laminated on one surface 10 a of the support sheet 10 . The composite sheet 1A for protective film formation is further provided with the release film 15 on the film 13 for protective film formation.

保護膜形成用複合片1A中，於基材11的一方的表面11a積層有黏著劑層12，於黏著劑層12的表面12a的整個面積層有保護膜形成用膜13，於保護膜形成用膜13的表面13a的一部分亦即周緣部附近的區域積層有治具用接著劑層16，於保護膜形成用膜13的表面13a中未積層治具用接著劑層16之面及治具用接著劑層16的表面16a(上表面及側面)積層有剝離膜15。 In the composite sheet for forming a protective film 1A, the adhesive layer 12 is laminated on one surface 11a of the base material 11, and the film 13 for forming a protective film is layered on the entire surface 12a of the adhesive layer 12. A part of the surface 13a of the film 13, that is, the region near the peripheral edge portion is laminated with the adhesive layer 16 for a jig, and the surface 13a of the film 13 for forming a protective film is not laminated with the adhesive layer 16 for a jig and the surface for a jig. The release film 15 is laminated on the surface 16a (the upper surface and the side surface) of the adhesive layer 16 .

保護膜形成用複合片1A中，硬化後之保護膜形成用膜13(亦即保護膜13')與支持片10之間的黏著力，換言之保護膜13'與黏著劑層12之間的黏著力較佳為50mN/25mm至1500mN/25mm。 In the protective film forming composite sheet 1A, the adhesive force between the protective film forming film 13 (that is, the protective film 13 ′) after curing and the support sheet 10 , in other words, the adhesion between the protective film 13 ′ and the adhesive layer 12 The force is preferably 50mN/25mm to 1500mN/25mm.

治具用接著劑層16例如可為含有接著劑成分之單層 結構，亦可為於成為芯材之片的雙面積層有含有接著劑成分之層之複數層結構。 The adhesive layer 16 for a jig may be, for example, a single layer containing an adhesive component The structure may be a plural-layer structure in which a layer containing an adhesive component is provided on the double-surface layer of the sheet to be the core material.

圖2所示之保護膜形成用複合片1A係以下述方式使用：在移除剝離膜15之狀態下，於保護膜形成用膜13的表面13a貼附半導體晶圓(省略圖示)的背面，並進一步將治具用接著劑層16的表面16a中的上表面貼附於環狀框等治具。 The composite sheet 1A for forming a protective film shown in FIG. 2 is used by attaching the back surface of a semiconductor wafer (not shown) to the surface 13 a of the film 13 for forming a protective film with the release film 15 removed. , and further attach the upper surface of the surface 16a of the adhesive layer 16 for a jig to a jig such as an annular frame.

圖3係以示意方式顯示可用於本發明之保護膜形成用複合片的另一實施形態之剖視圖。再者，圖3以後之圖中，對於既已說明之圖所示相同的構成要素，標附與該已說明之圖之情形相同的符號，並省略該符號的詳細說明。 3 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film that can be used in the present invention. 3 and later, the same components shown in the already described drawings are assigned the same reference numerals as those in the already described drawings, and the detailed description of the reference numerals is omitted.

關於此處所示之保護膜形成用複合片1B，除了不具備治具用接著劑層16之方面以外，與圖2所示之保護膜形成用複合片1A相同。亦即，保護膜形成用複合片1B中，於基材11的一方的表面11a積層有黏著劑層12，於黏著劑層12的表面12a的整個面積層有保護膜形成用膜13，於保護膜形成用膜13的表面13a的整個面積層有剝離膜15。 The composite sheet 1B for forming a protective film shown here is the same as the composite sheet 1A for forming a protective film shown in FIG. 2 except that it does not include the adhesive layer 16 for a jig. That is, in the composite sheet 1B for forming a protective film, the adhesive layer 12 is laminated on one surface 11 a of the base material 11 , and the film 13 for forming a protective film is layered on the entire surface 12 a of the adhesive layer 12 . The release film 15 is layered over the entire area of the surface 13 a of the film-forming film 13 .

圖3所示之保護膜形成用複合片1B係以下述方式使用：在移除剝離膜15之狀態下，於保護膜形成用膜13的 表面13a中的中央側的一部分區域貼附半導體晶圓(省略圖示)的背面，並進一步將保護膜形成用膜13的周緣部附近的區域貼附於環狀框等治具。 The composite sheet 1B for forming a protective film shown in FIG. 3 is used as follows: in the state where the release film 15 is removed, on the protective film forming film 13 The back surface of the semiconductor wafer (not shown) is attached to a part of the central area of the front surface 13a, and the area near the peripheral edge of the protective film forming film 13 is attached to a jig such as a ring frame.

圖4係以示意方式顯示可用於本發明之保護膜形成用複合片的又一實施形態之剖視圖。 FIG. 4 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film that can be used in the present invention.

關於此處所示之保護膜形成用複合片1C，除了不具備黏著劑層12之方面以外，與圖2所示之保護膜形成用複合片1A相同。亦即，保護膜形成用複合片1C中，支持片10僅由基材11構成。於基材11的一方的表面11a(支持片10的一方的表面10a)積層有保護膜形成用膜13，於保護膜形成用膜13的表面13a的一部分亦即周緣部附近的區域積層有治具用接著劑層16，於保護膜形成用膜13的表面13a中未積層治具用接著劑層16之面及治具用接著劑層16的表面16a(上表面及側面)積層剝離膜15。 The composite sheet 1C for forming a protective film shown here is the same as the composite sheet 1A for forming a protective film shown in FIG. 2 except that the adhesive layer 12 is not provided. That is, in the composite sheet 1C for protective film formation, the support sheet 10 consists only of the base material 11 . The protective film forming film 13 is laminated on one surface 11a of the substrate 11 (one surface 10a of the support sheet 10), and a protective film forming film 13 is laminated on a part of the surface 13a of the protective film forming film 13, that is, a region near the peripheral edge. The adhesive layer 16 is used, and the release film 15 is laminated on the surface 13a of the protective film forming film 13 on the surface where the adhesive layer 16 for jig is not laminated, and on the surface 16a (upper surface and side surface) of the adhesive layer 16 for jig. .

保護膜形成用複合片1C中，硬化後之保護膜形成用膜13(亦即保護膜)與支持片10之間的黏著力，換言之保護膜與基材11之間的黏著力較佳為50mN/25mm至1500mN/25mm。 In the protective film forming composite sheet 1C, the adhesive force between the protective film forming film 13 (that is, the protective film) after curing and the support sheet 10, in other words, the adhesive force between the protective film and the substrate 11 is preferably 50 mN /25mm to 1500mN/25mm.

圖4所示之保護膜形成用複合片1C係以下述方式使用：與圖2所示之保護膜形成用複合片1A同樣地，在移除剝離膜15之狀態下，於保護膜形成用膜13的表面13a 貼附半導體晶圓(省略圖示)的背面，並進一步將治具用接著劑層16的表面16a中的上表面貼附於環狀框等治具。 The composite sheet 1C for forming a protective film shown in FIG. 4 is used in the same manner as the composite sheet 1A for forming a protective film shown in FIG. Surface 13a of 13 The back surface of a semiconductor wafer (illustration omitted) is attached, and the upper surface of the surface 16a of the adhesive layer 16 for jigs is attached to a jig such as a ring frame.

圖5係以示意方式顯示可用於本發明之保護膜形成用複合片的又一實施形態之剖視圖。 FIG. 5 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film that can be used in the present invention.

關於此處所示之保護膜形成用複合片1D，除了不具備治具用接著劑層16之方面以外，與圖4所示之保護膜形成用複合片1C相同。亦即，保護膜形成用複合片1D中，於基材11的一方的表面11a積層有保護膜形成用膜13，於保護膜形成用膜13的表面13a的整個面積層有剝離膜15。 The composite sheet 1D for forming a protective film shown here is the same as the composite sheet 1C for forming a protective film shown in FIG. 4 except that it does not include the adhesive layer 16 for a jig. That is, in the composite sheet 1D for protective film formation, the film 13 for protective film formation is laminated|stacked on one surface 11a of the base material 11, and the release film 15 is laminated|stacked on the whole surface 13a of the film 13 for protective film formation.

圖5所示之保護膜形成用複合片1D係以下述方式使用：與圖3所示之保護膜形成用複合片1B同樣地，在移除剝離膜15之狀態下，於保護膜形成用膜13的表面13a中的中央側的一部分區域貼附半導體晶圓(省略圖示)的背面，並進一步將保護膜形成用膜13的周緣部附近的區域貼附於環狀框等治具。 The composite sheet 1D for forming a protective film shown in FIG. 5 is used in the same manner as the composite sheet 1B for forming a protective film shown in FIG. The back surface of a semiconductor wafer (not shown) is adhered to a part of the center side area of the front surface 13a of the front surface 13a, and the area near the peripheral edge of the protective film forming film 13 is adhered to a jig such as a ring frame.

圖6係以示意方式顯示可用於本發明之保護膜形成用複合片的又一實施形態之剖視圖。 FIG. 6 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film that can be used in the present invention.

關於此處所示之保護膜形成用複合片1E，除保護膜形成用膜之形狀不同之方面以外，與圖3所示之保護膜形成用複合片1B相同。亦即，保護膜形成用複合片1E於 基材11上具備黏著劑層12，於黏著劑層12上具備保護膜形成用膜23。支持片10為基材11及黏著劑層12之積層體，換言之，保護膜形成用複合片1E具有於支持片10的一方的表面10a上積層有保護膜形成用膜23之構成。保護膜形成用複合片1E中，進一步於保護膜形成用膜23上具備剝離膜15。 The composite sheet 1E for forming a protective film shown here is the same as the composite sheet 1B for forming a protective film shown in FIG. 3 except that the shape of the film for forming a protective film is different. That is, the composite sheet 1E for forming a protective film is The adhesive layer 12 is provided on the base material 11 , and the protective film-forming film 23 is provided on the adhesive layer 12 . The support sheet 10 is a laminate of the base material 11 and the adhesive layer 12 , in other words, the protective film-forming composite sheet 1E has a structure in which the protective film-forming film 23 is laminated on one surface 10 a of the support sheet 10 . In the composite sheet 1E for protective film formation, the release film 15 is further provided on the film 23 for protective film formation.

保護膜形成用複合片1E中，於基材11的一方的表面11a積層有黏著劑層12，於黏著劑層12的表面12a的一部分亦即中央側的區域積層有保護膜形成用膜23。於黏著劑層12的表面12a中未積層保護膜形成用膜23之面及保護膜形成用膜23的表面23a(上表面及側面)上積層有剝離膜15。 In the composite sheet 1E for protective film formation, the adhesive layer 12 is laminated on one surface 11a of the base material 11, and the protective film formation film 23 is laminated on a part of the surface 12a of the adhesive layer 12, that is, the central region. The release film 15 is laminated on the surface 12a of the adhesive layer 12 on which the protective film forming film 23 is not laminated and on the surface 23a (upper surface and side surface) of the protective film forming film 23 .

自上方往下俯視保護膜形成用複合片1E時，保護膜形成用膜23的表面積小於黏著劑層12，例如具有圓形狀等形狀。 When the composite sheet 1E for protective film formation is planarly viewed from above, the surface area of the film 23 for protective film formation is smaller than that of the adhesive layer 12, and has a shape such as a circular shape, for example.

保護膜形成用複合片1E中，硬化後之保護膜形成用膜23(亦即保護膜)與支持片10之間的黏著力，換言之保護膜與黏著劑層12之間的黏著力較佳為50mN/25mm至1500mN/25mm。 In the protective film forming composite sheet 1E, the adhesive force between the protective film forming film 23 (that is, the protective film) after curing and the support sheet 10, in other words, the adhesive force between the protective film and the adhesive layer 12 is preferably 50mN/25mm to 1500mN/25mm.

圖6所示之保護膜形成用複合片1E係以下述方式使 用：在移除剝離膜15之狀態下，於保護膜形成用膜23的表面23a貼附半導體晶圓(省略圖示)的背面，並進一步將黏著劑層12的表面12a中未積層保護膜形成用膜23之面貼附於環狀框等治具。 The composite sheet 1E for forming a protective film shown in FIG. 6 is used in the following manner Use: In the state where the release film 15 is removed, the back surface of the semiconductor wafer (not shown) is attached to the surface 23a of the protective film forming film 23, and the protective film is not laminated on the surface 12a of the adhesive layer 12. The surface of the film 23 for forming is attached to a jig such as a ring frame.

圖6所示之保護膜形成用複合片1E中，亦可與圖2及圖4所示之保護膜形成用複合片同樣地，於黏著劑層12的表面12a中未積層保護膜形成用膜23之面積層治具用接著劑層(省略圖示)。與圖2及圖4所示之保護膜形成用複合片同樣地，具備此種治具用接著劑層之保護膜形成用複合片1E係將治具用接著劑層的表面貼附於環狀框等治具而使用。 In the composite sheet 1E for forming a protective film shown in FIG. 6 , as in the composite sheet for forming a protective film shown in FIGS. 2 and 4 , the film for forming a protective film may not be laminated on the surface 12 a of the adhesive layer 12 . 23 is the adhesive layer for the area layer jig (not shown). Similar to the composite sheet for forming a protective film shown in FIGS. 2 and 4 , the composite sheet 1E for forming a protective film having such an adhesive layer for a jig adheres the surface of the adhesive layer for a jig to a ring. Frame and other fixtures are used.

如此，可用於本發明之保護膜形成用複合片中，無論支持片及保護膜形成用膜為何種形態，均可具備治具用接著劑層。但是，通常如圖2及圖4所示，作為具備治具用接著劑層之保護膜形成用複合片，較佳為於保護膜形成用膜上具備治具用接著劑層。 As described above, the composite sheet for forming a protective film of the present invention can be provided with an adhesive layer for a jig regardless of the form of the support sheet and the film for forming a protective film. However, as shown in FIGS. 2 and 4 , as a composite sheet for forming a protective film provided with an adhesive layer for a jig, it is preferable to include an adhesive layer for a jig on the film for forming a protective film.

可用於本發明之保護膜形成用複合片並不限定於圖2至圖6所示之保護膜形成用複合片，在無損本發明之功效之範圍內，亦可變更或刪除圖2至圖6所示之保護膜形成用複合片的一部分構成，或者對前文所說明之保護膜形成用複合片進而追加其他構成。 The composite sheet for forming a protective film that can be used in the present invention is not limited to the composite sheet for forming a protective film shown in Figs. The composite sheet for forming a protective film shown is a part of the structure, or another structure is further added to the composite sheet for forming a protective film described above.

例如，圖4及圖5所示之保護膜形成用複合片中，亦可於基材11與保護膜形成用膜13之間設置中間層。作為中間層，可根據目的選擇任意中間層。 For example, in the composite sheet for protective film formation shown in FIG. 4 and FIG. 5, an intermediate layer may be provided between the base material 11 and the film 13 for protective film formation. As the intermediate layer, any intermediate layer can be selected according to the purpose.

圖2、圖3及圖6所示之保護膜形成用複合片中，亦可於基材11與黏著劑層12之間設置中間層。亦即，可用於本發明之保護膜形成用複合片中，支持片亦可由基材、中間層及黏著劑層依序積層而成。此處，所謂中間層，與圖4及圖5所示之保護膜形成用複合片中可設置之中間層相同。 In the composite sheet for forming a protective film shown in FIGS. 2 , 3 and 6 , an intermediate layer may also be provided between the base material 11 and the adhesive layer 12 . That is, it can be used for the composite sheet for protective film formation of this invention, and a support sheet can also be formed by laminating a base material, an intermediate layer, and an adhesive layer in this order. Here, the so-called intermediate layer is the same as the intermediate layer that can be provided in the composite sheet for forming a protective film shown in FIGS. 4 and 5 .

圖2至圖6所示之保護膜形成用複合片中，可將前述中間層以外之層設置於任意部位。 In the composite sheet for protective film formation shown in FIGS. 2-6, the layer other than the said intermediate|middle layer can be provided in arbitrary places.

可用於本發明之保護膜形成用複合片中，亦可於剝離膜與和該剝離膜直接接觸之層之間產生一部分間隙。 The composite sheet for forming a protective film of the present invention may be used, and a part of the gap may be formed between the release film and the layer in direct contact with the release film.

可用於本發明之保護膜形成用複合片中，各層的大小或形狀可根據目的任意調節。 In the composite sheet for forming a protective film of the present invention, the size and shape of each layer can be arbitrarily adjusted according to the purpose.

可用於本發明之保護膜形成用複合片中，如後述般，較佳為黏著劑層等支持片中的與保護膜形成用膜直接接觸之層為非能量線硬化性。藉由使用此種保護膜形成用複合片，可更容易地拾取背面具備保護膜之半導體晶片。 In the composite sheet for forming a protective film of the present invention, as described later, it is preferable that the layer in direct contact with the film for forming a protective film in a support sheet such as an adhesive layer is non-energy ray curable. By using such a composite sheet for protective film formation, the semiconductor wafer provided with the protective film on the back surface can be picked up more easily.

支持片可為透明、不透明、或者根據目的而著色。 The support sheet can be transparent, opaque, or colored according to the purpose.

其中，保護膜形成用膜具有能量線硬化性之本發明 中，支持片較佳為使能量線透過之支持片。 Among them, the present invention in which the film for forming a protective film has energy ray curability Among them, the support sheet is preferably a support sheet that allows energy rays to pass through.

例如，支持片中，波長375nm之光之透過率較佳為30%以上，更佳為50%以上，尤佳為70%以上。藉由前述光之透過率為此種範圍，經由支持片對保護膜形成用膜照射能量線(紫外線)時，保護膜形成用膜之硬化度進一步提高。 For example, in the support sheet, the transmittance of light with a wavelength of 375 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the transmittance|permeability of the said light is such a range, when the film for protective film formation is irradiated with energy rays (ultraviolet rays) via a support sheet, the hardening degree of the film for protective film formation is further improved.

另一方面，支持片中，波長375nm之光之透過率的上限值並無特別限定，例如可設為95%。 On the other hand, in the support sheet, the upper limit value of the transmittance of light having a wavelength of 375 nm is not particularly limited, but can be set to, for example, 95%.

支持片中，波長532nm之光之透過率較佳為30%以上，更佳為50%以上，尤佳為70%以上。 In the support sheet, the transmittance of light with a wavelength of 532 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more.

藉由前述光之透過率為此種範圍，經由支持片對保護膜形成用膜或保護膜照射雷射光而於這些進行印字時，可更清晰地進行印字。 When the transmittance of the light is in such a range, when the film for forming a protective film or the protective film is irradiated with laser light through the support sheet and printing is performed on these, the printing can be performed more clearly.

另一方面，支持片中，波長532nm之光之透過率的上限值並無特別限定，例如可設為95%。 On the other hand, in the support sheet, the upper limit value of the transmittance of light having a wavelength of 532 nm is not particularly limited, but can be set to, for example, 95%.

支持片中，波長1064nm之光之透過率較佳為30%以上，更佳為50%以上，尤佳為70%以上。藉由前述光之透過率為此種範圍，經由支持片對保護膜形成用膜或保護膜照射雷射光而於這些進行印字時，可更清晰地進行印字。 In the support sheet, the transmittance of light with a wavelength of 1064 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. When the transmittance of the light is in such a range, when the film for forming a protective film or the protective film is irradiated with laser light through the support sheet and printing is performed on these, the printing can be performed more clearly.

另一方面，支持片中，波長1064nm之光之透過率的上限值並無特別限定，例如可設為95%。 On the other hand, in the support sheet, the upper limit value of the transmittance of light having a wavelength of 1064 nm is not particularly limited, but can be set to, for example, 95%.

其次，對構成支持片之各層，進行更詳細的說明。 Next, each layer constituting the support sheet will be described in more detail.

○基材 ○Substrate

前述基材為片狀或膜狀，作為前述基材的構成材料，例如可列舉各種樹脂。 The said base material is a sheet form or a film form, and various resins are mentioned as a constituent material of the said base material, for example.

作為前述樹脂，例如可列舉：低密度聚乙烯(LDPE；low density polyethylene)、直鏈低密度聚乙烯(LLDPE；linear low density polyethylene)、高密度聚乙烯(HDPE；high density polyethylene)等聚乙烯；聚丙烯、聚丁烯、聚丁二烯、聚甲基戊烯、降冰片烯樹脂等聚乙烯以外之聚烯烴；乙烯-乙酸乙烯酯共聚物、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯共聚物、乙烯-降冰片烯共聚物等乙烯系共聚物(使用乙烯作為單體而獲得之共聚物)；聚氯乙烯、氯乙烯共聚物等氯乙烯系樹脂(使用氯乙烯作為單體而獲得之樹脂)；聚苯乙烯；聚環烯烴；聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚萘二甲酸乙二酯、聚間苯二甲酸乙二酯、聚2,6-萘二羧酸乙二酯、全部結構單元具有芳香族環式基之全芳香族聚酯等聚酯；2種以上之前述聚酯之共聚物；聚(甲基)丙烯酸酯；聚胺基甲酸酯；聚丙烯酸胺基甲酸酯；聚醯亞胺；聚醯胺；聚碳酸酯；氟樹脂；聚縮醛；改質聚苯醚；聚苯硫醚；聚碸；聚醚酮等。 As the aforementioned resin, for example, polyethylenes such as low density polyethylene (LDPE; low density polyethylene), linear low density polyethylene (LLDPE; linear low density polyethylene), and high density polyethylene (HDPE; high density polyethylene) can be exemplified; Polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene- (Meth)acrylate copolymers, ethylene-norbornene copolymers and other vinyl-based copolymers (copolymers obtained by using ethylene as a monomer); vinyl chloride-based resins such as polyvinyl chloride and vinyl chloride copolymers (using chlorine resins obtained from ethylene as a monomer); polystyrene; polycyclic olefins; polyethylene terephthalate, polyethylene naphthalate, polyethylene naphthalate, polyethylene isophthalate Polyesters such as esters, polyethylene 2,6-naphthalene dicarboxylate, and wholly aromatic polyesters having aromatic cyclic groups in all structural units; copolymers of two or more of the foregoing polyesters; poly(methyl) Acrylate; Polyurethane; Polyurethane Acrylate; Polyimide; Polyamide; Polycarbonate; Fluorine Resin; Polyacetal; Modified Polyphenylene Ether; Polyphenylene Sulfide; Polyethylene Dust; polyether ketone, etc.

作為前述樹脂，例如亦可列舉前述聚酯與前述聚酯以外的樹脂之混合物等聚合物合金。前述聚酯與前述聚酯以外的樹脂之聚合物合金較佳為聚酯以外的樹脂之量為相 對較少量。 As said resin, polymer alloys, such as a mixture of the said polyester and resin other than the said polyester, can also be mentioned, for example. The polymer alloy of the polyester and the resin other than the polyester is preferably the amount of the resin other than the polyester. for smaller amounts.

作為前述樹脂，例如亦可列舉：前文所例示之前述樹脂之1種或2種以上交聯而成之交聯樹脂；使用前文所例示之前述樹脂之1種或2種以上之離子聚合物等改質樹脂。 Examples of the above-mentioned resins include: a cross-linked resin obtained by crosslinking one or more of the above-mentioned resins exemplified above; an ionic polymer using one or two or more of the above-mentioned resins exemplified above; Modified resin.

本說明書中，「(甲基)丙烯酸」的概念係包含有「丙烯酸」及「甲基丙烯酸」兩者。關於與(甲基)丙烯酸類似之用語亦相同。 In this specification, the concept of "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth)acrylic acid.

構成基材之樹脂可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The resin constituting the base material may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

基材可由1層(單層)構成，亦可由2層以上之複數層構成；於由複數層構成之情形時，這些複數層相互可相同亦可不同，這些複數層之組合並無特別限定。 The base material may be composed of one layer (single layer), or may be composed of two or more plural layers; when composed of plural layers, these plural layers may be the same or different from each other, and the combination of these plural layers is not particularly limited.

基材的厚度較佳為50μm至300μm，更佳為60μm至100μm。藉由基材的厚度為此種範圍，前述保護膜形成用複合片的可撓性、及對半導體晶圓或半導體晶片之貼附性進一步提高。 The thickness of the base material is preferably 50 μm to 300 μm, more preferably 60 μm to 100 μm. When the thickness of the base material is in such a range, the flexibility of the composite sheet for forming a protective film and the adhesion to a semiconductor wafer or a semiconductor chip are further improved.

此處，所謂「基材的厚度」意指基材整體的厚度，例如所謂由複數層構成之基材的厚度意指構成基材之全部層的合計厚度。 Here, "thickness of a base material" means the thickness of the whole base material, for example, the thickness of the base material which consists of a plurality of layers means the total thickness of all the layers which comprise a base material.

本說明書中，所謂「厚度」係指利用接觸式厚度計，測定對象物之任意5個部位，以所測得之厚度之平均顯示之值。 In this specification, the "thickness" refers to a value displayed as an average of the measured thicknesses at any five locations of the object to be measured by a contact thickness gauge.

基材較佳為厚度精度高，亦即任何部位的厚度不均均得到抑制。上述之構成材料中，作為可用於構成此種厚度精度高的基材之材料，例如可列舉：聚乙烯、聚乙烯以外的聚烯烴、聚對苯二甲酸乙二酯、乙烯-乙酸乙烯酯共聚物等。 It is preferable that the base material has high thickness accuracy, that is, thickness unevenness in any part is suppressed. Among the above-mentioned constituent materials, examples of materials that can be used to constitute such a base material with high thickness accuracy include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymers. things etc.

基材中，除前述樹脂等主要構成材料以外，亦可含有填充材料、著色劑、抗靜電劑、抗氧化劑、有機潤滑劑、觸媒、軟化劑(塑化劑)等公知的各種添加劑。 The base material may contain various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, softeners (plasticizers), and the like, in addition to the main constituent materials such as the aforementioned resins.

基材的光學特性滿足前文所說明之支持片的光學特性即可。亦即，基材可為透明、不透明、根據目的而著色，或者蒸鍍其他層。 The optical properties of the base material may satisfy the optical properties of the support sheet described above. That is, the substrate may be transparent, opaque, colored according to the purpose, or other layers may be vapor-deposited.

保護膜形成用膜具有能量線硬化性之本發明中，基材較佳為使能量線透過之基材。 In the present invention in which the film for forming a protective film has energy ray curability, the base material is preferably a base material that transmits energy rays.

基材的表面亦可經實施以下處理以提高與設置於該基材上之黏著劑層等其他層之密接性：利用噴砂處理、溶劑處理等之凹凸化處理；或者電暈放電處理、電子束照射處理、電漿處理、臭氧/紫外線照射處理、火焰處理、鉻 酸處理、熱風處理等氧化處理等。 The surface of the substrate can also be subjected to the following treatments to improve the adhesion with other layers such as the adhesive layer provided on the substrate: uneven treatment by sandblasting, solvent treatment, etc.; or corona discharge treatment, electron beam treatment Irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromium Acid treatment, hot air treatment and other oxidation treatments, etc.

基材的表面亦可經實施底塗(primer)處理。 The surface of the substrate may also be subjected to a primer treatment.

基材亦可具有抗靜電塗層或以下用途之層等：將保護膜形成用複合片重疊保存時，防止基材接著於其他片或基材接著於吸附台。 The base material may also have an antistatic coating or a layer for the following purposes: when the composite sheets for forming a protective film are stacked and stored, the base material can be prevented from adhering to other sheets or the base material to an adsorption table.

這些之中，就抑制因切割時刀片摩擦而導致基材產生斷片之方面而言，基材尤佳為表面經實施電子束照射處理。 Among these, it is particularly preferable that the surface of the base material is subjected to electron beam irradiation treatment in terms of suppressing the occurrence of fragmentation of the base material due to blade friction during dicing.

基材可利用公知的方法進行製造。例如，含有樹脂之基材可藉由使含有前述樹脂之樹脂組成物成形而進行製造。 The base material can be produced by a known method. For example, the resin-containing substrate can be produced by molding the resin composition containing the aforementioned resin.

○黏著劑層 ○Adhesive layer

前述黏著劑層為片狀或膜狀，含有黏著劑。 The aforementioned adhesive layer is in the form of a sheet or a film, and contains an adhesive.

作為前述黏著劑，例如可列舉：丙烯酸系樹脂、胺基甲酸酯系樹脂、橡膠系樹脂、聚矽氧系樹脂、環氧系樹脂、聚乙烯醚、聚碳酸酯、酯系樹脂等黏著性樹脂，較佳為丙烯酸系樹脂。 Examples of the aforementioned adhesives include adhesives such as acrylic resins, urethane resins, rubber-based resins, polysiloxane-based resins, epoxy-based resins, polyvinyl ethers, polycarbonates, and ester-based resins. The resin is preferably an acrylic resin.

本發明中，「黏著性樹脂」的概念係包含有具有黏著性之樹脂及具有接著性之樹脂兩者，例如不僅包含本身具有黏著性之樹脂，亦包含藉由與添加劑等其他成分併用而顯示黏著性之樹脂、或者藉由存在熱或水等觸發劑而顯示 接著性之樹脂等。 In the present invention, the concept of "adhesive resin" includes both resins with adhesiveness and resins with adhesiveness, for example, not only resins with adhesiveness themselves, but also those displayed by combining with other components such as additives. Adhesive resins, or displayed by the presence of triggers such as heat or water Adhesive resin, etc.

黏著劑層可由1層(單層)構成，亦可由2層以上之複數層構成；於由複數層構成之情形時，這些複數層相互可相同亦可不同，這些複數層之組合並無特別限定。 The adhesive layer may be composed of one layer (single layer), or may be composed of two or more layers; when composed of plural layers, these plural layers may be the same or different from each other, and the combination of these plural layers is not particularly limited .

黏著劑層的厚度較佳為1μm至100μm，更佳為1μm至60μm，尤佳為1μm至30μm。 The thickness of the adhesive layer is preferably 1 μm to 100 μm, more preferably 1 μm to 60 μm, particularly preferably 1 μm to 30 μm.

此處，所謂「黏著劑層的厚度」意指黏著劑層整體的厚度，例如所謂由複數層構成之黏著劑層的厚度意指構成黏著劑層之全部層的合計厚度。 Here, the "thickness of the adhesive layer" means the thickness of the entire adhesive layer, for example, the thickness of the adhesive layer composed of a plurality of layers means the total thickness of all the layers constituting the adhesive layer.

黏著劑層的光學特性滿足前文所說明之支持片的光學特性即可。亦即，黏著劑層可為透明、不透明、或者根據目的而著色。 The optical properties of the adhesive layer may satisfy the optical properties of the support sheet described above. That is, the adhesive layer may be transparent, opaque, or colored according to the purpose.

保護膜形成用膜具有能量線硬化性之本發明中，黏著劑層較佳為使能量線透過之黏著劑層。 In the present invention in which the film for forming a protective film has energy ray curability, the adhesive layer is preferably an adhesive layer that transmits energy rays.

黏著劑層可使用能量線硬化性黏著劑而形成，亦可使用非能量線硬化性黏著劑而形成。使用能量線硬化性之黏著劑所形成之黏著劑層可容易地調節硬化前及硬化後的物性。 The adhesive layer may be formed using an energy ray-curable adhesive or a non-energy ray-curable adhesive. The adhesive layer formed using the energy ray-curable adhesive can easily adjust the physical properties before and after curing.

<<黏著劑組成物>> <<Adhesive composition>>

黏著劑層可使用含有黏著劑之黏著劑組成物而形成。例如，於黏著劑層之形成對象面塗敷黏著劑組成物，視需要使黏著劑組成物乾燥，藉此可於目標部位形成黏著劑層。關於黏著劑層的更具體的形成方法，與其他層的形成方法一起，隨後詳細地進行說明。黏著劑組成物中的常溫下不會氣化的成分彼此的含量比率，通常與黏著劑層中的前述成分彼此的含量比率相同。本說明書中，所謂「常溫」意指不特別冷或特別熱的溫度，亦即平常的溫度，例如可列舉15℃至25℃之溫度等。 The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, the adhesive layer can be formed on the target site by applying the adhesive composition to the surface to be formed of the adhesive layer, and drying the adhesive composition if necessary. The more specific formation method of an adhesive bond layer is demonstrated in detail later together with the formation method of other layers. The content ratio of components that do not vaporize at room temperature in the adhesive composition is usually the same as the content ratio of the aforementioned components in the adhesive layer. In this specification, "normal temperature" means a temperature not particularly cold or particularly hot, that is, a normal temperature, for example, a temperature of 15°C to 25°C, and the like.

利用公知的方法塗敷黏著劑組成物即可，例如可列舉使用以下各種塗佈機之方法：氣刀塗佈機、刮刀塗佈機、棒式塗佈機、凹版塗佈機、輥式塗佈機、輥刀塗佈機、簾幕式塗佈機、模具塗佈機、刀式塗佈機、絲網塗佈機、繞線棒(Meyer bar)式塗佈機、刮棒式塗佈機(rod coater)、接觸式塗佈機等。 The adhesive composition may be applied by a known method, and examples thereof include methods using the following various coaters: air knife coater, knife coater, bar coater, gravure coater, roll coater Cloth machine, roll knife coater, curtain coater, die coater, knife coater, screen coater, Meyer bar coater, bar coater rod coater, contact coater, etc.

黏著劑組成物的乾燥條件並無特別限定，於黏著劑組成物含有後述溶劑之情形時，較佳為進行加熱乾燥，該情形時，較佳為於例如70℃至130℃且10秒至5分鐘之條件下進行乾燥。 The drying conditions of the adhesive composition are not particularly limited. When the adhesive composition contains the solvent described later, it is preferable to perform heating and drying. Dry in minutes.

於黏著劑層為能量線硬化性之情形時，作為含有能量線硬化性黏著劑之黏著劑組成物，亦即能量線硬化性之黏 著劑組成物，例如可列舉以下黏著劑組成物等：黏著劑組成物(I-1)，含有非能量線硬化性之黏著性樹脂(I-1a)(以下，有時簡記為「黏著性樹脂(I-1a)」)、及能量線硬化性化合物；黏著劑組成物(I-2)，含有能量線硬化性之黏著性樹脂(I-2a)(以下，有時簡記為「黏著性樹脂(I-2a)」)，該黏著性樹脂(I-2a)於非能量線硬化性之黏著性樹脂(I-1a)的側鏈導入有不飽和基；黏著劑組成物(I-3)，含有前述黏著性樹脂(I-2a)、及能量線硬化性化合物。 When the adhesive layer is energy ray curable, it is used as an adhesive composition containing an energy ray curable adhesive, that is, an energy ray curable adhesive. Adhesive composition, for example, the following adhesive composition can be mentioned: Adhesive composition (I-1), containing non-energy ray-curable adhesive resin (I-1a) (hereinafter, sometimes abbreviated as "adhesive" Resin (I-1a)”), and energy ray curable compound; Adhesive composition (I-2), containing energy ray curable adhesive resin (I-2a) (hereinafter, sometimes abbreviated as “adhesive” Resin (I-2a)"), the adhesive resin (I-2a) has an unsaturated group introduced into the side chain of the non-energy ray-curable adhesive resin (I-1a); the adhesive composition (I-3 ), containing the aforementioned adhesive resin (I-2a) and an energy ray curable compound.

<黏著劑組成物(I-1)> <Adhesive composition (I-1)>

如上所述，前述黏著劑組成物(I-1)含有非能量線硬化性之黏著性樹脂(I-1a)、及能量線硬化性化合物。 As mentioned above, the said adhesive composition (I-1) contains the non-energy ray curable adhesive resin (I-1a), and an energy ray curable compound.

[黏著性樹脂(I-1a)] [Adhesive resin (I-1a)]

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

作為前述丙烯酸系樹脂，例如可列舉：至少具有源自(甲基)丙烯酸烷基酯之結構單元之丙烯酸系聚合物。 As said acrylic resin, the acrylic polymer which has a structural unit derived from (meth)acrylic-acid alkylester at least is mentioned, for example.

前述丙烯酸系樹脂所具有之結構單元可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The structural unit which the said acrylic resin has may be only 1 type, and may be 2 or more types; In the case of 2 or more types, these combinations and ratios can be selected arbitrarily.

作為前述(甲基)丙烯酸烷基酯，例如可列舉構成烷基酯之烷基的碳數為1至20之(甲基)丙烯酸烷基酯，前述烷基較佳為直鏈狀或支鏈狀。 Examples of the above-mentioned (meth)acrylic acid alkyl ester include (meth)acrylic acid alkyl esters having 1 to 20 carbon atoms in the alkyl group constituting the alkyl ester, and the above-mentioned alkyl group is preferably linear or branched. shape.

作為(甲基)丙烯酸烷基酯，更具體而言，可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯(亦稱為(甲基)丙烯酸月桂酯)、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯(亦稱為(甲基)丙烯酸肉豆蔻酯)、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯(亦稱為(甲基)丙烯酸棕櫚酯)、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯(亦稱為(甲基)丙烯酸硬脂酯)、(甲基)丙烯酸十九烷基酯、(甲基)丙烯酸二十烷基酯等。 As the alkyl (meth)acrylate, more specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate can be mentioned. ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-butyl (meth)acrylate, 3-butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate (methyl)hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-octyl (meth)acrylate Nonyl ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (also known as (meth)acrylic acid) lauryl), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also known as myristyl (meth)acrylate), pentadecyl (meth)acrylate, Cetyl (meth)acrylate (also known as palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (also known as (meth)acrylate) base) stearyl acrylate), nonadecyl (meth)acrylate, eicosyl (meth)acrylate, and the like.

就黏著劑層的黏著力提高之方面而言，前述丙烯酸系聚合物較佳為具有源自前述烷基的碳數為4以上之(甲基)丙烯酸烷基酯之結構單元。就黏著劑層的黏著力進一步提高之方面而言，前述烷基的碳數較佳為4至12，更佳為4至8。前述烷基的碳數為4以上之(甲基)丙烯酸烷基酯較佳為丙烯酸烷基酯。 It is preferable that the said acrylic polymer has the structural unit which has the C4 or more (meth)acrylic-acid alkylester derived from the said alkyl group from the point which the adhesive force of an adhesive bond layer improves. The carbon number of the aforementioned alkyl group is preferably from 4 to 12, more preferably from 4 to 8, from the viewpoint of further improving the adhesive force of the adhesive layer. The (meth)acrylic acid alkyl ester in which the carbon number of the above-mentioned alkyl group is 4 or more is preferably an acrylic acid alkyl ester.

前述丙烯酸系聚合物較佳為除源自(甲基)丙烯酸烷 基酯之結構單元以外，進一步具有源自含官能基之單體之結構單元。 The aforementioned acrylic polymer is preferably derived from alkane (meth)acrylate In addition to the structural unit of the base ester, there is further a structural unit derived from a functional group-containing monomer.

作為前述含官能基之單體，例如可列舉以下單體：可藉由前述官能基與後述之交聯劑反應而成為交聯的起點，或者可藉由前述官能基與後述之含不飽和基之化合物中的不飽和基反應，而於丙烯酸系聚合物的側鏈導入不飽和基。 Examples of the functional group-containing monomer include the following monomers that can become an origin of crosslinking by reacting the functional group described above with a crosslinking agent described later, or a monomer that can be crosslinked by the functional group described above and an unsaturated group-containing monomer described later. The unsaturated group in the compound reacts, and the unsaturated group is introduced into the side chain of the acrylic polymer.

作為含官能基之單體中的前述官能基，例如可列舉：羥基、羧基、胺基、環氧基等。 As said functional group in a functional group containing monomer, a hydroxyl group, a carboxyl group, an amine group, an epoxy group, etc. are mentioned, for example.

亦即，作為含官能基之單體，例如可列舉：含羥基之單體、含羧基之單體、含胺基之單體、含環氧基之單體等。 That is, as a functional group containing monomer, a hydroxyl group containing monomer, a carboxyl group containing monomer, an amine group containing monomer, an epoxy group containing monomer, etc. are mentioned, for example.

作為前述含羥基之單體，例如可列舉：(甲基)丙烯酸羥基甲酯、(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2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等(甲基)丙烯酸羥基烷基酯；乙烯醇、烯丙醇等非(甲基)丙烯酸系不飽和醇(不具有(甲基)丙烯醯基骨架之不飽和醇)等。 Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. Hydroxyalkyl (meth)acrylates such as hydroxypropyl, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; vinyl alcohol, Non-(meth)acrylic unsaturated alcohols such as allyl alcohol (unsaturated alcohols having no (meth)acryloyl skeleton), and the like.

作為前述含羧基之單體，例如可列舉：(甲基)丙烯酸、丁烯酸等乙烯性不飽和單羧酸(具有乙烯性不飽和鍵之單羧酸)；反丁烯二酸、衣康酸、順丁烯二酸、檸康酸 等乙烯性不飽和二羧酸(具有乙烯性不飽和鍵之二羧酸)；前述乙烯性不飽和二羧酸之酐；甲基丙烯酸2-羧基乙酯等(甲基)丙烯酸羧基烷基酯等。 Examples of the carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, etc. acid, maleic acid, citraconic acid ethylenically unsaturated dicarboxylic acids (dicarboxylic acids having ethylenically unsaturated bonds); anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; carboxyalkyl (meth)acrylates such as 2-carboxyethyl methacrylate Wait.

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

構成前述丙烯酸系聚合物之含官能基之單體可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The functional group-containing monomer constituting the acrylic polymer may be only one type, or may be two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

前述丙烯酸系聚合物中，源自含官能基之單體之結構單元的含量相對於結構單元的總質量，較佳為1質量%至35質量%，更佳為2質量%至32質量%，尤佳為3質量%至30質量%。 In the aforementioned acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably 1 to 35% by mass, more preferably 2 to 32% by mass relative to the total mass of the structural unit, It is especially preferable that it is 3 mass % to 30 mass %.

前述丙烯酸系聚合物中，除源自(甲基)丙烯酸烷基酯之結構單元及源自含官能基之單體之結構單元以外，亦可進一步具有源自其他單體之結構單元。 In addition to the structural unit derived from the (meth)acrylic-acid alkylester and the structural unit derived from the monomer containing a functional group, the said acrylic polymer may have the structural unit derived from another monomer further.

前述其他單體只要能夠與(甲基)丙烯酸烷基酯等共聚合，則並無特別限定。 The other monomers described above are not particularly limited as long as they can be copolymerized with alkyl (meth)acrylate and the like.

作為前述其他單體，例如可列舉：苯乙烯、α-甲基苯乙烯、乙烯基甲苯、甲酸乙烯酯、乙酸乙烯酯、丙烯腈、丙烯醯胺等。 As said other monomer, styrene, (alpha)-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide, etc. are mentioned, for example.

構成前述丙烯酸系聚合物之前述其他單體可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The said other monomer which comprises the said acrylic polymer may be only 1 type, and may be 2 or more types; In the case of 2 or more types, these combinations and ratios can be selected arbitrarily.

前述丙烯酸系聚合物可用作上述之非能量線硬化性之黏著性樹脂(I-1a)。 The aforementioned acrylic polymer can be used as the aforementioned non-energy ray-curable adhesive resin (I-1a).

另一方面，使前述丙烯酸系聚合物中的官能基，與具有能量線聚合性不飽和基(能量線聚合性基)之含不飽和基之化合物反應而成之化合物可用作上述之能量線硬化性之黏著性樹脂(I-2a)。 On the other hand, a compound obtained by reacting a functional group in the aforementioned acrylic polymer with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group (energy ray polymerizable group) can be used as the aforementioned energy ray Curable adhesive resin (I-2a).

黏著劑組成物(I-1)所含有之黏著性樹脂(I-1a)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The adhesive resin (I-1a) contained in the adhesive composition (I-1) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

黏著劑組成物(I-1)中，黏著性樹脂(I-1a)的含量相對於前述黏著劑組成物(I-1)的總質量，較佳為5質量%至99質量%，更佳為10質量%至95質量%，尤佳為15質量%至90質量%。 In the adhesive composition (I-1), the content of the adhesive resin (I-1a) is preferably 5% by mass to 99% by mass relative to the total mass of the aforementioned adhesive composition (I-1), more preferably It is 10 to 95 mass %, and it is especially preferable that it is 15 to 90 mass %.

[能量線硬化性化合物] [Energy ray hardening compound]

作為黏著劑組成物(I-1)所含有之前述能量線硬化性化合物，可列舉：具有能量線聚合性不飽和基，且可藉由 照射能量線而硬化之單體或低聚物。 Examples of the energy ray curable compound contained in the adhesive composition (I-1) include those having an energy ray polymerizable unsaturated group, and which can be Monomers or oligomers hardened by irradiation with energy rays.

能量線硬化性化合物中，作為單體，例如可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇(甲基)丙烯酸酯等多元(甲基)丙烯酸酯；(甲基)丙烯酸胺基甲酸酯；聚酯(甲基)丙烯酸酯；聚醚(甲基)丙烯酸酯；環氧(甲基)丙烯酸酯等。 Among the energy ray curable compounds, examples of monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate and other polyvalent (meth)acrylates; (meth)acrylate aminomethyl Polyester (meth)acrylate; Polyether (meth)acrylate; Epoxy (meth)acrylate, etc.

能量線硬化性化合物中，作為低聚物，例如可列舉上述所例示之單體進行聚合而成之低聚物等。 Among the energy ray curable compounds, examples of the oligomers include oligomers obtained by polymerizing the monomers exemplified above.

就分子量相對較大，不易使黏著劑層的儲存彈性率降低之方面而言，能量線硬化性化合物較佳為(甲基)丙烯酸胺基甲酸酯、(甲基)丙烯酸胺基甲酸酯低聚物。 The energy ray curable compound is preferably urethane (meth)acrylate and urethane (meth)acrylate in that the molecular weight is relatively large and the storage elastic modulus of the adhesive layer is not easily reduced. Oligomer.

黏著劑組成物(I-1)所含有之前述能量線硬化性化合物可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The aforementioned energy ray curable compound contained in the adhesive composition (I-1) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

前述黏著劑組成物(I-1)中，前述能量線硬化性化合物的含量相對於前述黏著劑組成物(I-1)的總質量，較佳為1質量%至95質量%，更佳為5質量%至90質量%，尤佳為10質量%至85質量%。 In the aforementioned adhesive composition (I-1), the content of the aforementioned energy ray curable compound is preferably 1 to 95 mass % relative to the total mass of the aforementioned adhesive composition (I-1), more preferably 5% by mass to 90% by mass, particularly preferably 10% by mass to 85% by mass.

[交聯劑] [Crosslinking agent]

於使用除源自(甲基)丙烯酸烷基酯之結構單元以外，進一步具有源自含官能基之單體之結構單元之前述丙烯酸系聚合物作為黏著性樹脂(I-1a)之情形時，黏著劑組成物(I-1)較佳為進一步含有交聯劑。 In the case of using the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate as the adhesive resin (I-1a), The adhesive composition (I-1) preferably further contains a crosslinking agent.

前述交聯劑例如與前述官能基反應，使黏著性樹脂(I-1a)彼此交聯。 For example, the above-mentioned crosslinking agent reacts with the above-mentioned functional group to crosslink the adhesive resins (I-1a) to each other.

作為交聯劑，例如可列舉：甲苯二異氰酸酯、六亞甲基二異氰酸酯、苯二甲基二異氰酸酯、這些二異氰酸酯之加合物等異氰酸酯系交聯劑(具有異氰酸酯基之交聯劑)；乙二醇縮水甘油基醚等環氧系交聯劑(具有縮水甘油基之交聯劑)；六[1-(2-甲基)-氮丙啶基]三膦三嗪等氮丙啶系交聯劑(具有氮丙啶基之交聯劑)；鋁螯合物等金屬螯合物系交聯劑(具有金屬螯合物結構之交聯劑)；異氰脲酸酯系交聯劑(具有異氰脲酸骨架之交聯劑)等。 Examples of the crosslinking agent include isocyanate-based crosslinking agents (crosslinking agents having an isocyanate group) such as tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; Epoxy-based cross-linking agents such as ethylene glycol glycidyl ether (cross-linking agents having a glycidyl group); Cross-linking agent (cross-linking agent with aziridine group); metal chelate-based cross-linking agent such as aluminum chelate (cross-linking agent with metal chelate structure); isocyanurate-based cross-linking agent (crosslinking agent with isocyanuric acid skeleton) and the like.

就提高黏著劑的凝聚力而提高黏著劑層的黏著力之方面、及容易獲取等方面而言，交聯劑較佳為異氰酸酯系交聯劑。 The crosslinking agent is preferably an isocyanate-based crosslinking agent in terms of improving the cohesive force of the adhesive and improving the adhesive force of the adhesive layer, and from the viewpoint of easy availability.

黏著劑組成物(I-1)所含有之交聯劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The crosslinking agent contained in the adhesive composition (I-1) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

前述黏著劑組成物(I-1)中，交聯劑的含量相對於黏著 性樹脂(I-1a)的含量100質量份，較佳為0.01質量份至50質量份，更佳為0.1質量份至20質量份，尤佳為0.3質量份至15質量份。 In the aforementioned adhesive composition (I-1), the content of the crosslinking agent is relative to the adhesive The content of the resin (I-1a) is 100 parts by mass, preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, particularly preferably 0.3 to 15 parts by mass.

[光聚合起始劑] [Photopolymerization initiator]

黏著劑組成物(I-1)亦可進一步含有光聚合起始劑。對於含有光聚合起始劑之黏著劑組成物(I-1)，即便照射紫外線等相對較低能量之能量線，亦充分地進行硬化反應。 The adhesive composition (I-1) may further contain a photopolymerization initiator. In the adhesive composition (I-1) containing a photopolymerization initiator, even when irradiated with relatively low-energy energy rays such as ultraviolet rays, the curing reaction sufficiently proceeds.

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

作為前述光聚合起始劑，例如亦可使用1-氯蒽醌等醌化合物；胺等光增感劑等。 As the photopolymerization initiator, for example, quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines, and the like can also be used.

黏著劑組成物(I-1)所含有之光聚合起始劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The photopolymerization initiator contained in the adhesive composition (I-1) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

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

[其他添加劑] [Other additives]

黏著劑組成物(I-1)中，在無損本發明之功效之範圍內，亦可含有不屬於上述之任一種成分之其他添加劑。 The adhesive composition (I-1) may contain other additives that do not belong to any of the above-mentioned components within the scope of impairing the effect of the present invention.

作為前述其他添加劑，例如可列舉：抗靜電劑、抗氧化劑、軟化劑(塑化劑)、填充材料(填料)、防鏽劑、著色劑(顏料、染料)、增感劑、黏著賦予劑、反應延遲劑、交聯促進劑(觸媒)等公知的添加劑。 Examples of the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, adhesion imparting agents, Known additives such as reaction retarders and crosslinking accelerators (catalysts).

所謂反應延遲劑，例如，抑制因混入至黏著劑組成物(I-1)中之觸媒之作用，導致保存中之黏著劑組成物(I-1)中，進行目標外的交聯反應。作為反應延遲劑，例如可列舉藉由針對觸媒之螯合物形成螯合物錯合物之化合物，更具體而言，可列舉1分子中具有2個以上之羰基(-C(=O)-)之化合物。 The so-called reaction retarder suppresses, for example, the action of a catalyst mixed into the adhesive composition (I-1), which causes an unintended crosslinking reaction in the adhesive composition (I-1) during storage. As the reaction retarder, for example, a compound that forms a chelate complex by a chelate for a catalyst can be mentioned, and more specifically, a carbonyl group (-C(=O) having two or more carbonyl groups in one molecule can be mentioned. -) compounds.

黏著劑組成物(I-1)所含有之其他添加劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The other additives contained in the adhesive composition (I-1) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

黏著劑組成物(I-1)中，其他添加劑的含量並無特別限定，根據該其他添加劑的種類適宜選擇即可。 In the adhesive composition (I-1), the content of other additives is not particularly limited, and may be appropriately selected according to the type of the other additives.

[溶劑] [solvent]

黏著劑組成物(I-1)亦可含有溶劑。黏著劑組成物(I-1)藉由含有溶劑，對塗敷對象面之塗敷適性提高。 The adhesive composition (I-1) may contain a solvent. Since the adhesive composition (I-1) contains a solvent, the coating suitability to the coating target surface is improved.

前述溶劑較佳為有機溶劑，作為前述有機溶劑，例如可列舉：甲基乙基酮、丙酮等酮；乙酸乙酯等酯(羧酸酯)；四氫呋喃、二噁烷(dioxane)等醚；環己烷、正己烷等脂肪族烴；甲苯、二甲苯等芳香族烴；1-丙醇、2-丙醇等醇等。 The solvent is preferably an organic solvent. Examples of the organic solvent include ketones such as methyl ethyl ketone and acetone; esters (carboxylate) such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; Aliphatic hydrocarbons such as hexane and n-hexane; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol, and the like.

作為前述溶劑，例如，可將製造黏著性樹脂(I-1a)時所使用之溶劑不自黏著性樹脂(I-1a)中去除而直接於黏著劑組成物(I-1)中使用，亦可於製造黏著劑組成物(I-1)時另行添加與製造黏著性樹脂(I-1a)時所使用之溶劑相同種類或不同種類之溶劑。 As the aforementioned solvent, for example, the solvent used in the production of the adhesive resin (I-1a) can be directly used in the adhesive composition (I-1) without being removed from the adhesive resin (I-1a), or When manufacturing the adhesive composition (I-1), a solvent of the same or different type as the solvent used for the manufacture of the adhesive resin (I-1a) may be added separately.

黏著劑組成物(I-1)所含有之溶劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任 意選擇。 The solvent contained in the adhesive composition (I-1) may be only one type or two or more types; in the case of two or more types, these combinations and ratios may be arbitrary. Willing to choose.

黏著劑組成物(I-1)中，溶劑的含量並無特別限定，適宜調節即可。 In the adhesive composition (I-1), the content of the solvent is not particularly limited, and may be appropriately adjusted.

<黏著劑組成物(I-2)> <Adhesive composition (I-2)>

如上所述，前述黏著劑組成物(I-2)含有能量線硬化性之黏著性樹脂(I-2a)，該黏著性樹脂(I-2a)於非能量線硬化性之黏著性樹脂(I-1a)的側鏈導入有不飽和基。 As described above, the above-mentioned adhesive composition (I-2) contains the energy ray-curable adhesive resin (I-2a), the adhesive resin (I-2a) and the non-energy ray-curable adhesive resin (I-2a) -1a) An unsaturated group is introduced into the side chain.

[黏著性樹脂(I-2a)] [Adhesive resin (I-2a)]

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

前述含不飽和基之化合物除具有前述能量線聚合性不飽和基以外，進一步具有以下基：該基藉由與黏著性樹脂(I-1a)中的官能基反應，而可與黏著性樹脂(I-1a)鍵結。 The aforementioned unsaturated group-containing compound has, in addition to the aforementioned energy ray polymerizable unsaturated group, a further group that can react with the adhesive resin (I-1a) by reacting with the functional group in the adhesive resin (I-1a). I-1a) Bonding.

作為前述能量線聚合性不飽和基，例如可列舉：(甲基)丙烯醯基、乙烯基(亦稱為次乙基)、烯丙基(亦稱為2-丙烯基)等，較佳為(甲基)丙烯醯基。 Examples of the energy ray polymerizable unsaturated group include (meth)acryloyl group, vinyl group (also referred to as ethylene group), allyl group (also referred to as 2-propenyl group), and the like, preferably (Meth)acryloyl.

作為可與黏著性樹脂(I-1a)中的官能基鍵結之基，例如可列舉：可與羥基或胺基鍵結之異氰酸酯基及縮水甘油基、以及可與羧基或環氧基鍵結之羥基及胺基等。 As a group which can be bonded to the functional group in the adhesive resin (I-1a), for example, an isocyanate group and a glycidyl group which can be bonded to a hydroxyl group or an amino group, and a carboxyl group or an epoxy group which can be bonded The hydroxyl and amine groups, etc.

作為前述含不飽和基之化合物，例如可列舉：異氰酸(甲基)丙烯醯氧基乙酯、(甲基)丙烯醯基異氰酸酯、(甲基)丙烯酸縮水甘油酯等。 As said unsaturated group containing compound, (meth)acryloyloxyethyl isocyanate, (meth)acryloyl isocyanate, glycidyl (meth)acrylate etc. are mentioned, for example.

黏著劑組成物(I-2)所含有之黏著性樹脂(I-2a)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The adhesive resin (I-2a) contained in the adhesive composition (I-2) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

黏著劑組成物(I-2)中，黏著性樹脂(I-2a)的含量相對於前述黏著劑組成物(I-2)的總質量，較佳為5質量%至99質量%，更佳為10質量%至95質量%，尤佳為10質量%至90質量%。 In the adhesive composition (I-2), the content of the adhesive resin (I-2a) is preferably 5% to 99% by mass relative to the total mass of the aforementioned adhesive composition (I-2), more preferably It is 10 to 95 mass %, and it is especially preferable that it is 10 to 90 mass %.

[交聯劑] [Crosslinking agent]

於使用例如與黏著性樹脂(I-1a)中相同的具有源自含官能基之單體之結構單元之前述丙烯酸系聚合物作為黏著性樹脂(I-2a)之情形時，黏著劑組成物(I-2)亦可進一步含有交聯劑。 In the case of using, for example, the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer as in the adhesive resin (I-1a) as the adhesive resin (I-2a), the adhesive composition (I-2) may further contain a crosslinking agent.

作為黏著劑組成物(I-2)中的前述交聯劑，可列舉與黏著劑組成物(I-1)中的交聯劑相同的化合物。 As said crosslinking agent in an adhesive composition (I-2), the same compound as the crosslinking agent in an adhesive composition (I-1) is mentioned.

黏著劑組成物(I-2)所含有之交聯劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可 任意選擇。 The crosslinking agent contained in the adhesive composition (I-2) may be only one type or two or more types; in the case of two or more types, these combinations and ratios may be Arbitrary choice.

前述黏著劑組成物(I-2)中，交聯劑的含量相對於黏著性樹脂(I-2a)的含量100質量份，較佳為0.01質量份至50質量份，更佳為0.1質量份至20質量份，尤佳為0.3質量份至15質量份。 In the aforementioned adhesive composition (I-2), the content of the crosslinking agent is 100 parts by mass relative to the content of the adhesive resin (I-2a), preferably 0.01 parts by mass to 50 parts by mass, more preferably 0.1 parts by mass to 20 parts by mass, particularly preferably 0.3 to 15 parts by mass.

[光聚合起始劑] [Photopolymerization initiator]

黏著劑組成物(I-2)亦可進一步含有光聚合起始劑。對於含有光聚合起始劑之黏著劑組成物(I-2)，即便照射紫外線等相對較低能量之能量線，亦充分地進行硬化反應。 The adhesive composition (I-2) may further contain a photopolymerization initiator. In the adhesive composition (I-2) containing a photopolymerization initiator, even when irradiated with relatively low-energy energy rays such as ultraviolet rays, the curing reaction sufficiently proceeds.

作為黏著劑組成物(I-2)中的前述光聚合起始劑，可列舉與黏著劑組成物(I-1)中的光聚合起始劑相同的化合物。 As said photopolymerization initiator in an adhesive composition (I-2), the same compound as the photopolymerization initiator in an adhesive composition (I-1) is mentioned.

黏著劑組成物(I-2)所含有之光聚合起始劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The photopolymerization initiator contained in the adhesive composition (I-2) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

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

[其他添加劑] [Other additives]

黏著劑組成物(I-2)中，在無損本發明之功效之範圍內，亦可含有不屬於上述之任一種成分之其他添加劑。 The adhesive composition (I-2) may contain other additives that do not belong to any of the above-mentioned components within the scope of impairing the effect of the present invention.

作為黏著劑組成物(I-2)中的前述其他添加劑，可列舉與黏著劑組成物(I-1)中的其他添加劑相同的化合物。 As said other additive in an adhesive composition (I-2), the same compound as the other additive in an adhesive composition (I-1) is mentioned.

黏著劑組成物(I-2)所含有之其他添加劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The other additives contained in the adhesive composition (I-2) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

黏著劑組成物(I-2)中，其他添加劑的含量並無特別限定，根據該其他添加劑的種類適宜選擇即可。 In the adhesive composition (I-2), the content of other additives is not particularly limited, and may be appropriately selected according to the type of the other additives.

[溶劑] [solvent]

以與黏著劑組成物(I-1)之情形相同之目的，黏著劑組成物(I-2)亦可含有溶劑。 The adhesive composition (I-2) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1).

作為黏著劑組成物(I-2)中的前述溶劑，可列舉與黏著劑組成物(I-1)中的溶劑相同的溶劑。 As said solvent in an adhesive composition (I-2), the same solvent as the solvent in an adhesive composition (I-1) is mentioned.

黏著劑組成物(I-2)所含有之溶劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The solvent contained in the adhesive composition (I-2) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

黏著劑組成物(I-2)中，溶劑的含量並無特別限定，適宜調節即可。 In the adhesive composition (I-2), the content of the solvent is not particularly limited, and may be appropriately adjusted.

<黏著劑組成物(I-3)> <Adhesive composition (I-3)>

如上所述，前述黏著劑組成物(I-3)含有前述黏著性樹 脂(I-2a)、及能量線硬化性化合物。 As described above, the above-mentioned adhesive composition (I-3) contains the above-mentioned adhesive tree Lipid (I-2a), and energy ray sclerosing compound.

黏著劑組成物(I-3)中，黏著性樹脂(I-2a)的含量相對於前述黏著劑組成物(I-3)的總質量，較佳為5質量%至99質量%，更佳為10質量%至95質量%，尤佳為15質量%至90質量%。 In the adhesive composition (I-3), the content of the adhesive resin (I-2a) is preferably 5% by mass to 99% by mass relative to the total mass of the aforementioned adhesive composition (I-3), more preferably It is 10 to 95 mass %, and it is especially preferable that it is 15 to 90 mass %.

[能量線硬化性化合物] [Energy ray hardening compound]

作為黏著劑組成物(I-3)所含有之前述能量線硬化性化合物，可列舉具有能量線聚合性不飽和基，且可藉由照射能量線而硬化之單體及低聚物，可列舉與黏著劑組成物(I-1)所含有之能量線硬化性化合物相同的化合物。 Examples of the energy ray-curable compound contained in the adhesive composition (I-3) include monomers and oligomers that have an energy ray polymerizable unsaturated group and can be cured by irradiation with energy rays, and examples include The same compound as the energy ray curable compound contained in the adhesive composition (I-1).

黏著劑組成物(I-3)所含有之前述能量線硬化性化合物可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The above-mentioned energy ray curable compound contained in the adhesive composition (I-3) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

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

[光聚合起始劑] [Photopolymerization initiator]

黏著劑組成物(I-3)亦可進一步含有光聚合起始劑。對於含有光聚合起始劑之黏著劑組成物(I-3)，即便照射紫外 線等相對較低能量之能量線，亦充分地進行硬化反應。 The adhesive composition (I-3) may further contain a photopolymerization initiator. For the adhesive composition (I-3) containing a photopolymerization initiator, even if irradiated with ultraviolet Energy lines with relatively low energy such as lines can also fully undergo the hardening reaction.

作為黏著劑組成物(I-3)中的前述光聚合起始劑，可列舉與黏著劑組成物(I-1)中的光聚合起始劑相同的化合物。 As the photopolymerization initiator in the adhesive composition (I-3), the same compounds as the photopolymerization initiator in the adhesive composition (I-1) can be mentioned.

黏著劑組成物(I-3)所含有之光聚合起始劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The photopolymerization initiator contained in the adhesive composition (I-3) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

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

[其他添加劑] [Other additives]

黏著劑組成物(I-3)中，在無損本發明之功效之範圍內，亦可含有不屬於上述之任一種成分之其他添加劑。 The adhesive composition (I-3) may contain other additives that do not belong to any of the above-mentioned components within the scope of impairing the effect of the present invention.

作為前述其他添加劑，可列舉與黏著劑組成物(I-1)中的其他添加劑相同的溶劑。 As said other additive, the same solvent as the other additive in an adhesive composition (I-1) is mentioned.

黏著劑組成物(I-3)所含有之其他添加劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The other additives contained in the adhesive composition (I-3) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

黏著劑組成物(I-3)中，其他添加劑的含量並無特別限定，根據該其他添加劑的種類適宜選擇即可。 In the adhesive composition (I-3), the content of other additives is not particularly limited, and may be appropriately selected according to the type of the other additives.

[溶劑] [solvent]

以與黏著劑組成物(I-1)之情形相同之目的，黏著劑組成物(I-3)亦可含有溶劑。 The adhesive composition (I-3) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1).

作為黏著劑組成物(I-3)中的前述溶劑，可列舉與黏著劑組成物(I-1)中的溶劑相同的溶劑。 As said solvent in an adhesive composition (I-3), the same solvent as the solvent in an adhesive composition (I-1) is mentioned.

黏著劑組成物(I-3)所含有之溶劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The solvent contained in the adhesive composition (I-3) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

黏著劑組成物(I-3)中，溶劑的含量並無特別限定，適宜調節即可。 In the adhesive composition (I-3), the content of the solvent is not particularly limited, and may be appropriately adjusted.

<黏著劑組成物(I-1)至黏著劑組成物(I-3)以外之黏著劑組成物> <Adhesive composition (I-1) to adhesive compositions other than adhesive composition (I-3)>

前文主要對黏著劑組成物(I-1)、黏著劑組成物(I-2)及黏著劑組成物(I-3)進行了說明，但對於這些3種黏著劑組成物以外之全部黏著劑組成物(本說明書中，稱為「黏著劑組成物(I-1)至黏著劑組成物(I-3)以外之黏著劑組成物」)，亦可同樣地使用作為這些含有成分所說明之成分。 The adhesive composition (I-1), the adhesive composition (I-2), and the adhesive composition (I-3) have been described above, but for all adhesives other than these three adhesive compositions The composition (in this specification, referred to as "adhesive composition (I-1) to adhesive composition other than the adhesive composition (I-3)"), can be similarly used as the components described above. Element.

作為黏著劑組成物(I-1)至黏著劑組成物(I-3)以外之黏著劑組成物，除能量線硬化性之黏著劑組成物以外，亦可列舉非能量線硬化性之黏著劑組成物。 As the adhesive composition other than the adhesive composition (I-1) to the adhesive composition (I-3), in addition to the energy ray curable adhesive composition, a non-energy ray curable adhesive composition can also be used composition.

作為非能量線硬化性之黏著劑組成物，例如可列舉： 含有丙烯酸系樹脂、胺基甲酸酯系樹脂、橡膠系樹脂、聚矽氧系樹脂、環氧系樹脂、聚乙烯醚、聚碳酸酯、酯系樹脂等非能量線硬化性之黏著性樹脂(I-1a)之黏著劑組成物(I-4)，較佳為含有丙烯酸系樹脂之黏著劑組成物。 Examples of non-energy ray-curable adhesive compositions include: Non-energy ray-curable adhesive resins ( The adhesive composition (I-4) of I-1a) is preferably an adhesive composition containing an acrylic resin.

黏著劑組成物(I-1)至黏著劑組成物(I-3)以外之黏著劑組成物較佳為含有1種或2種以上之交聯劑，該交聯劑的含量可設為與上述之黏著劑組成物(I-1)等之情形相同。 The adhesive compositions other than the adhesive composition (I-1) to the adhesive composition (I-3) preferably contain one or more cross-linking agents, and the content of the cross-linking agent can be set to The same applies to the above-mentioned adhesive composition (I-1) and the like.

<黏著劑組成物(I-4)> <Adhesive composition (I-4)>

作為較佳的黏著劑組成物(I-4)，例如可列舉：含有前述黏著性樹脂(I-1a)及交聯劑之黏著劑組成物。 As a preferable adhesive composition (I-4), the adhesive composition containing the said adhesive resin (I-1a) and a crosslinking agent is mentioned, for example.

[黏著性樹脂(I-1a)] [Adhesive resin (I-1a)]

作為黏著劑組成物(I-4)中的黏著性樹脂(I-1a)，可列舉與黏著劑組成物(I-1)中的黏著性樹脂(I-1a)相同的樹脂。 As the adhesive resin (I-1a) in the adhesive composition (I-4), the same resin as the adhesive resin (I-1a) in the adhesive composition (I-1) can be mentioned.

黏著劑組成物(I-4)所含有之黏著性樹脂(I-1a)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The adhesive resin (I-1a) contained in the adhesive composition (I-4) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

黏著劑組成物(I-4)中，黏著性樹脂(I-1a)的含量相對於前述黏著劑組成物(I-4)的總質量，較佳為5質量%至99質量%，更佳為10質量%至95質量%，尤佳為15質量% 至90質量%。 In the adhesive composition (I-4), the content of the adhesive resin (I-1a) is preferably 5% by mass to 99% by mass relative to the total mass of the aforementioned adhesive composition (I-4), more preferably 10% by mass to 95% by mass, preferably 15% by mass to 90% by mass.

[交聯劑] [Crosslinking agent]

於使用除源自(甲基)丙烯酸烷基酯之結構單元以外，進一步具有源自含官能基之單體之結構單元之前述丙烯酸系聚合物作為黏著性樹脂(I-1a)之情形時，黏著劑組成物(I-4)較佳為進一步含有交聯劑。 In the case of using the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate as the adhesive resin (I-1a), The adhesive composition (I-4) preferably further contains a crosslinking agent.

作為黏著劑組成物(I-4)中的交聯劑，可列舉與黏著劑組成物(I-1)中的交聯劑相同的化合物。 As the crosslinking agent in the adhesive composition (I-4), the same compounds as the crosslinking agent in the adhesive composition (I-1) can be mentioned.

黏著劑組成物(I-4)所含有之交聯劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The crosslinking agent contained in the adhesive composition (I-4) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

前述黏著劑組成物(I-4)中，交聯劑的含量相對於黏著性樹脂(I-1a)的含量100質量份，較佳為0.01質量份至50質量份，更佳為0.1質量份至20質量份，尤佳為0.3質量份至15質量份。 In the aforementioned adhesive composition (I-4), the content of the crosslinking agent is 100 parts by mass relative to the content of the adhesive resin (I-1a), preferably 0.01 parts by mass to 50 parts by mass, more preferably 0.1 parts by mass to 20 parts by mass, particularly preferably 0.3 to 15 parts by mass.

[其他添加劑] [Other additives]

黏著劑組成物(I-4)中，在無損本發明之功效之範圍內，亦可含有不屬於上述之任一種成分之其他添加劑。 The adhesive composition (I-4) may contain other additives that do not belong to any of the above-mentioned components within the scope of impairing the effect of the present invention.

作為前述其他添加劑，可列舉與黏著劑組成物(I-1)中的其他添加劑相同的化合物。 As said other additive, the compound similar to the other additive in an adhesive composition (I-1) is mentioned.

黏著劑組成物(I-4)所含有之其他添加劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The other additives contained in the adhesive composition (I-4) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

黏著劑組成物(I-4)中，其他添加劑的含量並無特別限定，根據該其他添加劑的種類適宜選擇即可。 In the adhesive composition (I-4), the content of other additives is not particularly limited, and may be appropriately selected according to the type of the other additives.

[溶劑] [solvent]

以與黏著劑組成物(I-1)之情形相同之目的，黏著劑組成物(I-4)亦可含有溶劑。 The adhesive composition (I-4) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1).

作為黏著劑組成物(I-4)中的前述溶劑，可列舉與黏著劑組成物(I-1)中的溶劑相同的溶劑。 As said solvent in an adhesive composition (I-4), the same solvent as the solvent in an adhesive composition (I-1) is mentioned.

黏著劑組成物(I-4)所含有之溶劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The solvent contained in the adhesive composition (I-4) may be only one type or two or more types; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

黏著劑組成物(I-4)中，溶劑的含量並無特別限定，適宜調節即可。 In the adhesive composition (I-4), the content of the solvent is not particularly limited, and may be appropriately adjusted.

可用於本發明之保護膜形成用複合片中，黏著劑層較佳為非能量線硬化性。原因在於，若黏著劑層為能量線硬化性，則會有無法抑制於藉由照射能量線而使保護膜形成用膜硬化時黏著劑層亦同時硬化之情形。若黏著劑層與保護膜形成用膜同時硬化，則會有硬化後之保護膜形成用膜及黏著劑層於這些之界面黏附至無法剝離之程度之情 形。該情形時，難以將背面具備硬化後之保護膜形成用膜，亦即保護膜之半導體晶片(本說明書中，有時稱為「附有保護膜的半導體晶片」)，自具備硬化後之黏著劑層之支持片剝離，無法正常地拾取附有保護膜的半導體晶片。藉由本發明中的支持片中的黏著劑層設為非能量線硬化性，可確實地避免此種不良情形，從而可更容易地拾取附有保護膜的半導體晶片。 In the composite sheet for forming a protective film of the present invention, the adhesive layer is preferably non-energy ray curable. The reason is that when the adhesive layer is energy ray curable, it cannot be suppressed that the adhesive layer is also cured at the same time when the film for forming a protective film is cured by irradiating energy rays. When the adhesive layer and the film for forming a protective film are cured at the same time, the cured film for forming a protective film and the adhesive layer may adhere to the interface between these to the extent that they cannot be peeled off. shape. In this case, it is difficult to attach a semiconductor wafer having a film for forming a protective film after curing, that is, a protective film (in this specification, sometimes referred to as a "semiconductor wafer with a protective film") on the back surface, since it has an adhesive after curing. The support sheet of the agent layer was peeled off, and the semiconductor wafer with the protective film could not be picked up normally. By setting the adhesive layer in the support sheet in the present invention to be non-energy ray curable, such an inconvenience can be surely avoided, and the semiconductor wafer with the protective film can be picked up more easily.

本文對黏著劑層為非能量線硬化性之情形之功效進行了說明，但即便支持片中的與保護膜形成用膜直接接觸之層為黏著劑層以外之層，只要該層為非能量線硬化性，則亦發揮同樣的功效。 In this article, the effect of the case where the adhesive layer is non-energy ray curable has been described, but even if the layer in the support sheet that is in direct contact with the protective film-forming film is a layer other than the adhesive layer, as long as the layer is non-energy ray curable Sclerosis also exerts the same effect.

<<黏著劑組成物的製造方法>> <<Manufacturing method of adhesive composition>>

黏著劑組成物(I-1)至黏著劑組成物(I-3)、或者黏著劑組成物(I-4)等黏著劑組成物(I-1)至黏著劑組成物(I-3)以外之黏著劑組成物藉由下述方式而獲得：將前述黏著劑、及視需要之前述黏著劑以外的成分等用以構成黏著劑組成物之各成分加以調配。 Adhesive composition (I-1) to adhesive composition (I-3), or adhesive composition (I-4) such as adhesive composition (I-1) to adhesive composition (I-3) The adhesive composition other than the above is obtained by mixing the above-mentioned adhesive and, if necessary, components other than the above-mentioned adhesive, etc., for each component constituting the adhesive composition.

調配各成分時的添加順序並無特別限定，亦可同時添加2種以上之成分。 The order of addition at the time of preparing each component is not particularly limited, and two or more components may be added at the same time.

於使用溶劑之情形時，可藉由下述方式使用：將溶劑與溶劑以外的任一種調配成分混合而將該調配成分預先稀釋；亦可藉由下述方式使用：不將溶劑以外的任一種調 配成分預先稀釋而將溶劑與這些調配成分混合。 In the case of using a solvent, it can be used by mixing the solvent with any preparation component other than the solvent and diluting the preparation component in advance; it can also be used in the following way: not using any preparation component other than the solvent tune The formulating ingredients are pre-diluted and the solvent is mixed with these formulating ingredients.

調配時混合各成分之方法並無特別限定，自以下公知的方法中適宜選擇即可：使攪拌子或攪拌翼等旋轉而進行混合之方法；使用混合機而進行混合之方法；施加超音波而進行混合之方法等。 The method of mixing the components during preparation is not particularly limited, and may be appropriately selected from the following well-known methods: a method of mixing by rotating a stirrer, a stirring blade, etc.; a method of mixing using a mixer; Methods of mixing, etc.

關於添加及混合各成分時的溫度及時間，只要不使各調配成分劣化，則並無特別限定，適宜調節即可，溫度較佳為15℃至30℃。 The temperature and time at the time of adding and mixing each component are not particularly limited as long as each compounded component is not degraded, and may be appropriately adjusted, and the temperature is preferably 15°C to 30°C.

◎保護膜形成用片 ◎Sheet for forming protective film

本發明中，保護膜形成用膜除了以上述之保護膜形成用複合片之形式使用以外，亦可以於剝離膜上設置有保護膜形成用膜之保護膜形成用片之形式，貼附於前述半導體晶圓的背面後，貼附支持片而使用。 In the present invention, the film for forming a protective film may be used in the form of the above-mentioned composite sheet for forming a protective film, or in the form of a sheet for forming a protective film in which the film for forming a protective film is provided on a release film, and may be attached to the above-mentioned After the backside of the semiconductor wafer, a support sheet is attached and used.

此處可使用之保護膜形成用膜如上述之保護膜形成用複合片之項中所說明。 The film for forming a protective film that can be used here is as described in the section of the above-mentioned composite sheet for forming a protective film.

圖7係以示意方式顯示可用於本發明之保護膜形成用片2F的一實施形態之剖視圖。 FIG. 7 is a cross-sectional view schematically showing an embodiment of the sheet 2F for forming a protective film that can be used in the present invention.

此處所示之保護膜形成用片2F係於第1剝離膜15'上具備保護膜形成用膜13，於保護膜形成用膜13上具備第2剝離膜15"。 The sheet 2F for protective film formation shown here is equipped with the film 13 for protective film formation on the 1st peeling film 15', and is equipped with the 2nd peeling film 15" on the film 13 for protective film formation.

圖7所示之保護膜形成用片2F係以下述方式使用：在移除輕剝離側的第2剝離膜15"之狀態下，於保護膜形成用膜13的表面13a中央側的一部分區域貼附半導體晶 圓(省略圖示)的背面，並進一步在移除重剝離側的第1剝離膜15'之狀態下，於保護膜形成用膜13中的與表面13a為相反側的另一方的表面13b上貼附支持片，進而，將保護膜形成用膜13的周緣部附近的區域貼附於環狀框等治具。 The sheet 2F for forming a protective film shown in FIG. 7 is used in a state where the second peeling film 15 ″ on the light peeling side is removed, and is attached to a partial area of the center side of the surface 13 a of the film 13 for forming a protective film. With semiconductor crystal The back surface of the circle (not shown) is further on the other surface 13b on the opposite side to the surface 13a in the protective film forming film 13 in a state where the first release film 15' of the heavy peeling side is removed. The support sheet is attached, and further, the region in the vicinity of the peripheral edge portion of the protective film forming film 13 is attached to a jig such as an annular frame.

此處，將剝離力小的剝離膜稱為輕剝離側的剝離膜，將剝離力大的剝離膜稱為重剝離側的剝離膜。若使剝離力存在差異，則可防止在僅剝離輕剝離側的剝離膜時，保護膜形成用膜自重剝離側的剝離膜隆起之虞，或者保護膜形成用膜欲追隨於兩剝離膜而拉伸變形之情形。 Here, a release film with a small peeling force is referred to as a release film on the light peel side, and a release film with a large peel force is referred to as a release film on the heavy peel side. If there is a difference in peeling force, when only the peeling film on the light peeling side is peeled off, the peeling film on the peeling side of the film for protective film formation can be prevented from being raised by its own weight, or the film for forming a protective film can be prevented from being pulled following the two peeling films. The situation of stretching.

本發明中，保護膜形成用膜硬化而獲得之保護膜與支持片之間的黏著力較佳為50mN/25mm至1500mN/25mm，更佳為52mN/25mm至1450mN/25mm，尤佳為53mN/25mm至1430mN/25mm。藉由前述黏著力為前述下限值以上，拾取附有保護膜的半導體晶片時，目標外的附有保護膜的半導體晶片之拾取得到抑制，從而可高選擇性地拾取目標之附有保護膜的半導體晶片。藉由前述黏著力為前述上限值以下，拾取附有保護膜的半導體晶片時，半導體晶片之破裂及缺損得到抑制。如此，藉由前述黏著力為特定範圍內，保護膜形成用複合片具有良好的拾取適性。 In the present invention, the adhesive force between the protective film obtained by hardening the protective film forming film and the support sheet is preferably 50mN/25mm to 1500mN/25mm, more preferably 52mN/25mm to 1450mN/25mm, particularly preferably 53mN/ 25mm to 1430mN/25mm. When the above-mentioned adhesive force is equal to or more than the above-mentioned lower limit value, when picking up a semiconductor wafer with a protective film, the pickup of a semiconductor wafer with a protective film other than the target is suppressed, and the target with a protective film can be picked up with high selectivity. semiconductor wafers. When the said adhesive force is below the said upper limit value, when picking up the semiconductor wafer with a protective film, the cracking and the defect of a semiconductor wafer are suppressed. Thus, since the said adhesive force exists in a specific range, the composite sheet for protective film formation has favorable pick-up property.

本發明中，即便為保護膜形成用膜硬化後，只要維持支持片及保護膜形成用膜之硬化物(換言之，支持片及保 護膜)之積層結構，則亦將該積層結構體稱為「保護膜形成用複合片」。 In the present invention, even after the film for protective film formation is cured, as long as the cured product of the support sheet and the film for protective film formation (in other words, the support sheet and the protective film are maintained) protective film), the laminated structure is also referred to as a "composite sheet for forming a protective film".

保護膜與支持片之間的黏著力可利用以下方法進行測定。 The adhesive force between the protective film and the support sheet can be measured by the following method.

亦即，將寬度為25mm且長度為任意之保護膜形成用複合片，藉由該保護膜形成用複合片之保護膜形成用膜，貼附於被接著體。 That is, a composite sheet for forming a protective film having a width of 25 mm and an arbitrary length is attached to a to-be-adhered body through the film for forming a protective film of the composite sheet for forming a protective film.

接著，照射能量線使保護膜形成用膜硬化而形成保護膜後，自貼附於被接著體之該保護膜，將支持片以剝離速度300mm/min剝離。此時的剝離係設為以下所謂之180°剝離：以保護膜及支持片相互接觸之面彼此成為180°之角度之方式，將支持片沿該支持片的長度方向(保護膜形成用複合片的長度方向)剝離。然後，測定該180°剝離時的荷重(剝離力)，將該荷重(剝離力)的測定值設為前述黏著力(mN/25mm)。 Next, after irradiating an energy ray to harden the film for protective film formation to form a protective film, the support sheet was peeled off at a peeling speed of 300 mm/min from the protective film attached to the adherend. The peeling at this time is a so-called 180° peeling: the support sheet is taken along the longitudinal direction of the support sheet so that the surfaces of the protective film and the support sheet in contact with each other form an angle of 180° (the composite sheet for forming a protective film). length direction) peeled off. Then, the load (peeling force) at the time of the 180° peeling was measured, and the measured value of the load (peeling force) was defined as the aforementioned adhesive force (mN/25 mm).

供於測定之保護膜形成用複合片的長度只要為可穩定地檢測出黏著力之範圍，則並無特別限定，較佳為100mm至300mm。測定時，較佳為使保護膜形成用複合片成為貼附於被接著體之狀態，從而使保護膜形成用複合片之貼附狀態穩定化。 The length of the composite sheet for forming a protective film to be measured is not particularly limited as long as the adhesive force can be stably detected, but it is preferably 100 mm to 300 mm. At the time of measurement, it is preferable to stabilize the adhesion state of the composite sheet for protective film formation by making the composite sheet for protective film formation into the state adhered to the to-be-adhered body.

本發明中，保護膜形成用膜與前述支持片之間的黏著 力並無特別限定，例如可為80mN/25mm以上等，較佳為100mN/25mm以上，更佳為150mN/25mm以上，尤佳為200mN/25mm以上。藉由前述黏著力為100mN/25mm以上，切割時保護膜形成用膜與支持片之剝離得到抑制，例如，背面具備保護膜形成用膜之半導體晶片自支持片之飛散得到抑制。 In the present invention, the adhesion between the protective film forming film and the support sheet The force is not particularly limited, but may be, for example, 80 mN/25 mm or more, preferably 100 mN/25 mm or more, more preferably 150 mN/25 mm or more, and particularly preferably 200 mN/25 mm or more. When the adhesive force is 100 mN/25 mm or more, the peeling of the film for forming a protective film and the support sheet at the time of dicing is suppressed, for example, the scattering of the semiconductor wafer having the film for forming a protective film on the back surface from the support sheet is suppressed.

另一方面，保護膜形成用膜與前述支持片之間的黏著力的上限值並無特別限定，例如可設為4000mN/25mm、3500mN/25mm、3000mN/25mm等之任一者。但是，這些為一例。 On the other hand, the upper limit value of the adhesive force between the film for protective film formation and the said support sheet is not specifically limited, For example, it can be set to any of 4000mN/25mm, 3500mN/25mm, 3000mN/25mm, etc. However, these are examples.

作為本發明之另一態樣，前述積層體中的支持片與前述保護膜形成用膜之間的黏著力為10mN/25mm至30000mN/25mm，較佳為100mN/25mm至20000mN/25mm，更佳為150mN/25mm至10000mN/25mm，進而較佳為200mN/25mm至8000mN/25mm。 As another aspect of the present invention, the adhesive force between the support sheet in the laminate and the film for forming the protective film is 10mN/25mm to 30000mN/25mm, preferably 100mN/25mm to 20000mN/25mm, more preferably It is 150mN/25mm to 10000mN/25mm, and more preferably 200mN/25mm to 8000mN/25mm.

關於保護膜形成用膜與支持片之間的黏著力，除不藉由照射能量線使供於測定之保護膜形成用膜硬化之方面以外，可利用與上述之保護膜與支持片之間的黏著力相同的方法進行測定。 Regarding the adhesive force between the film for forming a protective film and the support sheet, except that the film for forming a protective film used for measurement is not cured by irradiating energy rays, the adhesive force between the above-mentioned protective film and the supporting sheet can be used. Adhesion was measured in the same way.

上述之保護膜與支持片之間的黏著力、及保護膜形成用膜與支持片之間的黏著力例如可藉由調節保護膜形成用膜的含有成分的種類及量、支持片中的設置保護膜形成 用膜之層的構成材料、該層的表面狀態等而適宜調節。 The adhesive force between the above-mentioned protective film and the supporting sheet, and the adhesive force between the protective film forming film and the supporting sheet can be adjusted, for example, by adjusting the type and amount of the components contained in the protective film forming film, and the setting in the supporting sheet. protective film formation It is suitably adjusted by the constituent material of the layer of the film, the surface state of the layer, and the like.

例如，保護膜形成用膜的含有成分的種類及量可藉由後述之保護膜形成用組成物的含有成分的種類及量進行調節。並且，藉由調節保護膜形成用組成物的含有成分中，例如不具有能量線硬化性基之聚合物(b)的種類及含量、填充材料(d)的含量、或交聯劑(f)的含量，可更容易地調節保護膜或保護膜形成用膜與支持片之間的黏著力。 For example, the kind and amount of the component contained in the film for forming a protective film can be adjusted by the kind and amount of the component contained in the composition for forming a protective film to be described later. Furthermore, among the components contained in the composition for forming a protective film, for example, the type and content of the polymer (b) not having an energy ray curable group, the content of the filler (d), or the crosslinking agent (f) , it is easier to adjust the adhesive force between the protective film or the protective film-forming film and the support sheet.

例如，於支持片中的設置保護膜形成用膜之層為黏著劑層之情形時，該層的構成材料可藉由調節黏著劑層的含有成分的種類及量而適宜調節。並且，黏著劑層的含有成分的種類及量可藉由上述之黏著劑組成物的含有成分的種類及量而進行調節。 For example, when the layer on which the protective film-forming film is provided in the support sheet is an adhesive layer, the constituent material of the layer can be appropriately adjusted by adjusting the types and amounts of components contained in the adhesive layer. In addition, the kinds and amounts of the components contained in the adhesive layer can be adjusted by the kinds and amounts of the components contained in the above-mentioned adhesive composition.

另一方面，於支持片中的設置保護膜形成用膜之層為基材之情形時，保護膜或保護膜形成用膜與支持片之間的黏著力，除基材的構成材料以外，亦可藉由基材的表面狀態進行調節。並且，基材的表面狀態例如可藉由實施前文作為提高基材與其他層之密接性之處理所列舉之表面處理而進行調節：利用噴砂處理、溶劑處理等之凹凸化處理；電暈放電處理、電子束照射處理、電漿處理、臭氧/紫外線照射處理、火焰處理、鉻酸處理、熱風處理等氧化處理；底塗處理等任一處理。 On the other hand, in the case where the layer on which the film for forming a protective film is provided in the support sheet is the base material, the adhesive force between the protective film or the film for forming a protective film and the support sheet, in addition to the constituent material of the base material, is also It can be adjusted by the surface state of the base material. In addition, the surface state of the base material can be adjusted, for example, by performing surface treatments exemplified as treatments for improving the adhesion between the base material and other layers: roughening treatment by sandblasting, solvent treatment, etc.; corona discharge treatment , Electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments; any treatment such as primer treatment.

保護膜形成用膜可列舉：具有能量線硬化性，例如含有能量線硬化性成分(a)之膜。 As a film for protective film formation, the film which has energy ray curability, for example, contains an energy ray curable component (a) is mentioned.

能量線硬化性成分(a)較佳為未硬化，較佳為具有黏著性，更佳為未硬化且具有黏著性。 The energy ray curable component (a) is preferably uncured, preferably has adhesiveness, and is more preferably uncured and has adhesiveness.

保護膜形成用膜可僅為1層(單層)，亦可為2層以上之複數層；於為複數層之情形時，這些複數層相互可相同亦可不同，這些複數層之組合並無特別限定。 The film for forming a protective film may be only one layer (single layer), or it may be a plurality of layers of two or more layers; in the case of a plurality of layers, these plural layers may be the same or different from each other, and the combination of these plural layers does not Specially limited.

保護膜形成用膜的厚度較佳為1μm至100μm，更佳為5μm至75μm，尤佳為5μm至50μm。藉由保護膜形成用膜的厚度為前述下限值以上，可形成保護能力更高的保護膜。藉由保護膜形成用膜的厚度為前述上限值以下，可抑制厚度過厚。 The thickness of the film for forming a protective film is preferably 1 μm to 100 μm, more preferably 5 μm to 75 μm, particularly preferably 5 μm to 50 μm. When the thickness of the film for protective film formation is more than the said lower limit, the protective film with higher protective ability can be formed. When the thickness of the film for protective film formation is below the said upper limit value, it can suppress that thickness becomes too thick.

此處，所謂「保護膜形成用膜的厚度」意指保護膜形成用膜整體的厚度，例如所謂由複數層構成之保護膜形成用膜的厚度意指構成保護膜形成用膜之全部層的合計厚度。 Here, the "thickness of the film for forming a protective film" means the thickness of the entire film for forming a protective film, for example, the thickness of the film for forming a protective film composed of a plurality of layers means the thickness of all layers constituting the film for forming a protective film. Total thickness.

關於使保護膜形成用膜硬化而形成保護膜時的硬化條件，只要保護膜成為充分發揮該保護膜的功能之程度的硬化度，則並無特別限定，根據保護膜形成用膜的種類適宜選擇即可。 The curing conditions at the time of curing the film for forming a protective film to form a protective film are not particularly limited as long as the protective film has a degree of curing sufficient to fully exhibit the function of the protective film, and it is appropriately selected according to the type of the film for forming a protective film. That's it.

例如，保護膜形成用膜之硬化時，能量線之照度較佳 為4mW/cm2至280mW/cm2。前述硬化時，能量線之光量較佳為3mJ/cm2至1000mJ/cm2。 For example, in the curing of the protective film-forming film, the illuminance of the energy ray is preferably 4 mW/cm 2 to 280 mW/cm 2 . During the aforementioned curing, the light amount of the energy ray is preferably 3 mJ/cm 2 to 1000 mJ/cm 2 .

<<保護膜形成用組成物>> <<The composition for forming a protective film>>

保護膜形成用膜可使用含有該保護膜形成用膜的構成材料之保護膜形成用組成物而形成。例如，於保護膜形成用膜之形成對象面塗敷保護膜形成用組成物，視需要使保護膜形成用組成物乾燥，藉此可於目標部位形成保護膜形成用膜。保護膜形成用組成物中的常溫下不會氣化的成分彼此的含量比率，通常與保護膜形成用膜中的前述成分彼此的含量比率相同。此處，所謂「常溫」如前文所說明。 The film for protective film formation can be formed using the composition for protective film formation containing the constituent material of the film for protective film formation. For example, the film for protective film formation can be formed in the target site|part by apply|coating the composition for protective film formation to the formation object surface of the film for protective film formation, and drying the composition for protective film formation as needed. The content ratio of the components that do not vaporize at room temperature in the composition for forming a protective film is usually the same as the content ratio of the above-mentioned components in the film for forming a protective film. Here, the so-called "normal temperature" is as described above.

利用公知的方法塗敷保護膜形成用組成物即可，例如可列舉使用以下各種塗佈機之方法：氣刀塗佈機、刮刀塗佈機、棒式塗佈機、凹版塗佈機、輥式塗佈機、輥刀塗佈機、簾幕式塗佈機、模具塗佈機、刀式塗佈機、絲網塗佈機、繞線棒式塗佈機、刮棒式塗佈機、接觸式塗佈機等。 The composition for forming a protective film may be applied by a known method, and examples thereof include methods using the following various coaters: air knife coater, knife coater, bar coater, gravure coater, roll coater, etc. Coater, Roller Knife Coater, Curtain Coater, Die Coater, Knife Coater, Screen Coater, Wire Rod Coater, Bar Coater, Contact coater, etc.

保護膜形成用組成物的乾燥條件並無特別限定，於保護膜形成用組成物含有後述溶劑之情形時，較佳為進行加熱乾燥，該情形時，較佳為於例如70℃至130℃且10秒至5分鐘之條件下進行乾燥。 The drying conditions of the composition for forming a protective film are not particularly limited, but when the composition for forming a protective film contains a solvent to be described later, it is preferable to perform heat drying. Dry under the conditions of 10 seconds to 5 minutes.

<保護膜形成用組成物(IV-1)> <Protection film-forming composition (IV-1)>

作為保護膜形成用組成物，例如可列舉含有前述能量線硬化性成分(a)之保護膜形成用組成物(IV-1)等。 As a composition for protective film formation, the composition for protective film formation (IV-1) etc. which contain the said energy-beam curable component (a) etc. are mentioned, for example.

[能量線硬化性成分(a)] [energy ray sclerosing component (a)]

能量線硬化性成分(a)係藉由照射能量線而硬化之成分，該成分用以對保護膜形成用膜賦予造膜性或可撓性等。 The energy ray-curable component (a) is a component that is cured by irradiation with an energy ray, and is used to impart film-forming properties, flexibility, and the like to the film for forming a protective film.

作為能量線硬化性成分(a)，例如可列舉：具有能量線硬化性基且重量平均分子量為80000至2000000之聚合物(a1)、及具有能量線硬化性基且分子量為100至80000之化合物(a2)。前述聚合物(a1)可至少一部分藉由後述之交聯劑(f)進行交聯，亦可不進行交聯。 Examples of the energy ray curable component (a) include a polymer (a1) having an energy ray curable group and a weight average molecular weight of 80,000 to 2,000,000, and a compound having an energy ray curable group and a molecular weight of 100 to 80,000. (a2). At least a part of the said polymer (a1) may be crosslinked by the crosslinking agent (f) mentioned later, and may not be crosslinked.

本說明書中，所謂重量平均分子量，只要無特別說明，則意指藉由凝膠滲透層析(GPC；Gel Permeation Chromatography)法所測定之聚苯乙烯換算值。 In this specification, the weight average molecular weight means a polystyrene conversion value measured by a gel permeation chromatography (GPC; Gel Permeation Chromatography) method unless otherwise specified.

(具有能量線硬化性基且重量平均分子量為80000至2000000之聚合物(a1)) (Polymer (a1) having an energy ray hardening group and having a weight average molecular weight of 80,000 to 2,000,000)

作為具有能量線硬化性基且重量平均分子量為80000至2000000之聚合物(a1)，例如可列舉丙烯酸系樹脂(a1-1)，該丙烯酸系樹脂(a1-1)係丙烯酸系聚合物(a11)與能量線硬化性化合物(a12)聚合而成，前述丙烯酸系聚合物(a11)具有可與其他化合物所具有之基反應之官能基，前述能量線硬化性化合物(a12)具有與前述官能基反應之基及 能量線硬化性雙鍵等能量線硬化性基。 Examples of the polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000 include an acrylic resin (a1-1) which is an acrylic polymer (a11) ) and an energy ray curable compound (a12), the acrylic polymer (a11) having a functional group reactive with groups possessed by other compounds, and the energy ray curable compound (a12) having a functional group reactive with the aforementioned functional group reaction base and Energy ray sclerosing groups such as energy ray sclerosing double bonds.

作為可與其他化合物所具有之基反應之前述官能基，例如可列舉：羥基、羧基、胺基、取代胺基(胺基的1個或2個氫原子被氫原子以外的基取代而成之基)、環氧基等。但是，就防止半導體晶圓或半導體晶片等的電路腐蝕之方面而言，前述官能基較佳為羧基以外的基。 Examples of the functional group that can react with groups contained in other compounds include a hydroxyl group, a carboxyl group, an amino group, and a substituted amino group (a group in which one or two hydrogen atoms of the amino group are substituted with a group other than a hydrogen atom). group), epoxy group, etc. However, it is preferable that the said functional group is a group other than a carboxyl group from the viewpoint of preventing circuit corrosion of a semiconductor wafer, a semiconductor wafer, or the like.

這些之中，前述官能基較佳為羥基。 Among these, the aforementioned functional group is preferably a hydroxyl group.

‧具有官能基之丙烯酸系聚合物(a11) ‧Acrylic polymer with functional group (a11)

前述具有官能基之丙烯酸系聚合物(a11)例如可列舉：使前述具有官能基之丙烯酸系單體與前述不具有官能基之丙烯酸系單體進行共聚合而成之聚合物，亦可為除這些單體以外，進一步使丙烯酸系單體以外的單體(非丙烯酸系單體)進行共聚合而成之聚合物。 Examples of the functional group-containing acrylic polymer (a11) include, for example, a polymer obtained by copolymerizing the functional group-containing acrylic monomer and the non-functional group-containing acrylic monomer. A polymer obtained by copolymerizing monomers other than acrylic monomers (non-acrylic monomers) in addition to these monomers.

另外，前述丙烯酸系聚合物(a11)可為無規共聚物，亦可為嵌段共聚物。 In addition, the aforementioned acrylic polymer (a11) may be a random copolymer or a block copolymer.

作為前述具有官能基之丙烯酸系單體，例如可列舉：含羥基之單體、含羧基之單體、含胺基之單體、含取代胺基之單體、含環氧基之單體等。 Examples of the functional group-containing acrylic monomer include hydroxyl group-containing monomers, carboxyl group-containing monomers, amine group-containing monomers, substituted amino group-containing monomers, epoxy group-containing monomers, and the like .

作為前述含羥基之單體，例如可列舉：(甲基)丙烯酸羥基甲酯、(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2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等(甲基)丙烯酸羥基烷基酯；乙烯醇、烯丙醇等非(甲基)丙烯酸系不飽和醇(不具有(甲基)丙烯醯基骨架之不飽和醇)等。 Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxy (meth)acrylate. propyl propyl ester, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. (meth) group) hydroxyalkyl acrylate; non-(meth)acrylic unsaturated alcohols such as vinyl alcohol and allyl alcohol (unsaturated alcohols not having a (meth)acryloyl skeleton), and the like.

作為前述含羧基之單體，例如可列舉：(甲基)丙烯酸、丁烯酸等乙烯性不飽和單羧酸(具有乙烯性不飽和鍵之單羧酸)；反丁烯二酸、衣康酸、順丁烯二酸、檸康酸等乙烯性不飽和二羧酸(具有乙烯性不飽和鍵之二羧酸)；前述乙烯性不飽和二羧酸之酐；甲基丙烯酸2-羧基乙酯等(甲基)丙烯酸羧基烷基酯等。 Examples of the carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, etc. Acid, maleic acid, citraconic acid and other ethylenically unsaturated dicarboxylic acids (dicarboxylic acids with ethylenically unsaturated bonds); the anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylate (meth)acrylic acid carboxyalkyl ester, etc.

前述具有官能基之丙烯酸系單體較佳為含羥基之單體、含羧基之單體，更佳為含羥基之單體。 The aforementioned acrylic monomer having a functional group is preferably a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and more preferably a hydroxyl group-containing monomer.

構成前述丙烯酸系聚合物(a11)之前述具有官能基之丙烯酸系單體可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The functional group-containing acrylic monomer constituting the acrylic polymer (a11) may be only one type or two or more types; in the case of two or more types, these combinations and ratios may be arbitrarily selected.

作為不具有前述官能基之丙烯酸系單體，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸 第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯(亦稱為(甲基)丙烯酸月桂酯)、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯(亦稱為(甲基)丙烯酸肉豆蔻酯)、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯(亦稱為(甲基)丙烯酸棕櫚酯)、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯(亦稱為(甲基)丙烯酸硬脂酯)等構成烷基酯之烷基的碳數為1至18之鏈狀結構之(甲基)丙烯酸烷基酯等。 Examples of the acrylic monomer not having the above-mentioned functional group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, (meth)acrylic acid tert-butyl, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, (meth)acrylate Lauryl acrylate (also known as lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (also known as meat (meth)acrylate) myristyl), pentadecyl (meth)acrylate, cetyl (meth)acrylate (also known as palmityl (meth)acrylate), heptadecyl (meth)acrylate, ( Alkyl (meth)acrylate having a chain structure with a carbon number of 1 to 18 in the alkyl group constituting the alkyl ester, such as octadecyl meth)acrylate (also known as stearyl (meth)acrylate) Wait.

另外，作為前述不具有官能基之丙烯酸系單體，例如亦可列舉：(甲基)丙烯酸甲氧基甲酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基甲酯、(甲基)丙烯酸乙氧基乙酯等含烷氧基烷基之(甲基)丙烯酸酯；包含(甲基)丙烯酸苯酯等(甲基)丙烯酸芳基酯等之具有芳香族基之(甲基)丙烯酸酯；非交聯性的(甲基)丙烯醯胺及其衍生物；(甲基)丙烯酸N,N-二甲胺基乙酯、(甲基)丙烯酸N,N-二甲胺基丙酯等非交聯性的具有三級胺基之(甲基)丙烯酸酯等。 Moreover, as an acryl-type monomer which does not have the said functional group, (meth)acrylate methoxymethyl, (meth)acrylate methoxyethyl, (meth)acrylate ethoxymethyl can also be mentioned, for example. (meth)acrylates containing alkoxyalkyl groups such as ethoxyethyl (meth)acrylates; aromatic groups containing aryl (meth)acrylates such as phenyl (meth)acrylates (meth)acrylate; non-crosslinkable (meth)acrylamide and its derivatives; (meth)acrylate N,N-dimethylaminoethyl ester, (meth)acrylate N,N- Non-crosslinkable (meth)acrylates having tertiary amine groups, such as dimethylaminopropyl ester, etc.

構成前述丙烯酸系聚合物(a11)之前述不具有官能基之丙烯酸系單體可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The acrylic monomer which does not have a functional group which comprises the said acrylic polymer (a11) may be only 1 type, and may be 2 or more types; In the case of 2 or more types, these combinations and ratios can be arbitrarily selected.

作為前述非丙烯酸系單體，例如可列舉：乙烯、降冰片烯等烯烴；乙酸乙烯酯；苯乙烯等。 Examples of the non-acrylic monomers include olefins such as ethylene and norbornene; vinyl acetate; styrene and the like.

構成前述丙烯酸系聚合物(a11)之前述非丙烯酸系單體可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The said non-acrylic-type monomer which comprises the said acrylic polymer (a11) may be only 1 type, and may be 2 or more types; In the case of 2 or more types, these combinations and ratios can be selected arbitrarily.

前述丙烯酸系聚合物(a11)中，由具有前述官能基之丙烯酸系單體衍生之結構單元之量相對於構成該丙烯酸系聚合物(a11)之結構單元之總質量的比例(含量)較佳為0.1質量%至50質量%，更佳為1質量%至40質量%，尤佳為3質量%至30質量%。藉由前述比例為此種範圍，可將由前述丙烯酸系聚合物(a11)與前述能量線硬化性化合物(a12)之共聚合所獲得之前述丙烯酸系樹脂(a1-1)中能量線硬化性基的含量容易地調節為使第1保護膜的硬化程度較佳之範圍。 In the aforementioned acrylic polymer (a11), the ratio (content) of the amount of the structural unit derived from the acrylic monomer having the aforementioned functional group to the total mass of the structural units constituting the acrylic polymer (a11) is preferable It is 0.1 mass % to 50 mass %, More preferably, it is 1 mass % to 40 mass %, Especially preferably, it is 3 mass % to 30 mass %. By setting the aforementioned ratio in such a range, the energy ray-curable group in the aforementioned acrylic resin (a1-1) obtained by the copolymerization of the aforementioned acrylic polymer (a11) and the aforementioned energy ray-curable compound (a12) can be The content is easily adjusted to a range in which the degree of hardening of the first protective film is preferable.

構成前述丙烯酸系樹脂(a1-1)之前述丙烯酸系聚合物(a11)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The said acrylic polymer (a11) which comprises the said acrylic resin (a1-1) may be only 1 type, and may be 2 or more types; In the case of 2 or more types, these combinations and ratios can be selected arbitrarily.

保護膜形成用組成物(IV-1)中，丙烯酸系樹脂(a1-1)的含量相對於前述保護膜形成用組成物(IV-1)的總質量，較佳為1質量%至40質量%，更佳為2質量%至30質量%， 尤佳為3質量%至20質量%。 In the composition for forming a protective film (IV-1), the content of the acrylic resin (a1-1) is preferably 1 to 40 mass % with respect to the total mass of the composition for forming a protective film (IV-1). %, more preferably 2% by mass to 30% by mass, It is especially preferable that it is 3 mass % to 20 mass %.

‧能量線硬化性化合物(a12) ‧Energy ray curable compound (a12)

前述能量線硬化性化合物(a12)較佳為具有選自由異氰酸酯基、環氧基及羧基所組成之群組中的1種或2種以上作為可與前述丙烯酸系聚合物(a11)所具有之官能基反應之基，更佳為具有異氰酸酯基作為前述基。於前述能量線硬化性化合物(a12)例如具有異氰酸酯基作為前述基之情形時，該異氰酸酯基與前述具有羥基作為官能基之丙烯酸系聚合物(a11)的該羥基容易反應。 The aforementioned energy ray-curable compound (a12) preferably has one or more selected from the group consisting of an isocyanate group, an epoxy group, and a carboxyl group as a compound that the aforementioned acrylic polymer (a11) has. More preferably, the functional group reacts with an isocyanate group as the aforementioned group. When the energy ray-curable compound (a12) has, for example, an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as a functional group.

前述能量線硬化性化合物(a12)較佳為於1分子中具有1個至5個前述能量線硬化性基，更佳為具有1個至3個。 It is preferable that the said energy ray hardening compound (a12) has 1 to 5 said energy ray hardening groups in 1 molecule, More preferably, it has 1 to 3 pieces.

作為前述能量線硬化性化合物(a12)，例如可列舉：異氰酸2-甲基丙烯醯氧基乙酯、間-異丙烯基-α,α-二甲基苄基異氰酸酯、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、多元醇化合物及(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等。 Examples of the energy ray curable compound (a12) include 2-methacryloyloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, and methacryloyl isocyanate. diisocyanate, allyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate; by reaction of diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth)acrylate Acryloyl monoisocyanate compound obtained; acryl monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound, polyol compound and hydroxyethyl (meth)acrylate, etc.

這些之中，前述能量線硬化性化合物(a12)較佳為異氰酸2-甲基丙烯醯氧基乙酯。 Among these, it is preferable that the said energy ray curable compound (a12) is 2-methacryloyloxyethyl isocyanate.

構成前述丙烯酸系樹脂(a1-1)之前述能量線硬化性化合物(a12)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 Only one type of the energy ray curable compound (a12) constituting the above-mentioned acrylic resin (a1-1) may be used, or two or more types may be sufficient; in the case of two or more types, these combinations and ratios can be arbitrarily selected.

前述丙烯酸系樹脂(a1-1)中，源自前述能量線硬化性化合物(a12)之能量線硬化性基的含量相對於源自前述丙烯酸系聚合物(a11)之前述官能基的含量之比例較佳為20莫耳%至120莫耳%，更佳為35莫耳%至100莫耳%，尤佳為50莫耳%至100莫耳%。藉由前述含量比例為此種範圍，由硬化所形成之保護膜的接著力變得更大。再者，於前述能量線硬化性化合物(a12)為一官能(於1分子中具有1個前述基)化合物之情形時，前述含量之比例的上限值成為100莫耳%，但於前述能量線硬化性化合物(a12)為多官能(於1分子中具有2個以上前述基)化合物之情形時，會有前述含量之比例的上限值超過100莫耳%之情形。 In the acrylic resin (a1-1), the ratio of the content of the energy ray curable group derived from the energy ray curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) It is preferably 20 mol% to 120 mol%, more preferably 35 mol% to 100 mol%, particularly preferably 50 mol% to 100 mol%. By making the said content ratio into such a range, the adhesive force of the protective film formed by hardening becomes large. Furthermore, in the case where the energy ray-curable compound (a12) is a monofunctional (having one of the aforementioned groups in 1 molecule) compound, the upper limit of the ratio of the aforementioned content is 100 mol%, but in the aforementioned energy When the linear curable compound (a12) is a polyfunctional (having two or more of the aforementioned groups in one molecule) compound, the upper limit of the ratio of the aforementioned content may exceed 100 mol %.

前述聚合物(a1)的重量平均分子量(Mw)較佳為100000至2000000，更佳為300000至1500000。 The weight average molecular weight (Mw) of the aforementioned polymer (a1) is preferably from 100,000 to 2,000,000, more preferably from 300,000 to 1,500,000.

於前述聚合物(a1)的至少一部分藉由交聯劑(f)進行交聯之情形時，前述聚合物(a1)可使不屬於上述說明之構 成前述丙烯酸系聚合物(a11)之任一單體且具有與交聯劑(f)反應之基之單體進行聚合，在前述與交聯劑(f)反應之基中進行交聯，亦可在源自前述能量線硬化性化合物(a12)之與前述官能基反應之基中進行交聯。 When at least a part of the above-mentioned polymer (a1) is cross-linked by the cross-linking agent (f), the above-mentioned polymer (a1) may not belong to the structure described above. Polymerization of a monomer that is any monomer of the aforementioned acrylic polymer (a11) and has a group reactive with the crosslinking agent (f), and crosslinking is carried out in the aforementioned group reacted with the crosslinking agent (f), also The crosslinking may be performed in a group derived from the aforementioned energy ray curable compound (a12) which reacts with the aforementioned functional group.

保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之前述聚合物(a1)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The above-mentioned polymer (a1) contained in the composition (IV-1) for forming a protective film and the film for forming a protective film may be only one type or two or more types; in the case of two or more types, these are combined and the ratio can be arbitrarily selected.

(具有能量線硬化性基且分子量為100至80000之化合物(a2)) (Compound (a2) having an energy ray hardening group and having a molecular weight of 100 to 80,000)

作為具有能量線硬化性基且分子量為100至80000之化合物(a2)所具有之能量線硬化性基，可列舉包含能量線硬化性雙鍵之基，作為較佳的該基，可列舉(甲基)丙烯醯基、乙烯基等。 Examples of the energy-ray-curable group of the compound (a2) having an energy-ray-curable group and a molecular weight of 100 to 80,000 include groups containing an energy-ray-curable double bond, and preferable examples of the group include (methyl base) acrylyl, vinyl, etc.

若前述化合物(a2)滿足上述條件，則並無特別限定，可列舉：具有能量線硬化性基之低分子量化合物、具有能量線硬化性基之環氧樹脂、具有能量線硬化性基之酚樹脂等。 The compound (a2) is not particularly limited as long as it satisfies the above-mentioned conditions, and examples thereof include a low molecular weight compound having an energy ray curable group, an epoxy resin having an energy ray curable group, and a phenol resin having an energy ray curable group. Wait.

前述化合物(a2)中，作為具有能量線硬化性基之低分子量化合物，例如可列舉多官能之單體或低聚物等，較佳為具有(甲基)丙烯醯基之丙烯酸酯系化合物。 In the said compound (a2), as a low molecular weight compound which has an energy ray hardening group, a polyfunctional monomer, an oligomer, etc. are mentioned, for example, Preferably it is an acrylate type compound which has a (meth)acryloyl group.

作為前述丙烯酸酯系化合物，例如可列舉：甲基丙烯酸2-羥基-3-(甲基)丙烯醯氧基丙酯、聚乙二醇二(甲基)丙烯酸酯、丙氧基化乙氧基化雙酚A二(甲基)丙烯酸酯、2,2-雙[4-((甲基)丙烯醯氧基聚乙氧基)苯基]丙烷、乙氧基化雙酚A二(甲基)丙烯酸酯、2,2-雙[4-((甲基)丙烯醯氧基二乙氧基)苯基]丙烷、9,9-雙[4-(2-(甲基)丙烯醯氧基乙氧基)苯基]茀、2,2-雙[4-((甲基)丙烯醯氧基聚丙氧基)苯基]丙烷、三環癸烷二甲醇二(甲基)丙烯酸酯(三環癸烷二羥甲基二(甲基)丙烯酸酯)、1,10-癸二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、聚丁二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、2,2-雙[4-((甲基)丙烯醯氧基乙氧基)苯基]丙烷、新戊二醇二(甲基)丙烯酸酯、乙氧基化聚丙二醇二(甲基)丙烯酸酯、2-羥基-1,3-二(甲基)丙烯醯氧基丙烷等2官能(甲基)丙烯酸酯；異氰脲酸三(2-(甲基)丙烯醯氧基乙基)酯、ε-己內酯改性異氰脲酸三-(2-(甲基)丙烯醯氧基乙基)酯、乙氧基化甘油三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、乙氧基化季戊四醇四(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇聚(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯等多官能(甲基)丙烯酸酯；(甲基)丙烯酸胺基甲 酸酯低聚物等多官能(甲基)丙烯酸酯低聚物等。 As said acrylate type compound, for example, 2-hydroxy-3-(meth)acryloyloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxy bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acrylooxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(methyl) ) acrylate, 2,2-bis[4-((meth)acryloyloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxy) ethoxy) phenyl] stilbene, 2,2-bis[4-((meth)acryloyloxypolypropoxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylate (tricyclodecane dimethanol di(meth)acrylate) Cyclodecane dimethylol di(meth)acrylate), 1,10-decanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9- Nonanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate Acrylates, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((methyl) ) acryloxyethoxy)phenyl]propane, neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-di(meth)acrylate 2-functional (meth)acrylates such as meth)acryloyloxypropane; tris(2-(meth)acrylooxyethyl) isocyanurate, ε-caprolactone-modified isocyanuric acid Tris-(2-(meth)acryloyloxyethyl)ester, ethoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate) Acrylates, di-trimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, Polyfunctional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate; aminomethyl (meth)acrylate Polyfunctional (meth)acrylate oligomers such as acid ester oligomers, etc.

前述化合物(a2)中，作為具有能量線硬化性基之環氧樹脂、具有能量線硬化性基之酚樹脂，例如可使用「日本特開2013-194102號公報」中的段落0043等中所記載之樹脂。此種樹脂亦符合構成後述之熱硬化性成分(h)之樹脂，但本發明中視作前述化合物(a2)。 Among the above-mentioned compounds (a2), as the epoxy resin having an energy ray-curable group and the phenol resin having an energy ray-curable group, for example, those described in paragraph 0043 of "Japanese Unexamined Patent Application Publication No. 2013-194102" can be used. of resin. This resin also corresponds to the resin constituting the thermosetting component (h) described later, but is regarded as the aforementioned compound (a2) in the present invention.

前述化合物(a2)的重量平均分子量較佳為100至30000，更佳為300至10000。 The weight average molecular weight of the aforementioned compound (a2) is preferably from 100 to 30,000, more preferably from 300 to 10,000.

保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之前述化合物(a2)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The above-mentioned compound (a2) contained in the composition (IV-1) for forming a protective film and the film for forming a protective film may be only one kind or two or more kinds; in the case of two or more kinds, these combinations and The ratio can be chosen arbitrarily.

[不具有能量線硬化性基之聚合物(b)] [Polymer (b) without energy ray curable group]

於保護膜形成用組成物(IV-1)及保護膜形成用膜含有前述化合物(a2)作為前述能量線硬化性成分(a)之情形時，較佳為進一步亦含有不具有能量線硬化性基之聚合物(b)。 When the composition (IV-1) for forming a protective film and the film for forming a protective film contain the above-mentioned compound (a2) as the above-mentioned energy ray curable component (a), it is preferable to further contain a non-energy ray curable component. base polymer (b).

前述聚合物(b)可至少一部分藉由交聯劑(f)進行交聯，亦可不進行交聯。 At least a part of the said polymer (b) may be crosslinked by the crosslinking agent (f), and may not be crosslinked.

作為不具有能量線硬化性基之聚合物(b)，例如可列 舉：丙烯酸系聚合物、苯氧基樹脂、胺基甲酸酯樹脂、聚酯、橡膠系樹脂、丙烯酸胺基甲酸酯樹脂、聚乙烯醇(PVA)、丁醛樹脂、聚酯胺基甲酸酯樹脂等。 Examples of the polymer (b) having no energy ray hardening group include, for example, Examples: acrylic polymer, phenoxy resin, urethane resin, polyester, rubber resin, urethane acrylate resin, polyvinyl alcohol (PVA), butyral resin, polyester urethane acid ester resin, etc.

這些之中，前述聚合物(b)較佳為丙烯酸系聚合物(以下，有時簡稱為「丙烯酸系聚合物(b-1)」)。 Among these, the aforementioned polymer (b) is preferably an acrylic polymer (hereinafter, abbreviated as "acrylic polymer (b-1)" in some cases).

丙烯酸系聚合物(b-1)可為公知的聚合物，例如可為1種丙烯酸系單體的均聚物，亦可為2種以上丙烯酸系單體的共聚物，還可為1種或2種以上丙烯酸系單體與1種或2種以上除丙烯酸系單體以外的單體(非丙烯酸系單體)之共聚物。 The acrylic polymer (b-1) may be a known polymer, for example, a homopolymer of one acrylic monomer, a copolymer of two or more acrylic monomers, or a single or A copolymer of two or more acrylic monomers and one or more monomers (non-acrylic monomers) other than acrylic monomers.

作為構成丙烯酸系聚合物(b-1)之前述丙烯酸系單體，例如可列舉：(甲基)丙烯酸烷基酯、具有環狀骨架之(甲基)丙烯酸酯、含縮水甘油基之(甲基)丙烯酸酯、含羥基之(甲基)丙烯酸酯、含取代胺基之(甲基)丙烯酸酯等。此處，所謂「取代胺基」，如上文所說明。 Examples of the aforementioned acrylic monomers constituting the acrylic polymer (b-1) include alkyl (meth)acrylates, (meth)acrylates having a cyclic skeleton, and (meth)acrylates having a glycidyl group. group) acrylate, hydroxyl group-containing (meth)acrylate, substituted amine group-containing (meth)acrylate, etc. Here, the so-called "substituted amino group" is as described above.

作為前述(甲基)丙烯酸烷基酯，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基) 丙烯酸正辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯(亦稱為(甲基)丙烯酸月桂酯)、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯(亦稱為(甲基)丙烯酸肉豆蔻酯)、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯(亦稱為(甲基)丙烯酸棕櫚酯)、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯(亦稱為(甲基)丙烯酸硬脂酯)等構成烷基酯之烷基的碳數為1至18之鏈狀結構之(甲基)丙烯酸烷基酯等。 Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate n-butyl meth)acrylate, isobutyl (meth)acrylate, 2nd butyl (meth)acrylate, 3rd butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylic acid Hexyl ester, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, (meth)acrylate n-octyl acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecane (meth)acrylate base ester (also known as lauryl (meth)acrylate), tridecyl (meth)acrylate, myristyl (meth)acrylate (also known as myristyl (meth)acrylate), Pentadecyl (meth)acrylate, cetyl (meth)acrylate (also known as palmityl (meth)acrylate), heptadecyl (meth)acrylate, (meth)acrylic acid Alkyl (meth)acrylate having a chain structure having a carbon number of 1 to 18 in the alkyl group constituting the alkyl ester, such as octadecyl ester (also referred to as stearyl (meth)acrylate), and the like.

作為前述具有環狀骨架之(甲基)丙烯酸酯，例如可列舉：(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊酯等(甲基)丙烯酸環烷基酯；(甲基)丙烯酸苄酯等(甲基)丙烯酸芳烷基酯；(甲基)丙烯酸二環戊烯酯等(甲基)丙烯酸環烯基酯；(甲基)丙烯酸二環戊烯氧基乙酯等(甲基)丙烯酸環烯氧基烷基酯等。 Examples of (meth)acrylates having the aforementioned cyclic skeleton include cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate and dicyclopentyl (meth)acrylate; ) Aralkyl acrylates such as benzyl acrylate; (meth) cycloalkenyl acrylates such as dicyclopentenyl (meth)acrylate; Dicyclopentenyloxyethyl (meth)acrylate, etc. (Meth)acrylic acid cycloalkenyloxyalkyl ester and the like.

作為前述含縮水甘油基之(甲基)丙烯酸酯，例如可列舉(甲基)丙烯酸縮水甘油酯等。 As said glycidyl group-containing (meth)acrylate, glycidyl (meth)acrylate etc. are mentioned, for example.

作為前述含羥基之(甲基)丙烯酸酯，例如可列舉：(甲基)丙烯酸羥基甲酯、(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2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等。 Examples of the hydroxyl group-containing (meth)acrylate include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylate ) 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and the like.

作為前述含取代胺基之(甲基)丙烯酸酯，例如可列舉(甲基)丙烯酸N-甲基胺基乙酯等。 As said substituted amino group containing (meth)acrylate, (meth)acrylate N-methylaminoethyl etc. are mentioned, for example.

作為構成丙烯酸系聚合物(b-1)之前述非丙烯酸系單體，例如可列舉：乙烯、降冰片烯等烯烴；乙酸乙烯酯；苯乙烯等。 As said non-acrylic-type monomer which comprises an acrylic-type polymer (b-1), olefin, such as ethylene and norbornene; vinyl acetate; styrene, etc. are mentioned, for example.

作為至少一部分藉由交聯劑(f)進行交聯且不具有前述能量線硬化性基之聚合物(b)，例如可列舉：前述聚合物(b)中的反應性官能基與交聯劑(f)反應之聚合物。 Examples of the polymer (b) which is at least partially cross-linked by the cross-linking agent (f) and does not have the above-mentioned energy ray curable group include the reactive functional group and the cross-linking agent in the above-mentioned polymer (b), for example. (f) The reacted polymer.

前述反應性官能基根據交聯劑(f)之種類等適宜選擇即可，並無特別限定。例如，於交聯劑(f)為多異氰酸酯化合物之情形時，作為前述反應性官能基，可列舉羥基、羧基、胺基等，這些之中，較佳為與異氰酸酯基之反應性高之羥基。於交聯劑(f)為環氧系化合物之情形時，作為前述反應性官能基，可列舉羧基、胺基、醯胺基等，這些之中，較佳為與環氧基之反應性高之羧基。但是，就防止半導體晶圓或半導體晶片的電路腐蝕之方面而言，前述反應性官能基較佳為羧基以外的基。 The reactive functional group may be appropriately selected according to the type of the crosslinking agent (f) and the like, and is not particularly limited. For example, when the crosslinking agent (f) is a polyisocyanate compound, the reactive functional group includes a hydroxyl group, a carboxyl group, an amine group, and the like, and among these, a hydroxyl group having high reactivity with an isocyanate group is preferred . When the crosslinking agent (f) is an epoxy-based compound, examples of the reactive functional group include a carboxyl group, an amino group, an amide group, and the like, and among these, a high reactivity with an epoxy group is preferred. the carboxyl group. However, the reactive functional group is preferably a group other than a carboxyl group from the viewpoint of preventing corrosion of a semiconductor wafer or a circuit of a semiconductor wafer.

作為具有前述反應性官能基且不具有能量線硬化性基之聚合物(b)，例如可列舉：至少使具有前述反應性官能基之單體進行聚合而獲得之聚合物。於丙烯酸系聚合物(b-1)之情形時，作為構成該丙烯酸系聚合物(b-1)之單體所 列舉之前述丙烯酸系單體及非丙烯酸系單體的任一者或兩者，使用具有前述反應性官能基之單體即可。例如，作為具有羥基作為反應性官能基之前述聚合物(b)，例如可列舉使含羥基之(甲基)丙烯酸酯進行聚合而獲得之聚合物，除此以外，亦可列舉使上文所列舉之前述丙烯酸系單體或非丙烯酸系單體中1個或2個以上氫原子被前述反應性官能基取代而成之單體進行聚合而獲得之聚合物。 As a polymer (b) which has the said reactive functional group and does not have an energy ray hardening group, the polymer obtained by polymerizing at least the monomer which has the said reactive functional group is mentioned, for example. In the case of the acrylic polymer (b-1), as the monomer constituting the acrylic polymer (b-1) Any one or both of the above-mentioned acrylic monomers and non-acrylic monomers may be used, and a monomer having the above-mentioned reactive functional group may be used. For example, as the polymer (b) having a hydroxyl group as a reactive functional group, for example, a polymer obtained by polymerizing a hydroxyl group-containing (meth)acrylate can be mentioned. A polymer obtained by polymerizing a monomer in which one or two or more hydrogen atoms of the aforementioned acrylic monomers or non-acrylic monomers are substituted with the aforementioned reactive functional groups.

具有反應性官能基之前述聚合物(b)中，由具有反應性官能基之單體衍生之結構單元的量相對於構成該聚合物(b)之結構單元的全部量之比例(含量)較佳為1質量%至25質量%，更佳為2質量%至20質量%。藉由前述比例為此種範圍，前述聚合物(b)中，交聯程度成為更佳的範圍。 In the aforementioned polymer (b) having a reactive functional group, the ratio (content) of the amount of the structural unit derived from the monomer having a reactive functional group to the total amount of the structural units constituting the polymer (b) is relatively Preferably it is 1 mass % - 25 mass %, More preferably, it is 2 mass % - 20 mass %. Since the said ratio is such a range, in the said polymer (b), the degree of crosslinking becomes a more preferable range.

就保護膜形成用組成物(IV-1)的造膜性更良好之方面而言，不具有能量線硬化性基之聚合物(b)的重量平均分子量(Mw)較佳為10000至2000000，更佳為100000至1500000。 The weight average molecular weight (Mw) of the polymer (b) not having an energy ray-curable group is preferably from 10,000 to 2,000,000 in terms of better film-forming properties of the protective film-forming composition (IV-1), More preferably, it is 100,000 to 1,500,000.

保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之不具有能量線硬化性基之聚合物(b)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The composition (IV-1) for forming a protective film and the polymer (b) that does not have an energy ray curable group contained in the film for forming a protective film may be one type or two or more types; In the above case, these combinations and ratios can be arbitrarily selected.

作為保護膜形成用組成物(IV-1)，可列舉含有前述聚合物(a1)及前述化合物(a2)的任一者或兩者之組成物。於保護膜形成用組成物(IV-1)含有前述化合物(a2)之情形時，較佳為亦進一步含有不具有能量線硬化性基之聚合物(b)，該情形時，亦較佳為進一步含有前述(a1)。保護膜形成用組成物(IV-1)亦可不含有前述化合物(a2)，且一併含有前述聚合物(a1)及不具有能量線硬化性基之聚合物(b)。 As the composition (IV-1) for forming a protective film, a composition containing either or both of the above-mentioned polymer (a1) and the above-mentioned compound (a2) can be mentioned. When the composition (IV-1) for forming a protective film contains the aforementioned compound (a2), it is preferable to further contain a polymer (b) without an energy ray curable group, and in this case, it is also preferable The above-mentioned (a1) is further contained. The composition (IV-1) for forming a protective film may not contain the above-mentioned compound (a2), and may also contain the above-mentioned polymer (a1) and the polymer (b) having no energy ray curable group together.

於保護膜形成用組成物(IV-1)含有前述聚合物(a1)、前述化合物(a2)及不具有能量線硬化性基之聚合物(b)之情形時，保護膜形成用組成物(IV-1)中，前述化合物(a2)的含量相對於前述聚合物(a1)及不具有能量線硬化性基之聚合物(b)的總含量100質量份，較佳為10質量份至400質量份，更佳為30質量份至350質量份。 When the composition (IV-1) for forming a protective film contains the polymer (a1), the compound (a2), and the polymer (b) without an energy ray curable group, the composition for forming a protective film ( In IV-1), the content of the aforementioned compound (a2) is preferably 10 to 400 parts by mass relative to 100 parts by mass of the total content of the aforementioned polymer (a1) and the polymer (b) having no energy ray hardening group parts by mass, more preferably 30 parts by mass to 350 parts by mass.

保護膜形成用組成物(IV-1)中，前述能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)的合計含量相對於溶劑以外的成分的總含量之比例(亦即保護膜形成用膜中的前述能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)的合計含量)較佳為5質量%至90質量%，更佳為10質量%至80質量%，尤佳為15質量%至70質量%。藉由前述合計含量之比例為此種範圍，保護膜形成用膜的能量線硬化性變得更良好。 In the composition (IV-1) for forming a protective film, the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group to the total content of components other than the solvent (That is, the total content of the energy ray curable component (a) and the polymer (b) not having an energy ray curable group in the film for forming a protective film) is preferably 5% by mass to 90% by mass, more preferably It is 10 to 80 mass %, and it is especially preferable that it is 15 to 70 mass %. Since the ratio of the said total content is such a range, the energy ray curability of the film for protective film formation becomes more favorable.

於保護膜形成用組成物(IV-1)含有前述能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)之情形時，保護膜形成用組成物(IV-1)及保護膜形成用膜中，前述聚合物(b)的含量相對於能量線硬化性成分(a)的含量100質量份，較佳為3質量份至160質量份，更佳為6質量份至130質量份。藉由前述聚合物(b)的前述含量為此種範圍，保護膜形成用膜的能量線硬化性變得更良好。 When the composition (IV-1) for forming a protective film contains the energy ray curable component (a) and the polymer (b) without an energy ray curable group, the composition for forming a protective film (IV-1) ) and the film for forming a protective film, the content of the aforementioned polymer (b) is preferably 3 to 160 parts by mass, more preferably 6 parts by mass relative to 100 parts by mass of the content of the energy ray curable component (a) to 130 parts by mass. When the said content of the said polymer (b) is such a range, the energy-beam curability of the film for protective film formation becomes more favorable.

保護膜形成用組成物(IV-1)中，除能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)以外，亦可根據目的含有選自由光聚合起始劑(c)、填充材料(d)、偶合劑(e)、交聯劑(f)、著色劑(g)、熱硬化性成分(h)及通用添加劑(z)所組成之群組中的1種或2種以上。例如，藉由使用含有前述能量線硬化性成分(a)及熱硬化性成分(h)之保護膜形成用組成物(IV-1)，所形成之保護膜形成用膜藉由加熱而對被接著體之接著力提高，由該保護膜形成用膜形成之保護膜的強度亦提高。 In the composition (IV-1) for forming a protective film, in addition to the energy ray curable component (a) and the polymer (b) having no energy ray curable group, a photopolymerization initiator may be contained according to the purpose 1 in the group consisting of (c), filler (d), coupling agent (e), crosslinking agent (f), colorant (g), thermosetting component (h) and general additive (z) species or two or more. For example, by using the protective film-forming composition (IV-1) containing the energy ray-curable component (a) and the thermosetting component (h), the formed protective-film-forming film is heated to a substrate. The adhesive force of the adhesive body is improved, and the strength of the protective film formed from the film for forming a protective film is also improved.

[光聚合起始劑(c)] [Photopolymerization initiator (c)]

作為光聚合起始劑(c)，例如可列舉：安息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香異丁醚、安息香苯甲酸、安息香苯甲酸甲酯、安息香二甲基縮酮等安息香化合物；苯乙酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮等苯乙酮化合物；雙 (2,4,6-三甲基苯甲醯基)苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦等醯基氧化膦化合物；苄基苯基硫化物、一硫化四甲基秋蘭姆等硫化物化合物；1-羥基環己基苯基酮等α-酮醇化合物；偶氮雙異丁腈等偶氮化合物；二茂鈦等二茂鈦化合物；噻噸酮等噻噸酮化合物；二苯甲酮、2-(二甲基胺基)-1-(4-嗎啉(morpholine)基苯基)-2-苄基-1-丁酮、乙酮，1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)等二苯甲酮化合物；過氧化物化合物；二乙醯等二酮化合物；苯偶醯；二苯偶醯；2,4-二乙基噻噸酮；1,2-二苯基甲烷；2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮；2-氯蒽醌等。 Examples of the photopolymerization initiator (c) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. Benzoin compounds; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, etc. Acetophenone Compound; Bis (2,4,6-trimethylbenzyl)phenylphosphine oxide, 2,4,6-trimethylbenzyldiphenylphosphine oxide and other acylphosphine oxide compounds; benzylphenyl sulfide sulfide compounds such as tetramethylthiuram monosulfide; α-keto alcohol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; Thioxanthone compounds such as thioxanthone; benzophenone, 2-(dimethylamino)-1-(4-morpholine (morpholine)ylphenyl)-2-benzyl-1-butanone, ethyl acetate Ketones, benzophenone compounds such as 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) ; Peroxide compounds; Diketone compounds such as diacetyl; Benzyl; Dibenzoyl; 2,4-diethylthioxanthone; base-1-[4-(1-methylvinyl)phenyl]acetone; 2-chloroanthraquinone, etc.

作為光聚合起始劑(c)，例如亦可使用1-氯蒽醌等醌化合物；胺等光增感劑等。 As the photopolymerization initiator (c), for example, quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines, and the like can also be used.

保護膜形成用組成物(IV-1)所含有之光聚合起始劑(c)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The photopolymerization initiator (c) contained in the composition (IV-1) for forming a protective film may be only one type or two or more types; in the case of two or more types, these combinations and ratios may be arbitrary choose.

於使用光聚合起始劑(c)之情形時，保護膜形成用組成物(IV-1)中，光聚合起始劑(c)的含量相對於能量線硬化性化合物(a)的含量100質量份，較佳為0.01質量份至20質量份，更佳為0.03質量份至10質量份，尤佳為0.05質量份至5質量份。 In the case of using the photopolymerization initiator (c), in the protective film-forming composition (IV-1), the content of the photopolymerization initiator (c) is 100 relative to the content of the energy ray curable compound (a) The mass part is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, particularly preferably 0.05 to 5 parts by mass.

[填充材料(d)] [filler (d)]

藉由保護膜形成用膜含有填充材料(d)，保護膜形成用膜硬化而獲得之保護膜容易調整熱膨脹係數，使該熱膨脹係數對於保護膜之形成對象物而言最佳化，藉此使用保護膜形成用複合片所獲得之封裝的可靠性進一步提高。藉由保護膜形成用膜含有填充材料(d)，可降低保護膜的吸濕率，或提高散熱性。 By containing the filler (d) in the film for forming a protective film, the protective film obtained by curing the film for forming a protective film can easily adjust the coefficient of thermal expansion and optimize the coefficient of thermal expansion for the object to which the protective film is to be formed. The reliability of the package obtained by the composite sheet for protective film formation is further improved. When the film for forming a protective film contains the filler (d), the moisture absorption rate of the protective film can be reduced or heat dissipation can be improved.

作為填充材料(d)，例如可列舉由導熱性材料構成之材料。 As a filler material (d), the material which consists of a thermally conductive material is mentioned, for example.

填充材料(d)可為有機填充材料及無機填充材料之任一者，較佳為無機填充材料。 The filler (d) may be any one of an organic filler and an inorganic filler, preferably an inorganic filler.

作為較佳的無機填充材料，例如可列舉：二氧化矽、氧化鋁、滑石、碳酸鈣、鈦白、鐵丹、碳化矽、氮化硼等的粉末；將這些無機填充材料球形化而成之珠粒；這些無機填充材料的表面改質品；這些無機填充材料的單晶纖維；玻璃纖維等。 As preferred inorganic fillers, for example, powders of silica, alumina, talc, calcium carbonate, titanium dioxide, iron dan, silicon carbide, boron nitride, etc. can be mentioned; these inorganic fillers are spherical Beads; surface modification products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc.

這些之中，無機填充材料較佳為二氧化矽或氧化鋁。 Among these, the inorganic filler is preferably silica or alumina.

填充材料(d)的平均粒徑並無特別限定，較佳為0.01μm至20μm，更佳為0.1μm至15μm，尤佳為0.3μm至10μm。藉由填充材料(d)的平均粒徑為此種範圍，可維持對保護膜之形成對象物之接著性，並且可抑制保護膜之光之透過率之降低。 The average particle diameter of the filler (d) is not particularly limited, but is preferably 0.01 μm to 20 μm, more preferably 0.1 μm to 15 μm, and particularly preferably 0.3 μm to 10 μm. When the average particle diameter of the filler (d) is in such a range, the adhesiveness to the formation object of the protective film can be maintained, and the reduction of the light transmittance of the protective film can be suppressed.

本說明書中，所謂「平均粒徑」只要無特別說明則意指藉由雷射繞射散射法所求出之粒度分佈曲線中累計值50%下的粒徑(D50)之值。 In this specification, unless otherwise specified, the "average particle size" means the value of the particle size (D 50 ) at 50% of the cumulative value in the particle size distribution curve obtained by the laser diffraction scattering method.

保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之填充材料(d)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The composition for forming a protective film (IV-1) and the filler (d) contained in the film for forming a protective film may be only one type or two or more types; in the case of two or more types, these combinations and The ratio can be chosen arbitrarily.

於使用填充材料(d)之情形時，保護膜形成用組成物(IV-1)中，填充材料(d)的含量相對於溶劑以外的全部成分的總含量之比例(亦即保護膜形成用膜中的填充材料(d)的含量)較佳為5質量%至83質量%，更佳為7質量%至78質量%。藉由填充材料(d)的含量為此種範圍，更容易調整上述之熱膨脹係數。 When the filler (d) is used, in the composition (IV-1) for forming a protective film, the ratio of the content of the filler (d) to the total content of all components other than the solvent (that is, for forming a protective film) The content of the filler (d) in the film is preferably 5 to 83% by mass, more preferably 7 to 78% by mass. When the content of the filler (d) is in such a range, the above-mentioned thermal expansion coefficient can be more easily adjusted.

[偶合劑(e)] [Coupling agent (e)]

藉由使用具有可與無機化合物或有機化合物反應之官能基之偶合劑作為偶合劑(e)，可提高保護膜形成用膜對被接著體之接著性及密接性。藉由使用偶合劑(e)，保護膜形成用膜硬化而獲得之保護膜無損耐熱性而耐水性提高。 By using the coupling agent which has a functional group which can react with an inorganic compound or an organic compound as a coupling agent (e), the adhesiveness and adhesiveness of the film for protective film formation with respect to a to-be-adhered body can be improved. By using the coupling agent (e), the protective film obtained by hardening the film for protective film formation does not impair the heat resistance and improves the water resistance.

偶合劑(e)較佳為具有可與能量線硬化性成分(a)、不具有能量線硬化性基之聚合物(b)等所具有之官能基反應 之官能基之化合物，更佳為矽烷偶合劑。 The coupling agent (e) preferably has a functional group reactive with the energy ray curable component (a), the polymer (b) having no energy ray curable group, and the like The functional group compound is more preferably a silane coupling agent.

作為較佳的前述矽烷偶合劑，例如可列舉：3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基甲基二乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-(2-胺基乙基胺基)丙基三甲氧基矽烷、3-(2-胺基乙基胺基)丙基甲基二乙氧基矽烷、3-(苯基胺基)丙基三甲氧基矽烷、3-苯胺基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、3-巰基丙基三甲氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、雙(3-三乙氧基矽烷基丙基)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。 Examples of preferable silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyl Triethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethyl Oxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyl Diethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane Oxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, ethylene trimethoxysilane, vinyltriacetoxysilane, imidazolylsilane, etc.

保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之偶合劑(e)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The composition for forming a protective film (IV-1) and the coupling agent (e) contained in the film for forming a protective film may be only one type or two or more types; in the case of two or more types, these combinations and The ratio can be chosen arbitrarily.

於使用偶合劑(e)之情形時，保護膜形成用組成物(IV-1)及保護膜形成用膜中，偶合劑(e)的含量相對於能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)的總含量100質量份，較佳為0.03質量份至20質量份，更佳為0.05質量份至10質量份，尤佳為0.1質量份至5質量份。藉由偶合劑(e)的前述含量為前述下限值以上，可 獲得更顯著的以下由使用偶合劑(e)所帶來之功效：填充材料(d)於樹脂中的分散性提高，或保護膜形成用膜與被接著體之接著性提高等。藉由偶合劑(e)的前述含量為前述上限值以下，可進一步抑制產生逸氣。 In the case of using the coupling agent (e), in the composition for forming a protective film (IV-1) and the film for forming a protective film, the content of the coupling agent (e) is relative to the energy ray curable component (a) and does not have The total content of the energy ray curable-based polymer (b) is 100 parts by mass, preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass . When the said content of the coupling agent (e) is more than the said lower limit value, it can be The following effects by the use of the coupling agent (e) are obtained more significantly: the dispersibility of the filler (d) in the resin is improved, or the adhesion between the protective film-forming film and the adherend is improved. When the said content of a coupling agent (e) is below the said upper limit, generation|occurrence|production of outgas can be suppressed further.

[交聯劑(f)] [Crosslinking agent (f)]

藉由使用交聯劑(f)，使上述之能量線硬化性成分(a)或不具有能量線硬化性基之聚合物(b)進行交聯，可調節保護膜形成用膜的初期接著力及凝聚力。 By using a crosslinking agent (f) to crosslink the energy ray curable component (a) or the polymer (b) without an energy ray curable group, the initial adhesion force of the protective film-forming film can be adjusted and cohesion.

作為交聯劑(f)，例如可列舉：有機多元異氰酸酯化合物、有機多元亞胺化合物、金屬螯合物系交聯劑(具有金屬螯合物結構之交聯劑)、氮丙啶系交聯劑(具有氮丙啶基之交聯劑)等。 Examples of the crosslinking agent (f) include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate-based crosslinking agents (crosslinking agents having a metal chelate structure), and aziridine-based crosslinking agents. agent (crosslinking agent with aziridine group), etc.

作為前述有機多元異氰酸酯化合物，例如可列舉：芳香族多元異氰酸酯化合物、脂肪族多元異氰酸酯化合物及脂環族多元異氰酸酯化合物(以下，有時將這些化合物統一簡稱為「芳香族多元異氰酸酯化合物等」)；前述芳香族多元異氰酸酯化合物等的三聚物、異氰脲酸酯體及加合物；使前述芳香族多元異氰酸酯化合物等與多元醇化合物反應而獲得之末端異氰酸酯胺基甲酸酯預聚物等。前述「加合物」意指前述芳香族多元異氰酸酯化合物、脂肪族多元異氰酸酯化合物或脂環族多元異氰酸酯化合物，與乙 二醇、丙二醇、新戊二醇、三羥甲基丙烷或蓖麻油等含低分子活性氫之化合物之反應物，作為前述加合物的示例，可列舉如後述之三羥甲基丙烷之苯二甲基二異氰酸酯加成物等。所謂「末端異氰酸酯胺基甲酸酯預聚物」意指具有胺基甲酸酯鍵，並且於分子末端部具有異氰酸酯基之預聚物。 Examples of the organic polyvalent isocyanate compound include: aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, and alicyclic polyvalent isocyanate compounds (hereinafter, these compounds may be collectively referred to as "aromatic polyvalent isocyanate compounds, etc."); Trimers, isocyanurate compounds, and adducts of the aforementioned aromatic polyvalent isocyanate compounds, etc.; terminal isocyanate urethane prepolymers, etc. obtained by reacting the aforementioned aromatic polyvalent isocyanate compounds, etc. with a polyol compound, etc. . The aforementioned "adduct" means the aforementioned aromatic polyvalent isocyanate compound, aliphatic polyvalent isocyanate compound or alicyclic polyvalent isocyanate compound, which is combined with ethyl alcohol. A reactant of a compound containing a low molecular weight active hydrogen such as glycol, propylene glycol, neopentyl glycol, trimethylolpropane, or castor oil, and examples of the aforementioned adduct include trimethylolpropane and benzene, which will be described later. Dimethyl diisocyanate adduct, etc. The term "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and having an isocyanate group at a molecular terminal.

作為前述有機多元異氰酸酯化合物，更具體而言，例如可列舉：2,4-甲苯二異氰酸酯；2,6-甲苯二異氰酸酯；1,3-苯二甲基二異氰酸酯；1,4-二甲苯二異氰酸酯；二苯基甲烷-4,4'-二異氰酸酯；二苯基甲烷-2,4'-二異氰酸酯；3-甲基二苯基甲烷二異氰酸酯；六亞甲基二異氰酸酯；異佛爾酮二異氰酸酯；二環己基甲烷-4,4'-二異氰酸酯；二環己基甲烷-2,4'-二異氰酸酯；對三羥甲基丙烷等多元醇的全部或一部分羥基，加成甲苯二異氰酸酯、六亞甲基二異氰酸酯及苯二甲基二異氰酸酯的任1種或2種以上而成之化合物；離胺酸二異氰酸酯等。 As said organic polyvalent isocyanate compound, more specifically, 2, 4- toluene diisocyanate; 2, 6- toluene diisocyanate; 1, 3- xylylene diisocyanate; 1, 4- xylene diisocyanate are mentioned, for example Isocyanates; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone Diisocyanate; Dicyclohexylmethane-4,4'-diisocyanate; Dicyclohexylmethane-2,4'-diisocyanate; All or part of the hydroxyl groups of polyols such as p-trimethylolpropane, added with toluene diisocyanate, Any one or two or more compounds of hexamethylene diisocyanate and xylylene diisocyanate; lysine diisocyanate, etc.

作為前述有機多元亞胺化合物，例如可列舉：N,N'-二苯基甲烷-4,4'-雙(1-氮丙啶甲醯胺)、三羥甲基丙烷-三-β-氮丙啶基丙酸酯、四羥甲基甲烷-三-β-氮丙啶基丙酸酯、N,N'-甲苯-2,4-雙(1-氮丙啶甲醯胺)三伸乙基三聚氰胺等。 As said organic polyvalent imine compound, for example, N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-nitrogen Propidyl propionate, tetramethylolmethane-tri-beta-aziridinyl propionate, N,N'-toluene-2,4-bis(1-aziridinecarboxamide) tris-ethyl melamine, etc.

於使用有機多元異氰酸酯化合物作為交聯劑(f)之情形時，作為能量線硬化性成分(a)或不具有能量線硬化性基之聚合物(b)，較佳為使用含羥基之聚合物。於交聯劑(f)具有異氰酸酯基，能量線硬化性成分(a)或不具有能量線硬化性基之聚合物(b)具有羥基之情形時，藉由交聯劑(f)與能量線硬化性成分(a)或不具有能量線硬化性基之聚合物(b)之反應，可將交聯結構簡便地導入至保護膜形成用膜中。 When an organic polyvalent isocyanate compound is used as the crosslinking agent (f), it is preferable to use a hydroxyl group-containing polymer as the energy ray curable component (a) or the polymer (b) without an energy ray curable group . When the crosslinking agent (f) has an isocyanate group, and the energy ray hardening component (a) or the polymer (b) without an energy ray hardening group has a hydroxyl group, the crosslinking agent (f) and the energy ray The reaction of the curable component (a) or the polymer (b) having no energy ray curable group can easily introduce a crosslinked structure into the film for forming a protective film.

保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之交聯劑(f)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The composition for forming a protective film (IV-1) and the crosslinking agent (f) contained in the film for forming a protective film may be only one type or two or more types; in the case of two or more types, these may be combined and the ratio can be arbitrarily selected.

於使用交聯劑(f)之情形時，保護膜形成用組成物(IV-1)中，交聯劑(f)的含量相對於能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)的總含量100質量份，較佳為0.01質量份至20質量份，更佳為0.1質量份至10質量份，尤佳為0.5質量份至5質量份。藉由交聯劑(f)的前述含量為前述下限值以上，可獲得更顯著的由使用交聯劑(f)所帶來之功效。藉由交聯劑(f)的前述含量為前述上限值以下，可抑制交聯劑(f)之過量使用。 When the crosslinking agent (f) is used, in the protective film-forming composition (IV-1), the content of the crosslinking agent (f) is relative to the energy ray curable component (a) and the energy ray curable component (a) without energy ray curability. The total content of the base polymer (b) is 100 parts by mass, preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, particularly preferably 0.5 to 5 parts by mass. When the said content of a crosslinking agent (f) is more than the said lower limit, the effect by using a crosslinking agent (f) is more remarkable. When the said content of a crosslinking agent (f) is below the said upper limit, excessive use of a crosslinking agent (f) can be suppressed.

[著色劑(g)] [Colorant (g)]

作為著色劑(g)，例如可列舉：無機系顏料、有機系 顏料、有機系染料等公知的著色劑。 As the coloring agent (g), for example, inorganic pigments, organic pigments can be mentioned. Well-known coloring agents such as pigments and organic dyes.

作為前述有機系顏料及有機系染料，例如可列舉：銨系色素、花青系色素、部花青系色素、克酮鎓(croconium)系色素、方酸鎓(squalilium)系色素、薁鎓系色素、聚次甲基系色素、萘醌系色素、吡喃鎓系色素、酞菁系色素、萘酞菁系色素、萘內醯胺系色素、偶氮系色素、縮合偶氮系色素、靛藍系色素、紫環酮(perinone)系色素、苝系色素、二噁烷系色素、喹吖啶酮系色素、異吲哚啉酮系色素、喹啉黃(quinophthalone)系色素、吡咯系色素、硫代靛藍系色素、金屬錯合物系色素(金屬錯鹽染料)、二硫醇金屬錯合物系色素、吲哚酚系色素、三烯丙基甲烷系色素、蒽醌系色素、萘酚系色素、次甲基偶氮系色素、苯并咪唑酮系色素、皮蒽酮系色素及士林(threne)系色素等。 Examples of the organic pigments and organic dyes include ammonium-based dyes, cyanine-based dyes, merocyanine-based dyes, croconium-based dyes, squalilium-based dyes, and azulium-based dyes. Pigment, polymethine type pigment, naphthoquinone type pigment, pyrylium type pigment, phthalocyanine type pigment, naphthalocyanine type pigment, naphthalamide type pigment, azo type pigment, condensed azo type pigment, indigo dyes, perinone dyes, perylene dyes, dioxane dyes, quinacridone dyes, isoindolinone dyes, quinophthalone dyes, pyrrole dyes, Thio-indigo-based dyes, metal complex dyes (metal complex dyes), dithiol metal complex dyes, indoxyl-based dyes, triallylmethane-based dyes, anthraquinone-based dyes, naphthol dyes, methine azo dyes, benzimidazolone dyes, picanthrone dyes, threne dyes, and the like.

作為前述無機系顏料，例如可列舉：碳黑、鈷系色素、鐵系色素、鉻系色素、鈦系色素、釩系色素、鋯系色素、鉬系色素、釕系色素、鉑系色素、ITO(Indium Tin Oxide；氧化銦錫)系色素、ATO(Antimony Tin Oxide；氧化銻錫)系色素等。 Examples of the inorganic pigments include carbon black, cobalt-based pigments, iron-based pigments, chromium-based pigments, titanium-based pigments, vanadium-based pigments, zirconium-based pigments, molybdenum-based pigments, ruthenium-based pigments, platinum-based pigments, and ITO. (Indium Tin Oxide; indium tin oxide)-based dye, ATO (Antimony Tin Oxide; antimony tin oxide)-based dye, and the like.

保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之著色劑(g)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The coloring agent (g) contained in the composition (IV-1) for forming a protective film and the film for forming a protective film may be only one type or two or more types; in the case of two or more types, these combinations and The ratio can be chosen arbitrarily.

於使用著色劑(g)之情形時，保護膜形成用膜中的著色劑(g)的含量根據目的適宜調節即可。例如，會有藉由雷射照射對保護膜實施印字之情形，藉由調節保護膜形成用膜中的著色劑(g)的含量，調節保護膜的透光性，可調節印字視認性。該情形時，保護膜形成用組成物(IV-1)中，著色劑(g)的含量相對於溶劑以外的全部成分的總含量之比例(亦即保護膜形成用膜中的著色劑(g)的含量)較佳為0.1質量%至10質量%，更佳為0.4質量%至7.5質量%，尤佳為0.8質量%至5質量%。藉由著色劑(g)的前述含量為前述下限值以上，可獲得更顯著的由使用著色劑(g)所帶來之功效。藉由著色劑(g)的前述含量為前述上限值以下，可抑制著色劑(g)之過量使用。 When using a coloring agent (g), content of the coloring agent (g) in the film for protective film formation may be adjusted suitably according to the objective. For example, the protective film may be printed by laser irradiation. By adjusting the content of the colorant (g) in the protective film-forming film, the light transmittance of the protective film can be adjusted to adjust the visibility of the printed characters. In this case, in the composition (IV-1) for forming a protective film, the ratio of the content of the colorant (g) to the total content of all components other than the solvent (that is, the colorant (g) in the film for forming a protective film ) content) is preferably 0.1 to 10 mass %, more preferably 0.4 to 7.5 mass %, particularly preferably 0.8 to 5 mass %. By making the said content of a coloring agent (g) more than the said lower limit, the effect by using a coloring agent (g) is more remarkable. Excessive use of a coloring agent (g) can be suppressed because the said content of a coloring agent (g) is below the said upper limit.

[熱硬化性成分(h)] [Thermosetting component (h)]

保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之熱硬化性成分(h)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The composition (IV-1) for forming a protective film and the thermosetting component (h) contained in the film for forming a protective film may be only one type or two or more types; in the case of two or more types, these Combinations and ratios can be arbitrarily selected.

作為熱硬化性成分(h)，例如可列舉：環氧系熱硬化性樹脂、熱硬化性聚醯亞胺、聚胺基甲酸酯、不飽和聚酯、聚矽氧樹脂等，較佳為環氧系熱硬化性樹脂。 As the thermosetting component (h), for example, epoxy-based thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, polysiloxane resins, etc. may be mentioned, and preferably Epoxy thermosetting resin.

(環氧系熱硬化性樹脂) (Epoxy thermosetting resin)

環氧系熱硬化性樹脂係由環氧樹脂(h1)及熱硬化劑(h2)構成。 The epoxy-based thermosetting resin is composed of an epoxy resin (h1) and a thermosetting agent (h2).

保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之環氧系熱硬化性樹脂可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The epoxy-based thermosetting resin contained in the composition (IV-1) for forming a protective film and the film for forming a protective film may be only one type or two or more types; in the case of two or more types, these Combinations and ratios can be arbitrarily selected.

‧環氧樹脂(h1) ‧Epoxy resin (h1)

作為環氧樹脂(h1)，可列舉公知的環氧樹脂，例如可列舉：多官能系環氧樹脂、聯苯化合物、雙酚A二縮水甘油醚及其氫化物、鄰甲酚酚醛清漆環氧樹脂、二環戊二烯型環氧樹脂、聯苯型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、伸苯基骨架型環氧樹脂等2官能以上之環氧化合物。 Examples of the epoxy resin (h1) include known epoxy resins, and examples thereof include polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, and o-cresol novolac epoxy resins. Resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, etc. compound.

作為環氧樹脂(h1)，亦可使用具有不飽和烴基之環氧樹脂。具有不飽和烴基之環氧樹脂相較於不具有不飽和烴基之環氧樹脂而言，與丙烯酸系樹脂之相容性較高。因此，藉由使用具有不飽和烴基之環氧樹脂，使用保護膜形成用複合片所獲得之封裝的可靠性提高。 As the epoxy resin (h1), an epoxy resin having an unsaturated hydrocarbon group can also be used. The epoxy resin having an unsaturated hydrocarbon group has higher compatibility with the acrylic resin than the epoxy resin having no unsaturated hydrocarbon group. Therefore, by using the epoxy resin which has an unsaturated hydrocarbon group, the reliability of the package obtained using the composite sheet for protective film formation improves.

作為具有不飽和烴基之環氧樹脂，例如可列舉：多官能系環氧樹脂的一部分環氧基更換為具有不飽和烴基之基而成之化合物。此種化合物例如藉由使(甲基)丙烯酸或其衍生物與環氧基進行加成反應而獲得。 As an epoxy resin which has an unsaturated hydrocarbon group, the compound which replaced some epoxy groups of a polyfunctional epoxy resin with the group which has an unsaturated hydrocarbon group is mentioned, for example. Such a compound is obtained, for example, by subjecting (meth)acrylic acid or a derivative thereof to an addition reaction with an epoxy group.

作為具有不飽和烴基之環氧樹脂，例如可列舉：於構成環氧樹脂之芳香環等上直接鍵結有具有不飽和烴基之基之化合物等。 As an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. by which the group which has an unsaturated hydrocarbon group is directly couple|bonded with the aromatic ring etc. which comprise an epoxy resin are mentioned, for example.

不飽和烴基為具有聚合性之不飽和基，作為該不飽和烴基的具體例，可列舉：次乙基(亦稱為乙烯基)、2-丙烯基(亦稱為烯丙基)、(甲基)丙烯醯基、(甲基)丙烯醯胺基等，較佳為丙烯醯基。 The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples of the unsaturated hydrocarbon group include ethylene (also referred to as vinyl), 2-propenyl (also referred to as allyl), (methyl) group) acrylyl group, (meth)acrylamide group, etc., preferably an acryl group.

環氧樹脂(h1)的數量平均分子量並無特別限定，就保護膜形成用膜的硬化性、以及保護膜的強度及耐熱性之方面而言，較佳為300至30000，更佳為400至10000，尤佳為500至3000。 The number average molecular weight of the epoxy resin (h1) is not particularly limited, but is preferably 300 to 30,000, more preferably 400 to 400, in terms of the curability of the protective film-forming film, and the strength and heat resistance of the protective film. 10000, preferably 500 to 3000.

本說明書中，所謂「數量平均分子量」，只要無特別說明，則意指藉由凝膠滲透層析(GPC)法所測定且以標準聚苯乙烯換算之值顯示之數量平均分子量。 In this specification, unless otherwise specified, the "number average molecular weight" means the number average molecular weight measured by gel permeation chromatography (GPC) and shown in terms of standard polystyrene.

環氧樹脂(h1)的環氧當量較佳為100g/eq至1000g/eq，更佳為150g/eq至800g/eq。 The epoxy equivalent of the epoxy resin (h1) is preferably 100 g/eq to 1000 g/eq, more preferably 150 g/eq to 800 g/eq.

本說明書中，所謂「環氧當量」意指包含1克當量的環氧基之環氧化合物的克數(g/eq)，可依據JIS K 7236：2001之方法進行測定。 In this specification, "epoxy equivalent" means the number of grams (g/eq) of the epoxy compound containing 1 gram equivalent of an epoxy group, and can be measured according to the method of JIS K 7236:2001.

環氧樹脂(h1)可單獨使用1種，亦可併用2種以上，於併用2種以上之情形時，這些組合及比率可任意選擇。 One type of epoxy resin (h1) may be used alone, or two or more types may be used in combination, and when two or more types are used in combination, these combinations and ratios can be arbitrarily selected.

‧熱硬化劑(h2) ‧Thermosetting agent (h2)

熱硬化劑(h2)發揮作為針對環氧樹脂(h1)之硬化劑的功能。 The thermosetting agent (h2) functions as a curing agent for the epoxy resin (h1).

作為熱硬化劑(h2)，例如可列舉：1分子中具有2個以上可與環氧基反應之官能基之化合物。作為前述官能基，例如可列舉：酚性羥基、醇性羥基、胺基、羧基、酸基經酐化而成之基等，較佳為酚性羥基、胺基、或酸基經酐化而成之基，更佳為酚性羥基或胺基。 As a thermosetting agent (h2), the compound which has two or more functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and an acid group formed by an anhydride, and preferably a phenolic hydroxyl group, an amino group, or an acid group formed by an anhydride. The base formed is more preferably a phenolic hydroxyl group or an amine group.

熱硬化劑(h2)中，作為具有酚性羥基之酚系硬化劑，例如可列舉：多官能酚樹脂、聯苯酚、酚醛清漆型酚樹脂、二環戊二烯系酚樹脂、芳烷基酚樹脂等。 Among the thermosetting agents (h2), examples of the phenol-based curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolak-type phenol resins, dicyclopentadiene-based phenol resins, and aralkylphenols. resin, etc.

熱硬化劑(h2)中，作為具有胺基之胺系硬化劑，例如可列舉：二氰二胺(以下，有時簡稱為「DICY」)等。 Among the thermosetting agents (h2), as an amine-based curing agent having an amine group, dicyandiamine (hereinafter, abbreviated as "DICY" in some cases), etc. may be mentioned, for example.

熱硬化劑(h2)亦可具有不飽和烴基。 The thermal hardener (h2) may also have an unsaturated hydrocarbon group.

作為具有不飽和烴基之熱硬化劑(h2)，例如可列舉：酚樹脂的一部分羥基被具有不飽和烴基之基取代而成之化合物、酚樹脂的芳香環上直接鍵結具有不飽和烴基之基而成之化合物等。 Examples of the thermosetting agent (h2) having an unsaturated hydrocarbon group include a compound in which a part of the hydroxyl groups of a phenol resin is substituted with a group having an unsaturated hydrocarbon group, and a group having an unsaturated hydrocarbon group directly bonded to the aromatic ring of the phenol resin. Compounds, etc.

熱硬化劑(h2)中的前述不飽和烴基與上述之具有不飽和烴基之環氧樹脂中的不飽和烴基相同。 The aforementioned unsaturated hydrocarbon group in the thermosetting agent (h2) is the same as the unsaturated hydrocarbon group in the above-mentioned epoxy resin having an unsaturated hydrocarbon group.

於使用酚系硬化劑作為熱硬化劑(h2)之情形時，就保 護膜自支持片之剝離性提高之方面而言，熱硬化劑(h2)較佳為軟化點或玻璃轉移溫度高的酚系硬化劑。 In the case of using a phenolic hardener as the thermal hardener (h2), the From the viewpoint of improving the peelability of the protective film from the support sheet, the thermosetting agent (h2) is preferably a phenol-based curing agent having a high softening point or glass transition temperature.

本說明書中，所謂「玻璃轉移溫度」，係使用示差掃描熱量計，測定試樣的DSC(Differential Scanning Calorimetry；示差掃描熱量)曲線，以所獲得之DSC曲線的反曲點溫度顯示。 In this specification, the "glass transition temperature" refers to measuring the DSC (Differential Scanning Calorimetry) curve of the sample using a differential scanning calorimeter, and displaying it as the inflection point temperature of the obtained DSC curve.

熱硬化劑(h2)中，例如，多官能酚樹脂、酚醛清漆型酚樹脂、二環戊二烯系酚樹脂、芳烷基酚樹脂等樹脂成分的數量平均分子量較佳為300至30000，更佳為400至10000，尤佳為500至3000。 In the thermosetting agent (h2), for example, the number-average molecular weight of resin components such as polyfunctional phenol resin, novolak-type phenol resin, dicyclopentadiene-based phenol resin, aralkylphenol resin is preferably 300 to 30,000, more Preferably, it is 400 to 10,000, and more preferably, it is 500 to 3,000.

熱硬化劑(h2)中，例如，聯苯酚、二氰二胺等非樹脂成分的分子量並無特別限定，例如較佳為60至500。 In the thermosetting agent (h2), for example, the molecular weight of non-resin components such as biphenol and dicyandiamine is not particularly limited, but is preferably 60 to 500, for example.

熱硬化劑(h2)可單獨使用1種，亦可併用2種以上；於併用2種以上之情形時，這些組合及比率可任意選擇。 A thermosetting agent (h2) may be used individually by 1 type, and may use 2 or more types together; When using 2 or more types together, these combinations and ratios can be selected arbitrarily.

於使用熱硬化性成分(h)之情形時，保護膜形成用組成物(IV-1)及保護膜形成用膜中，熱硬化劑(h2)的含量相對於環氧樹脂(h1)的含量100質量份，較佳為0.01質量份至20質量份。 In the case of using the thermosetting component (h), the content of the thermosetting agent (h2) relative to the content of the epoxy resin (h1) in the composition (IV-1) for forming a protective film and the film for forming a protective film 100 parts by mass, preferably 0.01 parts by mass to 20 parts by mass.

於使用熱硬化性成分(h)之情形時，保護膜形成用組成物(IV-1)及保護膜形成用膜中，熱硬化性成分(h)的含量 (例如，環氧樹脂(h1)及熱硬化劑(h2)的總含量)相對於不具有能量線硬化性基之聚合物(b)的含量100質量份，較佳為1質量份至500質量份。 In the case of using the thermosetting component (h), the content of the thermosetting component (h) in the composition for forming a protective film (IV-1) and the film for forming a protective film (For example, the total content of the epoxy resin (h1) and the thermosetting agent (h2)) is preferably 1 to 500 parts by mass relative to 100 parts by mass of the content of the polymer (b) having no energy ray hardening group share.

[通用添加劑(z)] [General Additives (z)]

通用添加劑(z)可為公知的通用添加劑，可根據目的而任意選擇，並無特別限定，作為較佳的通用添加劑，例如可列舉：塑化劑、抗靜電劑、抗氧化劑、吸氣劑等。 The general-purpose additive (z) can be a known general-purpose additive, and can be arbitrarily selected according to the purpose without particular limitation. As a preferred general-purpose additive, for example, plasticizers, antistatic agents, antioxidants, getters, etc. can be mentioned. .

保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之通用添加劑(z)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The composition for forming a protective film (IV-1) and the general-purpose additive (z) contained in the film for forming a protective film may be only one type or two or more types; in the case of two or more types, these combinations and The ratio can be chosen arbitrarily.

於使用通用添加劑(z)之情形時，保護膜形成用組成物(IV-1)及保護膜形成用膜中的通用添加劑(z)的含量並無特別限定，根據目的適宜選擇即可。 When the general-purpose additive (z) is used, the content of the general-purpose additive (z) in the composition (IV-1) for forming a protective film and the film for forming a protective film is not particularly limited, and may be appropriately selected according to the purpose.

[溶劑] [solvent]

保護膜形成用組成物(IV-1)較佳為進一步含有溶劑。含有溶劑之保護膜形成用組成物(IV-1)的操作性良好。 The protective film-forming composition (IV-1) preferably further contains a solvent. The solvent-containing composition for forming a protective film (IV-1) has good handleability.

前述溶劑並無特別限定，作為較佳的前述溶劑，例如可列舉：甲苯、二甲苯等烴；甲醇、乙醇、2-丙醇、異丁醇(亦稱為2-甲基丙烷-1-醇)、1-丁醇等醇；乙酸乙酯等酯；丙酮、甲基乙基酮等酮；四氫呋喃等醚；二甲基甲醯胺、N-甲基吡咯啶酮等醯胺(具有醯胺鍵之化合物)等。 The above-mentioned solvent is not particularly limited, and as the preferred above-mentioned solvent, for example, hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, and isobutanol (also known as 2-methylpropan-1-ol) ), alcohols such as 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; bond compound), etc.

保護膜形成用組成物(IV-1)所含有之溶劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些組合及比率可任意選擇。 The solvent contained in the composition (IV-1) for forming a protective film may be only one type or two or more types, and in the case of two or more types, these combinations and ratios can be arbitrarily selected.

就可將保護膜形成用組成物(IV-1)中的含有成分更均勻地混合之方面而言，保護膜形成用組成物(IV-1)所含有之溶劑較佳為甲基乙基酮、甲苯或乙酸乙酯等。 The solvent contained in the composition for forming a protective film (IV-1) is preferably methyl ethyl ketone, since the components contained in the composition for forming a protective film (IV-1) can be mixed more uniformly , toluene or ethyl acetate, etc.

本發明之一態樣中，保護膜形成用膜含有：作為能量線硬化性成分(a2)之三環癸烷二羥甲基二丙烯酸酯(含量：相對於保護膜成形用組成物(IV-1)中的固形物成分的總質量，為5質量%至35質量%，更佳為10質量%至30質量%)；作為不具有能量線硬化基之聚合物(b)之由源自丙烯酸丁酯之結構單元(相對於丙烯酸系樹脂的總質量，為5質量%至15質量%，更佳為7.5質量%至12.5質量%)、源自丙烯酸甲酯之結構單元(相對於丙烯酸系樹脂的總質量，為55質量%至85質量%，更佳為60質量%至80質量%)、源自甲基丙烯酸縮水甘油酯之結構單元(相對於丙烯酸系樹脂的總質量，為2質量%至8質量%，更佳為3質量%至7質量%)及丙烯酸-2-羥基乙酯(相對於丙烯酸系樹脂的總質量，為5質量%至25質量%，更佳為10質量%至20質量%)構成之丙烯酸系樹脂(含量：相對於保護膜形成用組成物(IV-1)中的固形物成分的總質量，為0.5質量%至30質量%，更佳為1質量%至25質量%)；作為光聚合 起始劑(c)之2-(二甲基胺基)-1-(5-嗎啉基苯基)-2-苄基-1-丁酮(含量：相對於保護膜形成用組成物(IV-1)中的固形物成分的總質量，為0.1質量%至0.5質量%，更佳為0.2質量%至0.4質量%)及乙酮，1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)(含量：相對於保護膜形成用組成物(IV-1)中的固形物成分的總質量，為0.1質量%至0.5質量%，更佳為0.2質量%至0.4質量%)；作為填充劑(d)之二氧化矽填料(含量：相對於保護膜形成用組成物(IV-1)中的固形物成分的總質量，為46質量%至86質量%，更佳為56質量%至76質量%)；作為偶合劑(e)之3-甲基丙烯醯氧基丙基三甲氧基矽烷(含量：相對於保護膜形成用組成物(IV-1)中的固形物成分的總質量，為0.1質量%至0.7質量%，更佳為0.3質量%至0.5質量%)；以及作為著色劑(g)之包含酞菁系藍色色素、異吲哚啉酮系黃色色素及蒽醌系紅色色素、以及苯乙烯丙烯酸樹脂之顏料(含量：相對於保護膜形成用組成物(IV-1)中的固形物成分的總質量，為0.5質量%至3.5質量%，更佳為1.0質量%至3.0質量%)(其中，各成分的含量之和相對於保護膜形成用組成物(IV-1)中的固形物成分的總質量不超過100質量%)。 In one aspect of the present invention, the film for forming a protective film contains: tricyclodecane dimethylol diacrylate (content: relative to the composition for forming a protective film (IV- 1) The total mass of the solid content is 5% by mass to 35% by mass, more preferably 10% by mass to 30% by mass); the polymer (b) that does not have an energy ray hardening group is derived from acrylic acid Structural unit of butyl ester (with respect to the total mass of acrylic resin, 5 to 15 mass %, more preferably 7.5 to 12.5 mass %), structural unit derived from methyl acrylate (with respect to acrylic resin total mass of 55 to 85 mass %, more preferably 60 to 80 mass %), structural units derived from glycidyl methacrylate (relative to the total mass of acrylic resin, 2 mass % to 8 mass %, more preferably 3 to 7 mass %) and 2-hydroxyethyl acrylate (relative to the total mass of the acrylic resin, 5 to 25 mass %, more preferably 10 to 25 mass % 20% by mass) of acrylic resin (content: 0.5% by mass to 30% by mass, more preferably 1% by mass to 25% by mass); as photopolymerization 2-(dimethylamino)-1-(5-morpholinylphenyl)-2-benzyl-1-butanone (content: relative to the composition for forming a protective film ( IV-1) The total mass of the solid content is 0.1% by mass to 0.5% by mass, more preferably 0.2% by mass to 0.4% by mass) and ethyl ketone, 1-[9-ethyl-6-(2- Methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) (content: relative to the solid content in the composition for forming a protective film (IV-1) The total mass of 0.1 to 0.5 mass %, more preferably 0.2 to 0.4 mass %); as the filler (d) silica filler (content: relative to the protective film-forming composition (IV- 1) The total mass of the solid content is 46% by mass to 86% by mass, more preferably 56% by mass to 76% by mass); 3-methacryloyloxypropyltrimethyl as the coupling agent (e) Oxysilane (content: 0.1% by mass to 0.7% by mass, more preferably 0.3% by mass to 0.5% by mass relative to the total mass of the solid content in the composition for forming a protective film (IV-1)); and As the colorant (g), a phthalocyanine-based blue dye, an isoindolinone-based yellow dye, an anthraquinone-based red dye, and a styrene acrylic resin pigment (content: relative to the protective film-forming composition (IV) The total mass of the solid content in -1) is 0.5% by mass to 3.5% by mass, more preferably 1.0% by mass to 3.0% by mass) (wherein, the sum of the contents of the respective components is relative to the composition for forming a protective film ( The total mass of the solid content in IV-1) does not exceed 100% by mass).

<<保護膜形成用組成物的製造方法>> <<The manufacturing method of the composition for protective film formation>>

保護膜形成用組成物(IV-1)等保護膜形成用組成物藉由將用以構成該保護膜形成用組成物之各成分加以調配 而獲得。 The composition for forming a protective film, such as the composition for forming a protective film (IV-1), is prepared by preparing the components for forming the composition for forming a protective film. and obtained.

調配各成分時的添加順序並無特別限定，亦可同時添加2種以上之成分。 The order of addition at the time of preparing each component is not particularly limited, and two or more components may be added at the same time.

於使用溶劑之情形時，可藉由下述方式使用：將溶劑與溶劑以外的任一種調配成分混合而將該調配成分預先稀釋；亦可藉由下述方式使用：不將溶劑以外的任一種調配成分預先稀釋而將溶劑與這些調配成分混合。 In the case of using a solvent, it can be used by mixing the solvent with any preparation component other than the solvent and diluting the preparation component in advance; it can also be used in the following way: not using any preparation component other than the solvent The formulating ingredients are pre-diluted and the solvent is mixed with these formulating ingredients.

調配時混合各成分之方法並無特別限定，自以下公知的方法中適宜選擇即可：使攪拌子或攪拌翼等旋轉而進行混合之方法；使用混合機而進行混合之方法；施加超音波而進行混合之方法等。 The method of mixing the components during preparation is not particularly limited, and may be appropriately selected from the following well-known methods: a method of mixing by rotating a stirrer, a stirring blade, etc.; a method of mixing using a mixer; Methods of mixing, etc.

關於添加及混合各成分時的溫度及時間，只要不使各調配成分劣化，則並無特別限定，適宜調節即可，溫度較佳為15℃至30℃。 The temperature and time at the time of adding and mixing each component are not particularly limited as long as each compounded component is not degraded, and may be appropriately adjusted, and the temperature is preferably 15°C to 30°C.

與可用於本發明之保護膜形成用複合片同樣地，作為貼附於半導體晶圓或半導體晶片中的與電路面為相反側的背面，且於支持片上具備顯示接著性之層之複合片，有切割晶粒接合片(dicing die bonding sheet)。 Similar to the composite sheet for forming a protective film that can be used in the present invention, as a composite sheet that is attached to the back surface of the semiconductor wafer or the semiconductor chip on the opposite side to the circuit surface, and has a layer showing adhesiveness on the support sheet, There is a dicing die bonding sheet.

但是，切割晶粒接合片所具備之接著劑層發揮以下功能：與半導體晶片一起自支持片拾取後，將該半導體晶片安裝於基板、引線框架、或其他半導體晶片等時，作為接著劑之功能。另一方面，關於可用於本發明之保護膜形成用複合片中的保護膜形成用膜，就與半導體晶片一起自支 持片拾取之方面而言，與前述接著劑層相同，但最終藉由硬化而成為保護膜，具有保護所貼附之半導體晶片的背面之功能。如此，本發明中的保護膜形成用膜的用途與切割晶粒接合片中的接著劑層不同，當然所要求之性能亦不同。反映該用途之差異，通常，若與切割晶粒接合片中的接著劑層進行比較，則保護膜形成用膜存在較硬，難以拾取之傾向。因此，通常難以將切割晶粒接合片中的接著劑層直接轉用作保護膜形成用複合片中的保護膜形成用膜。作為可用於本發明之具備能量線硬化性之保護膜形成用膜而成之保護膜形成用複合片，可適宜選擇使用附有保護膜的半導體晶片的拾取適性優異的保護膜形成用複合片。 However, the adhesive layer included in the dicing die-bonding sheet functions as an adhesive when the semiconductor wafer is mounted on a substrate, lead frame, or other semiconductor wafer after being picked up from the support sheet together with the semiconductor wafer. . On the other hand, the film for forming a protective film that can be used in the composite sheet for forming a protective film of the present invention is self-supporting together with the semiconductor wafer. In the aspect of holding and picking up, it is the same as the above-mentioned adhesive layer, but it becomes a protective film by curing finally, and has the function of protecting the back surface of the attached semiconductor wafer. In this way, the application of the film for forming a protective film in the present invention is different from that of the adhesive layer in the dicing die bonding sheet, and of course the required performance is also different. Reflecting the difference of this application, when compared with the adhesive layer in a dicing die-bonding sheet normally, the film for protective film formation is hard, and there exists a tendency for it to be difficult to pick up. Therefore, it is generally difficult to directly transfer the adhesive layer in the dicing die-bonding sheet as the film for forming a protective film in the composite sheet for forming a protective film. As the composite sheet for forming a protective film comprising the film for forming a protective film having energy ray curability that can be used in the present invention, a composite sheet for forming a protective film that is excellent in pick-up properties using a semiconductor wafer with a protective film can be appropriately selected.

◇保護膜形成用複合片的製造方法 ◇Manufacturing method of composite sheet for protective film formation

可用於本發明之保護膜形成用複合片可藉由將上述各層以成為對應的位置關係之方式依序積層而製造。各層之形成方法如前文所說明。 The composite sheet for protective film formation which can be used for this invention can be manufactured by laminating|stacking the said each layer sequentially so that it may become a corresponding positional relationship. The formation method of each layer is as described above.

例如，製造支持片時，於基材上積層黏著劑層之情形時，於基材上塗敷上述黏著劑組成物，視需要使黏著劑組成物乾燥即可。 For example, in the case of laminating an adhesive layer on a base material in the production of a support sheet, the above-mentioned adhesive composition is coated on the base material, and the adhesive composition may be dried as necessary.

另一方面，例如，於已積層於基材上之黏著劑層上進而積層保護膜形成用膜之情形時，可於黏著劑層上塗敷保護膜形成用組成物，直接形成保護膜形成用膜。保護膜形 成用膜以外之層亦可使用用以形成該層之組成物，利用同樣的方法，於黏著劑層上積層該層。如此，於使用任一種組成物，形成連續之2層之積層結構之情形時，可於由前述組成物形成之層上，進一步塗敷組成物而新形成層。 On the other hand, for example, when a film for forming a protective film is laminated on an adhesive layer on a substrate, the composition for forming a protective film can be applied on the adhesive layer to directly form a film for forming a protective film. . protective film A composition for forming the layer may be used for the layer other than the film-forming layer, and the layer may be laminated on the adhesive layer by the same method. In this way, in the case of forming a continuous two-layer laminated structure using any of the compositions, a new layer can be formed by further coating the composition on the layer formed of the above-mentioned composition.

但是，較佳為藉由下述方式而形成連續之2層之積層結構：於另一剝離膜上，使用前述組成物，預先形成這些2層中後積層之層，將該已形成之層中的與和前述剝離膜接觸之側為相反側的露出面，與既已形成之其餘層的露出面貼合。此時，前述組成物較佳為塗敷於剝離膜的剝離處理面。形成積層結構後，視需要移除剝離膜即可。 However, it is preferable to form a continuous two-layer laminate structure by using the above-mentioned composition on the other release film to form a layer of these two layers in advance, and then to form a layer of the two layers after the laminate, and to form a layer of the previously formed layer. The exposed surface on the opposite side is on the side that is in contact with the aforementioned release film, and is attached to the exposed surface of the remaining layers that have already been formed. In this case, it is preferable that the said composition is apply|coated to the peeling process surface of a peeling film. After the layered structure is formed, the release film may be removed as necessary.

例如，於製造於基材上積層黏著劑層，於前述黏著劑層上積層保護膜形成用膜而成之保護膜形成用複合片(支持片為基材及黏著劑層之積層物之保護膜形成用複合片)之情形時，於基材上塗敷黏著劑組成物，視需要使黏著劑組成物乾燥，藉此於基材上預先積層黏著劑層，另行於剝離膜上塗敷保護膜形成用組成物，視需要使保護膜形成用組成物乾燥，藉此於剝離膜上預先形成保護膜形成用膜。然後，將該保護膜形成用膜的露出面與已積層於基材上之黏著劑層的露出面貼合，於黏著劑層上積層保護膜形成用膜，藉此獲得保護膜形成用複合片。 For example, a composite sheet for forming a protective film is produced by laminating an adhesive layer on a base material and laminating a film for forming a protective film on the above-mentioned adhesive layer (the support sheet is the protective film of the laminate of the base material and the adhesive layer). In the case of forming a composite sheet), the adhesive composition is coated on the base material, and the adhesive composition is dried if necessary, whereby the adhesive layer is pre-laminated on the base material, and the protective film is separately coated on the release film. As for the composition, if necessary, the composition for forming a protective film is dried to form a film for forming a protective film on the release film in advance. Then, the exposed surface of the film for forming a protective film is bonded to the exposed surface of the adhesive layer laminated on the base material, and the film for forming a protective film is laminated on the adhesive layer to obtain a composite sheet for forming a protective film. .

於基材上積層黏著劑層之情形時，如上所述，亦可代替於基材上塗敷黏著劑組成物之方法，於剝離膜上塗敷黏 著劑組成物，視需要使黏著劑組成物乾燥，藉此於剝離膜上預先形成黏著劑層，將該層的露出面與基材的一方的表面貼合，藉此於基材上積層黏著劑層。 When the adhesive layer is laminated on the substrate, as described above, instead of the method of coating the adhesive composition on the substrate, the adhesive can be applied on the release film. The adhesive composition is dried as necessary, whereby an adhesive layer is formed on the release film in advance, and the exposed surface of the layer is bonded to one surface of the substrate, thereby laminating the adhesive on the substrate. agent layer.

任一種方法中，均於形成目標積層結構後的任意時間點移除剝離膜即可。 In either method, the release film may be removed at any point in time after the formation of the target laminate structure.

如此，構成保護膜形成用複合片之基材以外的層均可利用以下方法積層：預先形成於剝離膜上，再貼合於目標層的表面，因此視需要適宜選擇採用此種步驟之層，製造保護膜形成用複合片即可。 In this way, the layers other than the base material constituting the composite sheet for forming a protective film can be laminated by the following method: preliminarily formed on the release film, and then attached to the surface of the target layer. What is necessary is just to manufacture the composite sheet for protective film formation.

再者，保護膜形成用複合片通常以如下狀態保管：於該保護膜形成用複合片中的與支持片為相反側的最表層(例如，保護膜形成用膜)的表面貼合有剝離膜之狀態。因此，亦可藉由下述方式而獲得保護膜形成用複合片：於該剝離膜(較佳為該剝離膜的剝離處理面)上，塗敷保護膜形成用組成物等用以形成構成最表層之層之組成物，視需要使組成物乾燥，藉此於剝離膜上預先形成構成最表層之層，於該層中的與和剝離膜接觸之側為相反側的露出面上，利用上述任一種方法積層其餘各層，不移除剝離膜而保持貼合狀態不變。 In addition, the composite sheet for protective film formation is usually stored in a state in which a release film is attached to the surface of the outermost layer (for example, a film for protective film formation) on the opposite side to the support sheet in the composite sheet for protective film formation. state. Therefore, the composite sheet for forming a protective film can also be obtained by applying a composition for forming a protective film or the like on the peeling film (preferably, the peeling-treated surface of the peeling film) to form the optimal composition The composition of the layer of the surface layer is dried as necessary to form a layer constituting the outermost layer on the release film in advance, and on the exposed surface of the layer on the opposite side from the side in contact with the release film, using the above-mentioned method. In either method, the remaining layers are laminated without removing the release film and maintaining the attached state.

[實施例] [Example]

以下，藉由具體的實施例對本發明進行更詳細的說 明。但是，本發明並不受以下所示之實施例之任何限定。 Hereinafter, the present invention will be described in more detail by means of specific examples. Bright. However, the present invention is not limited at all by the examples shown below.

以下顯示用於製造保護膜形成用組成物之成分。 The components for producing the composition for forming a protective film are shown below.

‧能量線硬化性成分 ‧Energy ray curable ingredient

(a2)-1：三環癸烷二羥甲基二丙烯酸酯(日本化藥公司製造之「KAYARAD R-684」，2官能紫外線硬化性化合物，分子量304)。 (a2)-1: Tricyclodecane dimethylol diacrylate (“KAYARAD R-684” manufactured by Nippon Kayaku Co., Ltd., bifunctional ultraviolet curable compound, molecular weight 304).

‧不具有能量線硬化性基之聚合物 ‧Polymer without energy ray hardening group

(b)-1：使丙烯酸丁酯(以下，簡稱為「BA」)(10質量份)、丙烯酸甲酯(以下，簡稱為「MA」)(70質量份)、甲基丙烯酸縮水甘油酯(以下，簡稱為「GMA」)(5質量份)及丙烯酸-2-羥基乙酯(以下，簡稱為「HEA」)(15質量份)進行共聚合而成之丙烯酸系樹脂(重量平均分子量300000，玻璃轉移溫度-1℃)。 (b)-1: butyl acrylate (hereinafter abbreviated as “BA”) (10 parts by mass), methyl acrylate (hereinafter abbreviated as “MA”) (70 parts by mass), glycidyl methacrylate ( Hereinafter, abbreviated as "GMA") (5 parts by mass) and 2-hydroxyethyl acrylate (hereinafter, abbreviated as "HEA") (15 parts by mass) copolymerized with acrylic resin (weight average molecular weight 300,000, glass transition temperature -1°C).

‧光聚合起始劑 ‧Photopolymerization initiator

(c)-1：2-(二甲基胺基)-1-(4-嗎啉基苯基)-2-苄基-1-丁酮(BASF公司製造之「Irgacure(註冊商標)369」)。 (c)-1: 2-(dimethylamino)-1-(4-morpholinylphenyl)-2-benzyl-1-butanone ("Irgacure (registered trademark) 369" manufactured by BASF Corporation) ).

(c)-2：乙酮，1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)(BASF公司製造之「Irgacure(註冊商標)OXE02」)。 (c)-2: Ethanone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime ) ("Irgacure (registered trademark) OXE02" manufactured by BASF Corporation).

‧填充材料 ‧Filler

(d)-1：二氧化矽填料(溶融石英填料，平均粒徑8μm) (d)-1: silica filler (fused silica filler, average particle size 8 μm)

‧偶合劑 ‧Coupling agent

(e)-1：3-甲基丙烯醯氧基丙基三甲氧基矽烷(信越化 學工業公司製造之「KBM-503」，矽烷偶合劑)。 (e)-1: 3-Methacryloyloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. "KBM-503" manufactured by Gaku Industries, Ltd., silane coupling agent).

‧著色劑 ‧Colorant

(g)-1：將酞菁系藍色色素(Pigment Blue 15：3)32質量份、異吲哚啉酮系黃色色素(Pigment Yellow 139)18質量份、及蒽醌系紅色色素(Pigment Red 177)50質量份進行混合，以前述3種色素的合計量/苯乙烯丙烯酸樹脂量=1/3(質量比)之方式進行顏料化而獲得之顏料。 (g)-1: 32 parts by mass of a phthalocyanine-based blue dye (Pigment Blue 15:3), 18 parts by mass of an isoindolinone-based yellow dye (Pigment Yellow 139), and an anthraquinone-based red dye (Pigment Red 177) A pigment obtained by mixing 50 parts by mass and carrying out pigmentation such that the total amount of the above-mentioned three kinds of pigments/the amount of styrene acrylic resin=1/3 (mass ratio).

[實施例1] [Example 1]

<保護膜形成用複合片之製造> <Manufacture of the composite sheet for protective film formation>

(保護膜形成用組成物(IV-1)之製造) (Production of composition for forming protective film (IV-1))

使能量線硬化性成分(a2)-1、聚合物(b)-1、光聚合起始劑(c)-1、光聚合起始劑(c)-2、填充材料(d)-1、偶合劑(e)-1及著色劑(g)-1，以這些的含量(固形物成分量，質量份)成為表1所示之值之方式溶解或分散於甲基乙基酮中，於23℃下進行攪拌，藉此製備固形物成分濃度為50質量%之保護膜形成用組成物(IV-1)。 Energy ray hardening component (a2)-1, polymer (b)-1, photopolymerization initiator (c)-1, photopolymerization initiator (c)-2, filler (d)-1, The coupling agent (e)-1 and the coloring agent (g)-1 were dissolved or dispersed in methyl ethyl ketone so that the contents (solid content, parts by mass) of these became the values shown in Table 1, and then By stirring at 23 degreeC, the composition for protective film formation (IV-1) whose solid content concentration is 50 mass % was prepared.

(黏著劑組成物(I-2)之製造) (Manufacture of Adhesive Composition (I-2))

製備固形物成分濃度為30質量%之紫外線硬化性之黏著劑組成物(I-2)，該黏著劑組成物(I-2)含有丙烯酸系聚合物(100質量份，固形物成分)、六亞甲基二異氰酸酯系交聯劑(Nippon Polyurethane公司製造之「Coronate HL」，9質量份)、及寡聚[2-羥基-2-甲基-1-(4-(1-甲基乙烯基)苯基) 丙酮](DKSH公司製造之「KIP-150」，3質量份)，進一步含有作為溶劑之甲基乙基酮。前述丙烯酸系聚合物係使丙烯酸-2-乙基己酯(以下，簡記為「2EHA」)(70mol%)及HEA(30mol%)進行共聚合而成之丙烯酸系聚合物，與異氰酸2-甲基丙烯醯氧基乙酯(以下，簡記為「MOI」)(相對於前述丙烯酸系聚合物中的源自HEA之羥基的總莫耳數，異氰酸2-甲基丙烯醯氧基乙酯中的異氰酸酯基的總莫耳數成為0.8倍之量)反應而獲得，且於側鏈具有甲基丙烯醯氧基，重量平均分子量為600000。 A UV-curable adhesive composition (I-2) having a solid content concentration of 30% by mass was prepared, the adhesive composition (I-2) containing an acrylic polymer (100 parts by mass, solid content), six Methylene diisocyanate-based crosslinking agent ("Coronate HL" manufactured by Nippon Polyurethane, 9 parts by mass), and oligo[2-hydroxy-2-methyl-1-(4-(1-methylvinyl) ) phenyl) Acetone] ("KIP-150" manufactured by DKSH, 3 parts by mass), further containing methyl ethyl ketone as a solvent. The aforementioned acrylic polymer is an acrylic polymer obtained by copolymerizing 2-ethylhexyl acrylate (hereinafter, abbreviated as "2EHA") (70 mol %) and HEA (30 mol %), and isocyanate 2 -Methacryloyloxyethyl ester (hereinafter, abbreviated as "MOI") (2-methacryloyloxy isocyanate relative to the total number of moles of hydroxyl groups derived from HEA in the aforementioned acrylic polymer The total number of moles of isocyanate groups in the ethyl ester becomes 0.8 times the amount) obtained by reacting, and has a methacryloyloxy group in the side chain, and the weight average molecular weight is 600,000.

(支持片之製造) (Manufacture of Support Sheet)

於聚對苯二甲酸乙二酯製膜的單面經聚矽氧處理進行剝離處理之剝離膜(Lintec公司製造之「SP-PET381031」，厚度38μm)的前述剝離處理面，塗敷上述所獲得之黏著劑組成物(I-3)，於120℃下加熱乾燥2分鐘，藉此形成厚度10μm之非能量線硬化性之黏著劑層。 The above-mentioned peeling-treated surface of a peeling film (“SP-PET381031” manufactured by Lintec Co., Ltd., thickness 38 μm) whose one side was subjected to polysiloxane treatment and peeling treatment was applied to the polyethylene terephthalate film. The adhesive composition (I-3) was heated and dried at 120° C. for 2 minutes, thereby forming a non-energy ray-curable adhesive layer with a thickness of 10 μm.

接著，於該黏著劑層的露出面，貼合作為基材之聚丙烯系膜(厚度80μm)，藉此獲得於前述基材的一方的表面上具備前述黏著劑層之支持片(10)-7。 Next, on the exposed surface of the adhesive layer, a polypropylene-based film (thickness 80 μm) used as a base material was pasted to obtain a support sheet (10)- 7.

(保護膜形成用複合片之製造) (Manufacture of a composite sheet for forming a protective film)

於聚對苯二甲酸乙二酯製膜的單面經聚矽氧處理進行剝離處理之剝離膜(Lintec公司製造之 「SP-PET381031」，厚度38μm)的前述剝離處理面，藉由刀式塗佈機塗敷上述所獲得之保護膜形成用組成物(IV-1)，於100℃下乾燥2分鐘，藉此製作厚度25μm之能量線硬化性之保護膜形成用膜(13)-1。 A release film (manufactured by Lintec) that is peeled off by polysiloxane treatment on one side of the polyethylene terephthalate film "SP-PET381031", thickness 38 μm), the above-mentioned peeling-treated surface was coated with the above-obtained protective film-forming composition (IV-1) by a knife coater, and dried at 100° C. for 2 minutes, whereby A film (13)-1 for forming an energy ray curable protective film with a thickness of 25 μm was produced.

接著，自上述所獲得之支持片(10)-7中的黏著劑層移除剝離膜，於該黏著劑層的露出面貼合上述所獲得之保護膜形成用膜(13)-1的露出面，製作保護膜形成用複合片，該保護膜形成用複合片係基材、黏著劑層、保護膜形成用膜(13)-1及剝離膜於這些的厚度方向上依序積層而成。所獲得之保護膜形成用複合片之構成示於表2。 Next, the release film is removed from the adhesive layer in the above-obtained support sheet (10)-7, and the exposed surface of the above-obtained protective film-forming film (13)-1 is pasted on the exposed surface of the adhesive layer. On the surface, a composite sheet for forming a protective film in which a base material, an adhesive layer, a film (13)-1 for forming a protective film, and a release film are sequentially laminated in the thickness direction is produced. The composition of the obtained composite sheet for protective film formation is shown in Table 2.

<保護膜形成用複合片之評價> <Evaluation of the composite sheet for protective film formation>

(保護膜形成用膜與支持片之間的黏著力) (Adhesion between the protective film forming film and the support sheet)

將上述所獲得之保護膜形成用複合片裁斷成25mm×140mm之大小，自保護膜形成用複合片移除剝離膜，使保護膜形成用膜(13)-1的一方的表面露出，作為硬化前試片。另一方面，準備於SUS(stainless steel；不鏽鋼)製支持板(70mm×150mm)的表面貼合有雙面黏著帶之試片。然後，使用貼合機(Fuji公司製造之「LAMIPACKER LPD3214」)，將硬化前試片之保護膜形成用膜(13)-1的露出面貼附於支持板上之前述雙面黏著帶，藉此於支持板經由雙面黏著帶貼附硬化前試片。 The composite sheet for forming a protective film obtained above was cut into a size of 25 mm × 140 mm, the release film was removed from the composite sheet for forming a protective film, and one surface of the film (13)-1 for forming a protective film was exposed as a curing method. pre-test. On the other hand, a test piece in which a double-sided adhesive tape was attached to the surface of a support plate (70 mm×150 mm) made of SUS (stainless steel) was prepared. Then, using a laminating machine (“LAMIPACKER LPD3214” manufactured by Fuji Corporation), the exposed surface of the film (13)-1 for forming a protective film of the test piece before curing was attached to the double-sided adhesive tape on the support plate, using The pre-hardening test piece is attached to the support plate via a double-sided adhesive tape.

接著，使用精密萬能試驗機(島津製作所製造之「Autograph AG-IS」)，進行下述拉伸試驗：於剝離角度180°、測定溫度23℃、拉伸速度300mm/min之條件下，將支持片(10)-7(硬化前之黏著劑層與基材之積層物)自保護膜形成用膜(13)-1剝離，測定此時的荷重(剝離力)，設為保護膜形成用膜(13)-1與支持片(10)-7之間的黏著力。再者，作為前述荷重之測定值，將支持片(10)-7跨越長度100mm而剝離，於此時的測定值中，將最初剝離長度剛好10mm時及最後剝離長度剛好10mm時各自的測定值自有效值中排除在外，採用所得之值。結果示於表2。 Next, using a precision universal testing machine (“Autograph AG-IS” manufactured by Shimadzu Corporation), the following tensile test was carried out: under the conditions of a peel angle of 180°, a measurement temperature of 23° C., and a tensile speed of 300 mm/min, the supporting Sheet (10)-7 (a laminate of an adhesive layer and a base material before curing) was peeled off from the film (13)-1 for forming a protective film, the load (peeling force) at this time was measured, and it was set as a film for forming a protective film Adhesion between (13)-1 and support sheet (10)-7. Furthermore, as the measured value of the aforementioned load, the support sheet (10)-7 was peeled off over a length of 100 mm, and in the measured value at this time, the respective measured values when the first peeled length was just 10 mm and the last peeled length was just 10 mm were measured. Excluded from valid values, the resulting value is used. The results are shown in Table 2.

(保護膜與支持片之間的黏著力) (Adhesion between protective film and support sheet)

利用與上述之硬化前試片之黏著力之測定時相同的方法製作硬化前試片，於SUS製支持板經由雙面黏著帶貼附該硬化前試片。 The test piece before hardening was produced by the same method as the measurement of the adhesive force of the test piece before hardening described above, and the test piece before hardening was attached to the support plate made of SUS via a double-sided adhesive tape.

接著，使用紫外線照射裝置(Lintec公司製造之「RAD2000m/8」)，於照度195mW/cm2、光量170mJ/cm2之條件下，對硬化前試片照射紫外線，藉此使保護膜形成用膜(13)-1硬化，獲得硬化後試片。 Next, using an ultraviolet irradiation device (“RAD2000m/8” manufactured by Lintec Corporation), under the conditions of an illuminance of 195 mW/cm 2 and a light intensity of 170 mJ/cm 2 , the test piece before curing was irradiated with ultraviolet rays to form a film for forming a protective film. (13)-1 Hardening to obtain a hardened test piece.

接著，針對該硬化後試片，利用與上述之硬化前試片之情形相同的方法，測定保護膜形成用膜(13)-1硬化而成之保護膜與支持片(10)-7之間的黏著力。結果示於表2。 Next, with respect to the test piece after hardening, by the same method as the case of the test piece before hardening described above, the distance between the protective film formed by hardening the film (13)-1 for forming a protective film and the support sheet (10)-7 was measured. of adhesion. The results are shown in Table 2.

(切割評價) (Cut Evaluation)

將上述所獲得之保護膜形成用複合片，藉由該保護膜形成用複合片之保護膜形成用膜(13)-1，貼附於6吋矽晶圓(厚度100μm)之#2000研磨面，進而將該片固定於環狀框。 The composite sheet for forming a protective film obtained above is attached to the #2000 polished surface of a 6-inch silicon wafer (thickness 100 μm) through the film (13)-1 for forming a protective film of the composite sheet for forming a protective film (13)-1 , and then fix the sheet to the annular frame.

接著，使用切割刀片，將矽晶圓連同保護膜形成用膜(13)-1一起切割而單片化，獲得2mm×2mm之矽晶片。此時，目視確認有無矽晶片自支持片之飛散，將完全無矽晶片之飛散之情形判定為「○」，將或多或少地存在矽晶片之飛散之情形判定為「×」，對切割適性進行評價。結果示於表2。表2中的「晶片之飛散之抑制」一欄之記載為相應的結果。 Next, using a dicing blade, the silicon wafer is diced together with the film ( 13 )-1 for forming a protective film to be singulated to obtain a silicon wafer of 2 mm×2 mm. At this time, the presence or absence of scattering of the silicon wafers from the support sheet was visually confirmed, and the case where there was no scattering of the silicon wafers at all was judged as "○", and the case where there was more or less scattering of the silicon wafers was judged as "×". suitability for evaluation. The results are shown in Table 2. The column of "Suppression of chip scattering" in Table 2 is the corresponding result.

切割時，亦無切削水向保護膜與支持片之間浸入。 During cutting, no cutting water penetrates between the protective film and the support sheet.

(拾取評價) (pick up evaluation)

接著，使用紫外線照射裝置(Lintec公司製造之「RAD2000m/8」)，於照度195mW/cm2、光量170mJ/cm2之條件下，自支持片(10)-7側對保護膜形成用膜(13)-1照射紫外線，藉此使保護膜形成用膜(13)-1硬化，成為保護膜。 Next, using an ultraviolet irradiation device (“RAD2000m/8” manufactured by Lintec), under the conditions of an illuminance of 195 mW/cm 2 and a light intensity of 170 mJ/cm 2 , the protective film-forming film ( 13)-1 The film (13)-1 for protective film formation is hardened by irradiating an ultraviolet-ray, and becomes a protective film.

接著，使用黏晶機(Canon Machinery公司製造之「BESTEM-D02」)，拾取20個附有保護膜之矽晶片。此時，使用數位顯微鏡(Keyence公司製造，VHX-100，倍率：100倍)對切割所得之矽晶片之切斷面進行觀察。於確認到20μm以上之寬度或深度之破裂、缺損之情形時，產生碎 片，判定為不良(×)，於未確認到此種缺損之情形時，判定為良好(○)。結果示於表2。表2中的「晶片之破裂、缺損之抑制」一欄之記載為相應的結果。 Next, a die bonder (“BESTEM-D02” manufactured by Canon Machinery) was used to pick up 20 silicon wafers with protective films. At this time, the cut surface of the cut silicon wafer was observed using a digital microscope (manufactured by Keyence Corporation, VHX-100, magnification: 100 times). When cracks or defects with a width or depth of 20 μm or more are confirmed, cracks occur. The sheet was judged to be defective (x), and when such a defect was not confirmed, it was judged to be good (◯). The results are shown in Table 2. In Table 2, the column of "Suppression of chipping and chipping" is the corresponding result.

<保護膜形成用片之製造及評價> <Manufacture and evaluation of sheet for forming protective film>

[實施例2] [Example 2]

於聚對苯二甲酸乙二酯製膜的單面經聚矽氧處理進行剝離處理之第1剝離膜(Lintec公司製造之「SP-PET382150」，厚度38μm)的前述剝離處理面，藉由刀式塗佈機塗敷上述所獲得之保護膜形成用組成物(IV-1)，於100℃下乾燥2分鐘，藉此製作厚度25μm之能量線硬化性之保護膜形成用膜(13)-1。 The peeling-treated side of the first peeling film (“SP-PET382150” manufactured by Lintec, thickness 38 μm), which was treated with polysiloxane on one side of the polyethylene terephthalate film, was peeled off with a knife. The above-obtained protective film-forming composition (IV-1) was coated with a type coater, and dried at 100° C. for 2 minutes, thereby producing an energy-ray-curable protective film-forming film (13) with a thickness of 25 μm— 1.

接著，於所獲得之保護膜形成用膜(13)-1的露出面，貼合聚對苯二甲酸乙二酯製膜的單面經聚矽氧處理進行剝離處理之第2剝離膜(Lintec公司製造之「SP-PET381031」，厚度38μm)的剝離面，獲得由第1剝離膜(圖7中的第1剝離膜15'：25μm)、及第2剝離膜15"構成之保護膜形成用片。 Next, on the exposed surface of the obtained film (13)-1 for forming a protective film, a second release film (Lintec) whose one side of the polyethylene terephthalate film was subjected to a polysiloxane treatment and was subjected to a peeling treatment was attached. The peeling surface of "SP-PET381031" manufactured by the company, thickness 38 μm), obtained a protective film formation composed of a first peeling film (15' of the first peeling film: 25 μm in FIG. 7) and a second peeling film 15". piece.

剝離上述所獲得之保護膜形成用片之第2剝離膜後，於6吋矽晶圓(厚度100μm)之#2000研磨面，貼附上述所獲得之保護膜形成用膜(13)-1，獲得由6吋矽晶圓、保護膜形成用膜(13)-1、及第1剝離膜構成之積層體。 After peeling off the second release film of the sheet for forming a protective film obtained above, the film (13)-1 for forming a protective film obtained above was attached to the #2000 polished surface of a 6-inch silicon wafer (thickness 100 μm). A laminate composed of a 6-inch silicon wafer, a protective film forming film (13)-1, and a first release film was obtained.

自上述所獲得之積層體移除第1剝離膜，另外，自以與實施例1相同的方式獲得之支持片(10)-7中的黏著劑層移除剝離膜，於支持片(10)-7中的黏著劑層之露出面，貼附保護膜形成用膜(13)-1及第1剝離膜，且藉由該保護膜形成用膜(13)-1貼附，進而將該片固定於環狀框，靜置30分鐘。 The first release film was removed from the laminate obtained above, and further, the release film was removed from the adhesive layer in the support sheet (10)-7 obtained in the same manner as in Example 1, and the release film was removed from the support sheet (10) On the exposed surface of the adhesive layer in -7, the protective film forming film (13)-1 and the first release film are pasted, and the protective film forming film (13)-1 is pasted, and the sheet is further It was fixed in a ring frame and allowed to stand for 30 minutes.

接著，使用切割刀片，將矽晶圓連同保護膜形成用膜(13)-1一起切割而單片化，獲得2mm×2mm之矽晶片。此時，目視確認有無矽晶片自支持片之飛散，將完全無矽晶片之飛散之情形判定為「○」，將或多或少地存在矽晶片之飛散之情形判定為「×」，對切割適性進行評價。結果示於表2。表2中的「晶片之飛散之抑制」一欄之記載為相應的結果。 Next, using a dicing blade, the silicon wafer is diced together with the film ( 13 )-1 for forming a protective film to be singulated to obtain a silicon wafer of 2 mm×2 mm. At this time, the presence or absence of scattering of the silicon wafers from the support sheet was visually confirmed, and the case where there was no scattering of the silicon wafers at all was judged as "○", and the case where there was more or less scattering of the silicon wafers was judged as "×". suitability for evaluation. The results are shown in Table 2. The column of "Suppression of chip scattering" in Table 2 is the corresponding result.

[實施例3] [Example 3]

<保護膜形成用複合片之製造> <Manufacture of the composite sheet for protective film formation>

(保護膜形成用組成物(IV-1)之製造) (Production of composition for forming protective film (IV-1))

如表1所示，將聚合物(b)-1的含量(調配量)設為2質量份代替22質量份，將填充材料(d)-1的含量(調配量)設為76質量份代替56質量份，除此方面以外，利用與實施例1相同的方法製備保護膜形成用組成物(IV-1)。 As shown in Table 1, the content (compounding amount) of the polymer (b)-1 was 2 parts by mass instead of 22 parts by mass, and the content (compounding amount) of the filler (d)-1 was 76 parts by mass instead of A composition (IV-1) for forming a protective film was prepared by the same method as in Example 1 except for this point of 56 parts by mass.

(保護膜形成用複合片之製造) (Manufacture of a composite sheet for forming a protective film)

使用上述所獲得之保護膜形成用組成物(IV-1)，除此 方面以外，利用與實施例1相同的方法製作厚度25μm之能量線硬化性之保護膜形成用膜(13)-2。 Using the above-obtained composition for forming a protective film (IV-1), other than Except the point, the film (13)-2 for energy ray curable protective film formation of thickness 25 micrometers was produced by the method similar to Example 1.

使用該保護膜形成用膜(13)-2代替保護膜形成用膜(13)-1，除此方面以外，利用與實施例1相同的方法製造保護膜形成用複合片。 A composite sheet for forming a protective film was produced by the same method as in Example 1 except that the film (13)-2 for forming a protective film was used in place of the film (13)-1 for forming a protective film.

所獲得之保護膜形成用複合片之構成示於表2。 The composition of the obtained composite sheet for protective film formation is shown in Table 2.

<保護膜形成用複合片之製造及評價> <Manufacture and evaluation of the composite sheet for protective film formation>

使用上述所獲得之保護膜形成用複合片，利用與實施例1相同的方法，進行切割評價及拾取評價。結果示於表2。 Using the composite sheet for forming a protective film obtained above, by the same method as in Example 1, dicing evaluation and pick-up evaluation were performed. The results are shown in Table 2.

[實施例4] [Example 4]

<保護膜形成用複合片之製造及評價> <Manufacture and evaluation of the composite sheet for protective film formation>

對與製造支持片(10)-7時所使用之基材相同的基材(聚丙烯系膜，厚度80μm)的表面，實施電暈放電處理。如表2所示，使用僅由該進行了表面處理之基材構成之支持片(10)-8代替支持片(10)-7，除此方面以外，利用與實施例1相同的方法製造及評價保護膜形成用複合片。結果示於表2。再者，本實施例中，於相當於支持片(10)-2之前述基材的電暈放電處理面，設置保護膜形成用膜(13)-1。 The corona discharge treatment was performed on the surface of the same base material (polypropylene film, thickness 80 micrometers) as the base material used for manufacturing the support sheet (10)-7. As shown in Table 2, except that the support sheet (10)-8 composed of only the surface-treated base material was used instead of the support sheet (10)-7, the same method as in Example 1 was used to manufacture and The composite sheet for protective film formation was evaluated. The results are shown in Table 2. In addition, in this Example, the film (13)-1 for protective film formation was provided on the corona discharge-treated surface of the said base material corresponding to the support sheet (10)-2.

使用上述所獲得之保護膜形成用複合片，利用與實施例1相同的方法，進行切割評價及拾取評價。結果示於表2。 Using the composite sheet for forming a protective film obtained above, by the same method as in Example 1, dicing evaluation and pick-up evaluation were performed. The results are shown in Table 2.

[比較例1] [Comparative Example 1]

<保護膜形成用複合片之製造及評價> <Manufacture and evaluation of the composite sheet for protective film formation>

將利用與實施例1相同的方法獲得之保護膜形成用複合片，藉由該保護膜形成用複合片之保護膜形成用膜(13)-1，貼附於6吋矽晶圓(厚度100μm)之#2000研磨面，進而將該片固定於環狀框，靜置30分鐘。 The composite sheet for forming a protective film obtained by the same method as in Example 1 was attached to a 6-inch silicon wafer (thickness 100 μm) through the protective film forming film (13)-1 of the composite sheet for forming a protective film (13)-1. ) of the #2000 polished surface, the sheet was further fixed to a ring frame, and left to stand for 30 minutes.

接著，使用紫外線照射裝置(Lintec公司製造之「RAD2000m/8」)，於照度195mW/cm2、光量170mJ/cm2之條件下，自支持片(10)-7側對保護膜形成用膜(13)-1照射紫外線，藉此使保護膜形成用膜(13)-1硬化，成為保護膜。 Next, using an ultraviolet irradiation device (“RAD2000m/8” manufactured by Lintec), under the conditions of an illuminance of 195 mW/cm 2 and a light intensity of 170 mJ/cm 2 , the protective film-forming film ( 13)-1 The film (13)-1 for protective film formation is hardened by irradiating an ultraviolet-ray, and becomes a protective film.

接著，使用切割刀片，將矽晶圓連同保護膜形成用膜(13)-1一起切割而單片化，獲得2mm×2mm之矽晶片。此時，目視確認有無矽晶片自支持片之飛散，將完全無矽晶片之飛散之情形判定為「○」，將或多或少地存在矽晶片之飛散之情形判定為「×」，對切割適性進行評價。結果示於表2。表2中的「晶片之飛散之抑制」一欄之記載為相應的結果。 Next, using a dicing blade, the silicon wafer is diced together with the film ( 13 )-1 for forming a protective film to be singulated to obtain a silicon wafer of 2 mm×2 mm. At this time, the presence or absence of scattering of the silicon wafers from the support sheet was visually confirmed, and the case where there was no scattering of the silicon wafers at all was judged as "○", and the case where there was more or less scattering of the silicon wafers was judged as "×". suitability for evaluation. The results are shown in Table 2. The column of "Suppression of chip scattering" in Table 2 is the corresponding result.

切割時有切削水向保護膜與支持片之間浸入。 When cutting, cutting water is immersed between the protective film and the support sheet.

[比較例2] [Comparative Example 2]

<保護膜形成用片之製造及評價> <Manufacture and evaluation of sheet for forming protective film>

利用與實施例2相同的方法製作由6吋矽晶圓、保護 膜形成用膜(13)-1、及第1剝離膜構成之積層體。 Using the same method as Example 2 to fabricate a 6-inch silicon wafer, protect A layered product composed of a film for film formation (13)-1 and a first release film.

自所獲得之積層體移除第1剝離膜，另外，自以與實施例1相同的方式獲得之支持片(10)-7中的黏著劑層移除剝離膜，於支持片(10)-7中的黏著劑層之露出面，貼附保護膜形成用膜(13)-1及第1剝離膜，藉由該保護膜形成用膜(13)-1貼附，進而將該片固定於環狀框，靜置30分鐘。 The first release film was removed from the obtained laminate, and further, the release film was removed from the adhesive layer in the support sheet (10)-7 obtained in the same manner as in Example 1, and the support sheet (10)- On the exposed surface of the adhesive layer in 7, the protective film forming film (13)-1 and the first release film are pasted, and the protective film forming film (13)-1 is pasted, and then the sheet is fixed on the Ring box, let stand for 30 minutes.

接著，使用紫外線照射裝置(Lintec公司製造之「RAD2000m/8」)，於照度195mW/cm2、光量170mJ/cm2之條件下，自支持片(10)-7側對保護膜形成用膜(13)-1照射紫外線，藉此使保護膜形成用膜(13)-1硬化，成為保護膜。 Next, using an ultraviolet irradiation device (“RAD2000m/8” manufactured by Lintec), under the conditions of an illuminance of 195 mW/cm 2 and a light intensity of 170 mJ/cm 2 , the protective film-forming film ( 13)-1 The film (13)-1 for protective film formation is hardened by irradiating an ultraviolet-ray, and becomes a protective film.

接著，使用切割刀片，將矽晶圓連同保護膜形成用膜(13)-1一起切割而單片化，獲得2mm×2mm之矽晶片。此時，目視確認有無矽晶片自支持片之飛散，將完全無矽晶片之飛散之情形判定為「○」，將或多或少地存在矽晶片之飛散之情形判定為「×」，對切割適性進行評價。結果示於表2。表2中的「晶片之飛散之抑制」一欄之記載為相應的結果。 Next, using a dicing blade, the silicon wafer is diced together with the film ( 13 )-1 for forming a protective film to be singulated to obtain a silicon wafer of 2 mm×2 mm. At this time, the presence or absence of scattering of the silicon wafers from the support sheet was visually confirmed, and the case where there was no scattering of the silicon wafers at all was judged as "○", and the case where there was more or less scattering of the silicon wafers was judged as "×". suitability for evaluation. The results are shown in Table 2. The column of "Suppression of chip scattering" in Table 2 is the corresponding result.

切割時有切削水向保護膜與支持片之間浸入。 When cutting, cutting water is immersed between the protective film and the support sheet.

[比較例3] [Comparative Example 3]

<保護膜形成用複合片之製造及評價> <Manufacture and evaluation of the composite sheet for protective film formation>

利用與實施例3相同的方法製造保護膜形成用複合片。所獲得之保護膜形成用複合片之構成示於表2。 By the same method as Example 3, the composite sheet for protective film formation was manufactured. The composition of the obtained composite sheet for protective film formation is shown in Table 2.

將上述所獲得之保護膜形成用複合片，藉由該保護膜形成用複合片之保護膜形成用膜(13)-2，貼附於6吋矽晶圓(厚度100μm)之#2000研磨面，進而將該片固定於環狀框，靜置30分鐘。 The composite sheet for forming a protective film obtained above is attached to the #2000 polished surface of a 6-inch silicon wafer (thickness 100 μm) through the film (13)-2 for forming a protective film of the composite sheet for forming a protective film (13)-2 , and then the sheet was fixed to a ring frame and left to stand for 30 minutes.

接著，使用紫外線照射裝置(Lintec公司製造之「RAD2000m/8」)，於照度195mW/cm2、光量170mJ/cm2之條件下，自支持片(10)-7側對保護膜形成用膜(13)-1照射紫外線，藉此使保護膜形成用膜(13)-1硬化，成為保護膜。 Next, using an ultraviolet irradiation device (“RAD2000m/8” manufactured by Lintec), under the conditions of an illuminance of 195 mW/cm 2 and a light intensity of 170 mJ/cm 2 , the protective film-forming film ( 13)-1 The film (13)-1 for protective film formation is hardened by irradiating an ultraviolet-ray, and becomes a protective film.

接著，使用切割刀片，將矽晶圓連同保護膜形成用膜(13)-1一起切割而單片化，獲得2mm×2mm之矽晶片。此時，目視確認有無矽晶片自支持片之飛散，將完全無矽晶片之飛散之情形判定為「○」，將或多或少地存在矽晶片之飛散之情形判定為「×」，對切割適性進行評價。結果示於表2。表2中的「晶片之飛散之抑制」一欄之記載為相應的結果。 Next, using a dicing blade, the silicon wafer is diced together with the film ( 13 )-1 for forming a protective film to be singulated to obtain a silicon wafer of 2 mm×2 mm. At this time, the presence or absence of scattering of the silicon wafers from the support sheet was visually confirmed, and the case where there was no scattering of the silicon wafers at all was judged as "○", and the case where there was more or less scattering of the silicon wafers was judged as "×". suitability for evaluation. The results are shown in Table 2. The column of "Suppression of chip scattering" in Table 2 is the corresponding result.

切割時有切削水向保護膜與支持片之間浸入。 When cutting, cutting water is immersed between the protective film and the support sheet.

Figure 106113972-A0305-02-0104-1
Figure 106113972-A0305-02-0104-1
Figure 106113972-A0305-02-0105-2
Figure 106113972-A0305-02-0105-2

Figure 106113972-A0305-02-0105-3
Figure 106113972-A0305-02-0105-3

根據實施例1至實施例4之結果可明確，於切割半導體晶圓，接著對保護膜形成用膜照射能量線而使保護膜形成用膜硬化之情形時，切割時矽晶片之飛散得到抑制，切割適性亦優異，亦可防止切削水向保護膜形成用膜與支持 片之間浸入。推測實施例1至實施例4中，切割半導體晶圓時之保護膜形成用膜與支持片之間的黏著力處於250mN/25mm至6900mN/25mm之相對較高之黏著力之範圍內，藉此可抑制切割時矽晶片之飛散，亦可防止切削水向保護膜形成用膜與支持片之間浸入。 From the results of Examples 1 to 4, it is clear that when the semiconductor wafer is diced and then the protective film-forming film is irradiated with energy rays to harden the protective film-forming film, scattering of the silicon wafer during dicing is suppressed, Also excellent in cutting suitability, and also prevents cutting water from flowing into the protective film formation film and support Dip between slices. It is presumed that in Examples 1 to 4, the adhesive force between the film for forming a protective film and the support sheet at the time of dicing the semiconductor wafer is in the range of relatively high adhesive force of 250 mN/25 mm to 6900 mN/25 mm, whereby The scattering of silicon wafers during dicing can be suppressed, and cutting water can be prevented from infiltrating between the protective film-forming film and the support sheet.

相對於此，比較例1至比較例3中，對保護膜形成用膜照射能量線而使保護膜形成用膜硬化後，切割半導體晶圓。該情形時，推測保護膜與支持片之間的黏著力處於55mN/25mm至70mN/25mm之範圍，前述黏著力小，無法防止切削水向保護膜與支持片之間浸入。 On the other hand, in Comparative Examples 1 to 3, after irradiating the film for protective film formation with energy rays and curing the film for protective film formation, the semiconductor wafer was diced. In this case, it is presumed that the adhesive force between the protective film and the support sheet is in the range of 55 mN/25 mm to 70 mN/25 mm, and the aforementioned adhesive force is small and cannot prevent the infiltration of cutting water between the protective film and the support sheet.

(產業可利用性) (Industrial Availability)

本發明可用於製造半導體裝置。 The present invention can be used to manufacture semiconductor devices.

10‧‧‧支持片 10‧‧‧Support Sheet

11‧‧‧基材 11‧‧‧Substrate

12‧‧‧黏著劑層 12‧‧‧Adhesive layer

13‧‧‧保護膜形成用膜 13‧‧‧Film for forming protective film

13'‧‧‧保護膜 13'‧‧‧Protective film

16‧‧‧治具用接著劑層 16‧‧‧Adhesive layer for jig

17‧‧‧環狀框 17‧‧‧Ring frame

18‧‧‧半導體晶圓 18‧‧‧Semiconductor Wafers

19‧‧‧半導體晶片 19‧‧‧Semiconductor Chips

20‧‧‧切割刀片 20‧‧‧Cutting blades

21‧‧‧能量線照射裝置 21‧‧‧Energy ray irradiation device

Claims (5)

一種附有保護膜的半導體晶片的製造方法，係對依序具備有支持片、能量線硬化性之保護膜形成用膜及半導體晶圓之積層體中的前述半導體晶圓進行切割，接著對前述保護膜形成用膜照射能量線而使前述保護膜形成用膜硬化；前述半導體晶圓係貼附於前述保護膜形成用膜之表面的一部分，前述積層體中的支持片與前述保護膜形成用膜之間的黏著力為80mN/25mm以上。 A method for producing a semiconductor wafer with a protective film, which comprises dicing the semiconductor wafer in a laminate having a support sheet, a film for forming a protective film with energy ray curability, and a semiconductor wafer in this order, and then dicing the semiconductor wafer. The film for forming a protective film is irradiated with energy rays to cure the film for forming a protective film; the semiconductor wafer is attached to a part of the surface of the film for forming a protective film, the support sheet in the laminate and the film for forming a protective film The adhesive force between the films is 80mN/25mm or more. 如請求項1所記載之附有保護膜的半導體晶片的製造方法，其中前述積層體中的支持片與前述保護膜形成用膜之間的黏著力為80mN/25mm至1()000mN/25mm。 The method for producing a semiconductor wafer with a protective film as set forth in claim 1, wherein the adhesive force between the support sheet in the laminate and the film for forming a protective film is 80 mN/25mm to 1()000 mN/25mm. 如請求項1或2所記載之附有保護膜的半導體晶片的製造方法，其中前述積層體係於前述半導體晶圓貼附前述保護膜形成用膜後，於前述保護膜形成用膜貼附支持片而成。 The method for producing a semiconductor wafer with a protective film according to claim 1 or 2, wherein the build-up system affixes a support sheet to the film for forming a protective film after the film for forming a protective film is pasted on the semiconductor wafer. made. 如請求項1或2所記載之附有保護膜的半導體晶片的製造方法，其中前述積層體係將於支持片上具備前述保護膜形成用膜而成之保護膜形成用複合片的前述保護膜形成用膜側貼附於前述半導體晶圓而成。 The method for producing a semiconductor wafer with a protective film as set forth in claim 1 or 2, wherein the lamination system is used for forming the protective film of the composite sheet for forming a protective film in which the film for forming a protective film is provided on a support sheet. The film side is attached to the aforementioned semiconductor wafer. 一種半導體裝置的製造方法，係拾取藉由如請求項1至4中任一項所記載之附有保護膜的半導體晶片的 製造方法所獲得之附有保護膜的半導體晶片，並將前述半導體晶片連接於基板。 A method of manufacturing a semiconductor device, comprising picking up a semiconductor wafer with a protective film as described in any one of claims 1 to 4 The semiconductor wafer with a protective film obtained by the manufacturing method is connected to a substrate.
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