TWI781099B - Protective film forming film, composite sheet for forming protective film and the using of energy line curable film - Google Patents

Protective film forming film, composite sheet for forming protective film and the using of energy line curable film Download PDF

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TWI781099B
TWI781099B TW106113974A TW106113974A TWI781099B TW I781099 B TWI781099 B TW I781099B TW 106113974 A TW106113974 A TW 106113974A TW 106113974 A TW106113974 A TW 106113974A TW I781099 B TWI781099 B TW I781099B
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protective film
film
forming
mass
meth
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TW201806767A (en
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山本大輔
稻男洋一
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日商琳得科股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67132—Apparatus for placing on an insulating substrate, e.g. tape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers

Abstract

A protective film forming film having a property in which, when the protective film forming film is irradiated with an enegy line and thereby a protective film is formed, the ball tack value of the protective film at the inclined angle 30° is 2 or less on JIS Z0237:2010.

Description

保護膜形成用膜、保護膜形成用複合片、以及能量線硬化性膜的用途 Application of protective film forming film, protective film forming composite sheet, and energy ray curable film

本發明係關於一種保護膜形成用膜及保護膜形成用複合片。 The present invention relates to a film for forming a protective film and a composite sheet for forming a protective film.

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2016-092013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. 2016-092013 filed in Japan on April 28, 2016, and the content of this application is incorporated herein.

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, semiconductor devices have been manufactured in the industry using a mounting method called a so-called face down method. In the flip-chip method, a semiconductor wafer having electrodes such as bumps on the circuit surface is used, and the electrodes are bonded to the substrate. For this reason, the back surface of the semiconductor wafer opposite 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之情形。 will form on the backside of the bare semiconductor wafer containing organic material 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，可藉由硬化使保護膜形成用膜形成保護膜，且亦可進一步將支持片用作切割片(dicing sheet)，從而可成為保護膜形成用膜與切割片成為一體之保護膜形成用複合片。 In order to form such a protective film, the composite sheet for protective film formation which provided the film for protective film formation for forming a protective film on a support sheet is used, for example. In the composite sheet for forming a protective film, the film for forming a protective film can be formed into a protective film by curing, and the support sheet can be further used as a dicing sheet, so that the film for forming a protective film and the dicing sheet can become Composite sheet for integral protective film formation.

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進行硬化而形成保護膜。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, a composite sheet for forming a protective film mainly using a film for forming a thermosetting protective film that is cured by heating to form a protective film. In this case, for example, the protective film formation composite sheet is attached to the back surface of the semiconductor wafer (the surface opposite to the electrode formation surface) with a thermosetting protective film formation film, and the protective film is formed by heating. The film is hardened to form a protective film, and the semiconductor wafer is divided into semiconductor wafers together with the protective film by dicing. Then, the semiconductor wafer is picked up by pulling it away from the support sheet as it is while maintaining the protective film attached thereto. In addition, hardening and dicing of the film for protective film formation may be performed in 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 generally 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 irradiating energy rays such as ultraviolet rays to form a protective film. For example, there are disclosed: an energy ray-curable protective film formed on a peeling film (see Patent Document 1); Document 2).

[先前技術文獻] [Prior Art Literature]

[專利文獻] [Patent Document]

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 Unexamined Patent Publication No. 2010-031183.

對於拾取後的附有保護膜的半導體晶片，為了於下一步驟中使用，會有包裝於如圖7所示之壓紋載帶(emboss carrier tape)102，且該壓紋載帶102以捲繞於捲盤(reel)之狀態進行保管、搬送、或商業交易之情形。收納於前述壓紋載帶102時，通常對於拾取後的附有保護膜的半導體晶片101係使半導體晶片的電路面側朝向壓紋載帶102的口袋102a的底部，使保護膜側朝向前述口袋102a的開口部進行收納，並貼附構成壓紋載帶102的蓋部之蓋帶(cover tape)103，藉此將前述開口部封閉而進行包裝。將附有保 護膜的半導體晶片101於下一步驟中使用時，例如將包裝有附有保護膜的半導體晶片101之壓紋載帶102連同捲盤一起設置於貼片機(mounter)，對基板安裝附有保護膜的半導體晶片101。此時，剝離前述蓋帶103，自壓紋載帶102的口袋102a中取出附有保護膜的半導體晶片101，但會有附有保護膜的半導體晶片101藉由保護膜附著於蓋帶103而成為對基板安裝附有保護膜的半導體晶片101之安裝步驟之障礙之情形。 For the semiconductor wafer with protective film after picking up, in order to use in the next step, there will be packaged in emboss carrier tape (emboss carrier tape) 102 as shown in Figure 7, and this emboss carrier tape 102 rolls Storage, transportation, or commercial transactions in a state wound on a reel. When stored in the aforementioned embossed carrier tape 102, generally, for the semiconductor wafer 101 with a protective film after picking up, the circuit surface side of the semiconductor wafer faces the bottom of the pocket 102a of the embossed carrier tape 102, and the protective film side faces the aforementioned pocket. The opening part of 102a is accommodated, and the cover tape (cover tape) 103 which comprises the cover part of the embossed carrier tape 102 is affixed, and the said opening part is closed by this, and packaging is performed. will be accompanied by When the semiconductor wafer 101 of the protective film is used in the next step, for example, the embossed carrier tape 102 packaged with the semiconductor wafer 101 with the protective film 101 is set on a mounter (mounter) together with the reel, and the substrate is mounted with Protective film for the semiconductor wafer 101 . At this time, the above-mentioned cover tape 103 is peeled off, and the semiconductor wafer 101 with the protective film is taken out from the pocket 102a of the embossed carrier tape 102, but the semiconductor wafer 101 with the protective film will be attached to the cover tape 103 by the protective film. It becomes an obstacle to the mounting step of mounting the protective film-attached semiconductor wafer 101 on the substrate.

因此，本發明之目的在於提供一種能量線硬化性之保護膜形成用膜以及具備前述保護膜形成用膜之保護膜形成用複合片，前述保護膜形成用膜具有以下特性：可於半導體晶圓或半導體晶片的背面形成保護膜，將進行切割而拾取之附有保護膜的半導體晶片收納於壓紋載帶的口袋時，可抑制附有保護膜的半導體晶片附著於蓋帶。 Therefore, an object of the present invention is to provide an energy ray-curable protective film forming film and a protective film forming composite sheet comprising the protective film forming film. The protective film forming film has the following characteristics: Or a protective film is formed on the back of the semiconductor wafer, and when the semiconductor wafer with the protective film that is diced and picked up is stored in the pocket of the embossed carrier tape, the semiconductor wafer with the protective film can be prevented from adhering to the cover tape.

為了解決上述課題，本發明提供一種保護膜形成用膜，為能量線硬化性之保護膜形成用膜，對前述保護膜形成用膜照射能量線而成為保護膜時，依據JIS Z0237：2010於傾斜角30°下所測定之前述保護膜的球黏性(ball tack)值為2以下。 In order to solve the above-mentioned problems, the present invention provides a film for forming a protective film, which is an energy ray curable film for forming a protective film. When the film for forming a protective film is irradiated with energy rays to form a protective film, it can The ball tack value of the protective film measured at an angle of 30° is 2 or less.

本發明之保護膜形成用膜中，較佳為前述保護膜形成用膜係含有能量線硬化性成分(a)。 In the film for forming a protective film of the present invention, it is preferable that the film for forming a protective film contains an energy ray curable component (a).

本發明之保護膜形成用膜中，較佳為前述保護膜形成用膜進一步含有光聚合起始劑(c)。 In the film for protective film formation of this invention, it is preferable that the said film for protective film formation further contains a photoinitiator (c).

本發明之保護膜形成用膜中，較佳為相對於能量線硬化性成分(a)100質量份，前述光聚合起始劑(c)的含量為2.0質量份至12.0質量份。 In the film for protective film formation of this invention, it is preferable that content of the said photoinitiator (c) is 2.0 mass parts - 12.0 mass parts with respect to 100 mass parts of energy ray curable components (a).

另外，本發明提供一種保護膜形成用複合片，係於支持片上具備上述任一項所記載之保護膜形成用膜。 Moreover, this invention provides the composite sheet for protective film formation which has the film for protective film formation of any one of said above on a support sheet.

亦即，本發明包含以下之態樣。 That is, the present invention includes the following aspects.

[1]一種保護膜形成用膜，為能量線硬化性之保護膜形成用膜；保護膜形成用膜具有以下特性：照射能量線而成為保護膜時，依據JIS Z0237：2010於傾斜角30°下所測定之前述保護膜的球黏性值為2以下。 [1] A film for forming a protective film, which is an energy ray curable film for forming a protective film; the film for forming a protective film has the following characteristics: When the protective film is formed by irradiating energy rays, it can be formed at an inclination angle of 30° according to JIS Z0237:2010 The ball tack value of the protective film measured below is 2 or less.

[2]如[1]所記載之保護膜形成用膜，其中前述保護膜形成用膜係含有能量線硬化性成分(a)。 [2] The film for forming a protective film according to [1], wherein the film for forming a protective film contains an energy ray curable component (a).

[3]如[2]所記載之保護膜形成用膜，其中前述保護膜形成用膜進一步含有光聚合起始劑(c)。 [3] The film for forming a protective film according to [2], wherein the film for forming a protective film further contains a photopolymerization initiator (c).

[4]如[3]所記載之保護膜形成用膜，其中相對於能量線硬化性成分(a)100質量份，前述光聚合起始劑(c)的含量為2.0質量份至12.0質量份。 [4] The film for forming a protective film according to [3], wherein the photopolymerization initiator (c) is contained in an amount of 2.0 parts by mass to 12.0 parts by mass relative to 100 parts by mass of the energy ray-curable component (a). .

[5]一種保護膜形成用複合片，係於支持片上具備如[1]至[4]中任一項所記載之保護膜形成用膜。 [5] A composite sheet for forming a protective film comprising the film for forming a protective film according to any one of [1] to [4] on a support sheet.

根據本發明，提供一種能量線硬化性之保護膜形成用膜以及具備前述保護膜形成用膜之保護膜形成用複合片，前述保護膜形成用膜具有以下特性：將附有保護膜的半導體晶片收納於壓紋載帶的口袋時，可抑制附有保護膜的半導體晶片附著於蓋帶。 According to the present invention, there are provided an energy ray curable film for forming a protective film and a composite sheet for forming a protective film comprising the film for forming a protective film. The film for forming a protective film has the following characteristics: a semiconductor wafer with a protective film When stored in a pocket of an embossed carrier tape, semiconductor wafers with a protective film can be prevented from adhering to the cover tape.

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

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

10:支持片 10: Support piece

10a:(支持片的)表面 10a: Surface (of support 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 adhesive layer)

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

13a、23a:(保護膜形成用膜的)表面 13a, 23a: surface (of film for protective film formation)

13b:(保護膜形成用膜中的與表面為相反側的另一方的)表面 13b: (the other side opposite to the surface in the film for forming a protective 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: Surface (of the adhesive layer for jigs)

101:附有保護膜的半導體晶片 101: Semiconductor wafer with protective film

102:壓紋載帶 102: Embossed carrier tape

102a:(壓紋載帶的)口袋 102a: pocket (of embossed carrier tape)

103:蓋帶 103: cover tape

圖1係以示意方式顯示本發明之保護膜形成用膜的一實施形態之剖視圖。 Fig. 1 is a cross-sectional view schematically showing one embodiment of the film for forming a protective film of the present invention.

圖2係以示意方式顯示本發明之保護膜形成用複合片的另一實施形態之剖視圖。 Fig. 2 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film of the present invention.

圖3係以示意方式顯示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. 3 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film of the present invention.

圖4係以示意方式顯示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 of the present invention.

圖5係以示意方式顯示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 of the present invention.

圖6係以示意方式顯示本發明之保護膜形成用膜的一實施形態之剖視圖。 Fig. 6 is a cross-sectional view schematically showing one embodiment of the film for forming a protective film of the present invention.

圖7係以示意方式顯示將附有保護膜的半導體晶片收納於壓紋載帶的口袋並貼附蓋帶而封蓋的狀態以及剝離前述蓋帶後的狀態之剖視圖。 7 is a cross-sectional view schematically showing a state in which a semiconductor wafer with a protective film is housed in a pocket of an embossed carrier tape, and a cover tape is attached and sealed, and a state in which the cover tape is peeled off.

◇保護膜形成用膜 ◇Film for protective film formation

本發明之保護膜形成用膜為能量線硬化性之保護膜形成用膜，且具有以下特性：對前述保護膜形成用膜照射能量線而成為保護膜時，依據JIS Z0237：2010於傾斜角30°下所測定之前述保護膜的球黏性值為2以下。 The film for forming a protective film of the present invention is an energy ray-curable film for forming a protective film, and has the following characteristics: When the film for forming a protective film is irradiated with energy rays to form a protective film, it can be formed at an inclination angle of 30° in accordance with JIS Z0237:2010. The ball tack value of the above-mentioned protective film measured under the temperature of 2° is 2 or less.

本發明之保護膜形成用膜可於至少一方的表面具有第1剝離膜，亦可於另一方的表面進一步具有第2剝離膜。本發明之保護膜形成用膜可以捲繞成捲筒狀之長條狀膜之形式提供。 The film for protective film formation of this invention may have a 1st release film on at least one surface, and may further have a 2nd release film on the other surface. The film for protective film formation of this invention can be provided as the elongated film wound up in roll form.

圖1係以示意方式顯示本發明之保護膜形成用膜的一實施形態之剖視圖。圖1中，依序積層有第1剝離膜15'、保護膜形成用膜13及第2剝離膜15"。 Fig. 1 is a cross-sectional view schematically showing one embodiment of the film for forming a protective film of the present invention. In FIG. 1, the 1st peeling film 15', the film 13 for protective film formation, and the 2nd peeling film 15" are laminated|stacked in this order.

本說明書中，會有將保護膜形成用膜中之貼附於半導體晶圓的背面(亦即，與電路面為相反側的表面)之表面稱為「表面(α)」，將與貼附於半導體晶圓的背面之表面為相反側的表面稱為「表面(β)」之情形。 In this specification, the surface of the film for forming a protective film attached to the back surface of the semiconductor wafer (that is, the surface opposite to the circuit surface) is referred to as "surface (α)". The case where the surface on the back side of the semiconductor wafer is the surface on the opposite side is called "surface (β)".

對本發明之保護膜形成用膜照射能量線而成為保護膜時，依據JIS Z0237：2010於傾斜角30°下所測定之前述保護膜中的至少一方的表面(β)的球黏性值為2以下。 When the film for forming a protective film of the present invention is irradiated with energy rays to form a protective film, the spherical viscosity value of at least one surface (β) of the protective film measured at an inclination angle of 30° in accordance with JIS Z0237:2010 is 2 the following.

亦即，作為一態樣，本發明之保護膜形成用膜較佳為具有能量線硬化性，用以於半導體晶圓或半導體晶片的背面形成保護膜，且具有以下特性：對前述保護膜形成用膜照射能量線而成為保護膜時，依據JIS Z0237：2010於傾斜 角30°下所測定之前述保護膜中的與貼附於前述半導體晶圓或半導體晶片之側的表面(α)為相反側的表面(β)的球黏性值為0以上且2以下，更佳為具有前述球黏性值為0以上且未達2之特性。 That is, as an aspect, the film for forming a protective film of the present invention preferably has energy ray curability, is used to form a protective film on a semiconductor wafer or the back surface of a semiconductor wafer, and has the following characteristics: When the film is irradiated with energy rays to form a protective film, it must be tilted according to JIS Z0237:2010 The ball viscosity value of the surface (β) of the protective film on the opposite side to the surface (α) attached to the semiconductor wafer or the side of the semiconductor wafer measured at an angle of 30° is not less than 0 and not more than 2, More preferably, it has the characteristic that the aforementioned ball viscosity value is 0 or more and less than 2.

關於保護膜形成用膜的組成等，將於後文進行敘述。 The composition and the like of the film for protective film formation will be described later.

本發明之保護膜形成用膜可用作構成後述之保護膜形成用複合片之保護膜形成用膜。 The film for protective film formation of this invention can be used as the film for protective film formation which comprises the composite sheet for protective film formation mentioned later.

另外，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而使用，此時的保護膜形成用膜及基材片可適宜使用後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基材片。 In addition, instead of using the composite sheet for protective film formation, after affixing the film for protective film formation on the back surface of the semiconductor wafer, the support sheet may be attached to the film for protective film formation. In this case, the film for protective film formation and The film for protective film formation and the base material sheet which were demonstrated in description of the composite sheet for protective film formation mentioned later can be used suitably for a base sheet.

本發明中，保護膜形成用膜除了以後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再貼附支持片而使用。 In the present invention, the film for forming a protective film may be used in the form of a composite sheet for forming a protective film described later, and may be attached to the aforementioned semiconductor as a sheet for forming a protective film in which a film for forming a protective film is provided on a release film. A support sheet is attached to the back of the wafer for use.

例如，圖1係以示意方式顯示使用本發明之保護膜形成用膜之保護膜形成用片2F的一實施形態之剖視圖。 For example, FIG. 1 is a cross-sectional view schematically showing one embodiment of a sheet for forming a protective film 2F using the film for forming a protective film of the present invention.

此處所示之保護膜形成用片2F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 release film 15', and is equipped with the 2nd release film 15" on the film 13 for protective film formation.

圖1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(亦即保護膜形成用膜13中的具備第2剝離膜15"之側的表面)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上貼附基材片，再將保護膜形成用膜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. 1 is used in the following manner: In the state where the second peeling film 15" on the light peeling side is removed, in the center of the surface 13a of the film 13 for protective film formation (that is, the surface on the side with the second peeling film 15" in the film 13 for protective film formation) Part of the area on the side is attached to the back surface of a semiconductor wafer (not shown), and further, in the state of removing the first release film 15' on the heavy release side, it is placed on the opposite side to the surface 13a of the protective film forming film 13 A base material sheet is stuck on the other surface 13b of the other side, and the area|region near the peripheral edge part of the film 13 for protective film formation is stuck to jigs, such as a ring 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, the peeling film with a small peeling force is called the peeling film of a light peeling side, and the peeling film with a large peeling force is called the peeling film of a heavy peeling side. If there is a difference in the peeling force, when only the peeling film on the light peeling side is peeled off, the risk that the peeling film on the peeling side of the protective film forming film will rise from the weight, or the protective film forming film will follow the two peeling films. Stretch deformation.

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

本發明之保護膜形成用複合片係於支持片上具備能量線硬化性之保護膜形成用膜而成。 The composite sheet for forming a protective film of the present invention is formed of a film for forming a protective film having energy ray curability on a support sheet.

再者，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 addition, in this specification, "the film for protective film formation" means the film for protective film formation before hardening, and "protective film" means the film of the film for protective film formation after hardening.

本說明書中，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 this specification, the term "energy ray" means an electromagnetic wave or a charged particle beam having energy quanta; examples of the aforementioned energy ray include ultraviolet rays, radiation, electron beams, and the like.

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, for example, can be obtained by using high-pressure mercury lamps, fusion (Fusion) H A type lamp, a xenon lamp, a black light lamp, or an LED (Light-Emitting Diode; light-emitting diode) lamp, etc. are used as an ultraviolet source for irradiation. The electron beam may be irradiated with an electron beam generated by an electron beam accelerator or the like.

本說明書中，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 this specification, "energy ray curability" means the property of being cured by irradiation of energy ray, and "non-energy ray curability" means the property of not being cured even when irradiated with energy ray.

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，亦可為8000mN/25mm以下，亦可為7000mN/25mm以下。 The adhesive force between the support sheet in the above-mentioned laminate and the above-mentioned film for forming a protective film is not particularly limited, for example, it may be 80 mN/25 mm or more, may be 100 mN/25 mm or more, may be 150 mN/25 mm or more, or may be It is 200mN/25mm or more; In addition, the upper limit is not particularly limited, and may be 10000mN/25mm or less, 8000mN/25mm or less, or 7000mN/25mm or less.

亦即，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可為80mN/25mm至10000mN/25mm，亦可為150mN/25mm至8000mN/25mm，亦可為200mN/25mm至7000mN/25mm。 That is, the adhesive force between the support sheet in the aforementioned laminate and the aforementioned film for forming a protective film may be 80mN/25mm to 10000mN/25mm, or 150mN/25mm to 8000mN/25mm, or 200mN/25mm to 200mN/25mm. 7000mN/25mm.

藉由將前述黏著力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。另外，藉由將前述黏著力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。 By adjusting the above-mentioned adhesive force to be more than the above-mentioned lower limit value, scattering of silicon wafers during dicing is suppressed, and it is also possible to prevent cutting water from penetrating between the film for protective film formation and the support sheet. In addition, when the protective film is formed by adjusting the adhesive force to be below the upper limit value and then cured by irradiation with energy rays, the adhesive force between the protective film and the support sheet can be easily and appropriately adjusted.

前述保護膜形成用膜藉由照射能量線進行硬化而成為保護膜。該保護膜用以對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)進行保護。保護膜形成用膜為軟質，可容易地貼附於貼附對象物。並且，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。 The said film for protective film formation becomes a protective film by hardening by irradiating an energy ray. This protective film is used to protect the semiconductor wafer or the back surface (the surface opposite to the electrode formation surface) of the semiconductor wafer. The film for protective film formation is soft and can be easily attached to an object to be attached. In addition, when the film for forming a protective film is irradiated with energy rays to form a protective film, the adhesive force between the protective film and the support sheet is preferably from 50 mN/25 mm to 1500 mN/25 mm, more preferably from 52 mN/25 mm to 1450 mN/25 mm. 25mm, preferably 53mN/25mm to 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。另外，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。 When the above-mentioned adhesive force is more than the above-mentioned lower limit value, when picking up the semiconductor wafer with the protective film, the pickup of the semiconductor wafer with the protective film outside the target is suppressed, so that the target semiconductor wafer with the protective film can be picked up with high selectivity. of semiconductor wafers. Moreover, when the said adhesive force is below the said upper limit, when picking up the semiconductor wafer with a protective film, cracking and chipping of a semiconductor wafer are suppressed. Thus, the composite sheet for protective film formation has favorable pick-up property by the said adhesive force being in a specific range.

另外，本發明之一實施形態之保護膜形成用複合片中，藉由前述保護膜形成用膜為能量線硬化性，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。 In addition, in the composite sheet for forming a protective film according to an embodiment of the present invention, since the film for forming a protective film is energy ray curable, compared with the conventional protective film forming film having thermosetting properties, the composite sheet for forming a protective film In the case of a composite sheet, a protective film can be formed by hardening in a short time.

作為本發明之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。 The thickness of the semiconductor wafer or the semiconductor wafer used as the object of the protective film forming composite sheet of the present invention is not particularly limited, but it is preferably 30 μm to 1000 μm, and more preferably 100 μm in order to obtain a more remarkable effect of the present invention. to 300 μm.

以下，對本發明之構成進行詳細說明。 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 composed of one layer (single layer), or may be composed of multiple layers of two or more layers. When the support sheet is composed of multiple layers, the constituent materials and thicknesses of these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited as long as the effect of the present invention is not impaired.

再者，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」，再者所謂「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」。 Furthermore, in this specification, it is not limited to the case of the support sheet. The so-called "a plurality of layers may be the same or different from each other" means "all the layers may be the same, or all the layers may be different, or only some layers may be the same". The term "a plurality of layers are different from each other" means "at least one of the constituent materials and thickness of each layer is different from each other".

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 preferred support sheet, for example, a support sheet formed by laminating an adhesive layer on a base material in direct contact, a support sheet formed by laminating an adhesive layer on a base material through an intermediate layer, a support sheet formed by laminating an adhesive layer only on a base material, Supporting sheets made of materials, etc.

以下，按照上述支持片之每個種類，參照圖式說明本發明之保護膜形成用複合片之示例。再者，以下之說明中所使用之圖中，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 protective film formation of the present invention will be described for each type of the above-mentioned support sheet with reference to the drawings. In addition, in the drawings used in the following description, in order to facilitate the understanding of the features of the present invention, the main parts may be enlarged and displayed for convenience, and the dimensional ratio of each component is not limited to the actual one. same.

圖2係以示意方式顯示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 one embodiment of the composite sheet for forming a protective film of 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具有以下構成：於支持片10的一方的表面10a(例如支持片10中的黏著劑層12側的表面)上積層有保護膜形成用膜13。另外，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 equipped with the adhesive agent layer 12 on the base material 11, and is equipped with the film 13 for protective film formation on the adhesive agent layer 12. The support sheet 10 is a laminate of the base material 11 and the adhesive layer 12. In other words, the composite sheet 1A for forming a protective film has the following structure: Surface) is laminated with the film 13 for protective film formation. Moreover, 1 A of composite sheets for protective film formation are equipped with the peeling film 15 on the film 13 for protective film formation further.

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(亦即黏著劑層12中的與和基材11接觸之側為相反側的面)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(亦即保護膜形成用膜13中的與和黏著劑層12接觸之側為相反側的面)的一部分亦即表面13a的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，亦即治具用接著劑層16中的與和保護膜形成用膜13接觸之側為相反側的面以及治具用接著劑層16的側面)積層有剝離膜15。 In the composite sheet 1A for forming a protective film, the adhesive layer 12 is laminated on one surface 11a of the base material 11, and the surface 12a of the adhesive layer 12 (that is, the side of the adhesive layer 12 that is in contact with the base material 11) The film 13 for forming a protective film is layered over the entire surface of the film 13 on the opposite side), and the surface 13a of the film 13 for forming a protective film (that is, the side of the film 13 for forming a protective film that is in contact with the adhesive layer 12 is the opposite side) The adhesive layer 16 for the jig is laminated on a part of the surface 13a, that is, the area near the periphery of the surface 13a, and the adhesive layer 16 for the jig is not deposited on the surface 13a of the protective film forming film 13 The surface 16a of the adhesive layer 16 for jigs (the upper surface, that is, the side opposite to the side in contact with the film 13 for forming a protective film in the adhesive layer 16 for jigs and the side surface of the adhesive layer 16 for jigs ) is laminated with a release film 15.

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)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 1A, the adhesive force between the hardened protective film-forming film 13 (that is, the protective film) and the support sheet 10, in other words, the protection The adhesive force between the film and the adhesive layer 12 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 jig adhesive layer 16 may have, for example, a single-layer structure containing an adhesive component, or may have a multi-layer structure in which a layer containing an adhesive component is included in the double-layered layer of the core sheet.

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 protective film forming composite sheet 1A shown in FIG. 2 is used in such a manner that the back surface of a semiconductor wafer (not shown) is attached to the surface 13a of the protective film forming film 13 with the peeling film 15 removed. , and further stick the upper surface of the surface 16a of the adhesive layer 16 for a jig to a jig such as a ring frame.

圖3係以示意方式顯示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，對與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。 Fig. 3 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film of the present invention. In addition, in the figures after FIG. 3 , the same symbols as those shown in the already-described figures are attached to the same constituent elements as those shown in the already-described figures, and detailed explanations of the symbols are 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(亦即黏著劑層12中的與和基材11接觸之側為相反側的面)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(亦即保護膜形成用膜13中的與和黏著劑層12接觸之側為相反側的面)的整個面積層有剝離膜15。 The composite sheet 1B for protective film formation shown here is the same as the composite sheet 1A for protective film formation shown in FIG. 2 except the point which does not have the adhesive agent layer 16 for jigs. That is, in the protective film forming composite sheet 1B, the adhesive layer 12 is laminated on one surface 11a of the substrate 11, and the surface 12a of the adhesive layer 12 (that is, the adhesive layer 12 and the substrate 11 (the side in contact with the opposite side) is provided with a film 13 for forming a protective film over the entire area of the protective film. The release film 15 is layered over the entire surface 13a of the film 13 for protective film formation (that is, the surface opposite to the side in contact with the adhesive layer 12 in the film 13 for protective film formation).

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 in such a manner that a semiconductor wafer is attached to a part of the center side of the surface 13 a of the surface 13 a of the protective film forming film 13 in a state where the peeling film 15 is removed. (illustration omitted), and further stick the region near the periphery of the film 13 for protective film formation to a jig such as a ring frame.

圖4係以示意方式顯示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 of 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。並且，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(亦即保護膜形成用膜13中的與和基材11接觸之側為相反側的面)的一部分亦即表面13a的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(上表面亦即治具用接著劑層16中的與和保護膜形成用膜13接觸之側為相反側的面以及治具用接著劑層16的側面)積層有剝離膜15。 1 C of composite sheets for protective film formation shown here are the same as 1 A of composite sheets for protective film formation shown in FIG. 2 except the point which does not have the adhesive agent layer 12. That is, in 1 C of composite sheets for protective film formation, the support sheet 10 consists of the base material 11 only. And, on one surface 11a of the substrate 11 (one surface 10a of the support sheet 10), the film 13 for forming a protective film is laminated, and on the surface 13a of the film 13 for forming a protective film (that is, the film 13 for forming a protective film Adhesive layer 16 for the jig is laminated on the surface 13a of the surface 13a, which is a part of the surface opposite to the side in contact with the base material 11), that is, the area near the peripheral portion of the surface 13a, and is not laminated on the surface 13a of the protective film forming film 13. The surface of the jig adhesive layer 16 and the surface 16a of the jig adhesive layer 16 (the upper surface, that is, the side opposite to the side in contact with the protective film forming film 13 in the jig adhesive layer 16 and the side surface of the adhesive layer 16 for jigs) the release film 15 is laminated.

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 cured protective film forming film 13 (that is, the protective film) and the support sheet 10, in other words, the adhesive force between the protective film and the base material 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 protective film forming composite sheet 1C shown in FIG. 4 is used in the same manner as the protective film forming composite sheet 1A shown in FIG. 2 , with the release film 15 removed, on the protective film forming film The surface 13a of 13 is attached to the back surface of a semiconductor wafer (not shown), and the upper surface of the surface 16a of the adhesive layer 16 for jigs is further attached to jigs such as ring frames.

圖5係以示意方式顯示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 of 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(亦即保護膜形成用膜13中的與和基材11接觸之側為相反側的面)的整個面積層有剝離膜15。 The composite sheet 1D for protective film formation shown here is the same as 1 C of composite sheets for protective film formation shown in FIG. 4 except the point which does not have the adhesive agent layer 16 for jigs. That is, in the composite sheet 1D for forming a protective film, the film 13 for forming a protective film is laminated on one surface 11 a of the substrate 11 , and the film 13 for forming a protective film is laminated on the surface 13 a of the film 13 for forming a protective film (that is, the film 13 for forming a protective film The release film 15 is layered over the entire area of the surface opposite to the side in contact with the substrate 11 .

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. In the state where the film 15 is peeled off, the back surface of a semiconductor wafer (not shown) is attached to the central part of the surface 13a of the protective film forming film 13, and the vicinity of the peripheral edge of the protective film forming film 13 is further bonded. The area attached to the ring frame and other jigs.

圖6係以示意方式顯示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 of the present invention.

關於此處所示之保護膜形成用複合片1E，除了保護膜形成用膜之形狀不同之方面以外，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1E係於基材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23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1E具有以下構成：於支持片10的一方的表面10a(例如支持片10中的黏著劑層12側的表面)上積層有保護膜形成用膜23。另外，保護膜形成用複合片1E係進一步於保護膜形成用膜23上具備剝離膜15。 The composite sheet 1E for protective film formation shown here is the same as 1 A of composite sheets for protective film formation shown in FIG. 2 except the point which differs in the shape of the film for protective film formation. That is, the composite sheet 1E for protective film formation is equipped with the adhesive agent layer 12 on the base material 11, and is equipped with the film 23 for protective film formation on the adhesive agent layer 12. The support sheet 10 is a laminate of the base material 11 and the adhesive layer 12. In other words, the composite sheet 1E for forming a protective film has the following structure: The film 23 for protective film formation is laminated|stacked on the surface of . Moreover, the composite sheet 1E for protective film formation is equipped with the release film 15 further 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(亦即黏著劑層12中的與和基材11接觸之側為相反側的面)的一部分亦即表面12a的中央側的區域積層有保護膜形成用膜23。並且，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，亦即保護 膜形成用膜23中的與和黏著劑層12接觸之側為相反側的面；及保護膜形成用膜23的側面)上積層有剝離膜15。 In the composite sheet 1E for forming a protective film, the adhesive layer 12 is laminated on one surface 11a of the base material 11, and the surface 12a of the adhesive layer 12 (that is, the side of the adhesive layer 12 that is in contact with the base material 11) The film 23 for protective film formation is laminated|stacked in the area|region of the center side of the surface 12a which is a part of the surface on the opposite side). In addition, on the surface 12a of the adhesive layer 12, the surface on which the film 23 for forming a protective film is not laminated and the surface 23a of the film 23 for forming a protective film (the upper surface, that is, the protective The release film 15 is laminated on the surface of the film 23 for film formation which is the opposite side to the side in contact with the adhesive layer 12 ; and the side surface of the film 23 for protective film formation).

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，並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 the adhesive agent layer 12, and it has shapes, 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 cured protective film forming film 23 (that is, the protective film) 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 protective film formation shown in FIG. 6 is used in such a manner that the back surface of a semiconductor wafer (not shown) is attached to the surface 23a of the film 23 for protective film formation with the peeling film 15 removed. , and further stick the surface 12a of the adhesive layer 12 on which the protective film forming film 23 is not laminated to a jig such as a ring frame.

再者，圖6所示之保護膜形成用複合片1E中，亦可與圖2及圖4所示同樣地，於黏著劑層12的表面12a中未積層保護膜形成用膜13之面積層治具用接著劑層(省略圖示)。具備此種治具用接著劑層之保護膜形成用複合片1E係以下述方式使用：與圖2及圖4所示之保護膜形成用複合片同樣地，將治具用接著劑層的表面貼附於環狀框等治具。 Furthermore, in the composite sheet 1E for forming a protective film shown in FIG. 6 , similarly to those shown in FIGS. 2 and 4 , the surface 12 a of the adhesive layer 12 may not have a built-up layer of the film 13 for forming a protective film. Adhesive layer for jig (illustration omitted). The composite sheet 1E for forming a protective film provided with such an adhesive layer for jigs is used in the following manner: similarly to the composite sheet for forming a protective film shown in FIGS. 2 and 4 , the surface of the adhesive layer for jigs is covered. Attached to jigs such as ring frames.

如此，關於本發明之保護膜形成用複合片，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本發明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。 Thus, the composite sheet for protective film formation of this invention may be provided with the adhesive agent layer for jigs regardless of what form the support sheet and the film for protective film formation are. However, generally, as shown in FIGS. 2 and 4 , as the composite sheet for protective film formation of the present invention having an adhesive layer for jigs, it is preferable to have an adhesive layer for jigs on the film for protective film formation.

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一步追加其他構成。 The composite sheet for forming a protective film of the present invention is not limited to the composite sheet for forming a protective film shown in FIGS. 2 to 6, and the composite sheet shown in FIGS. A part of the composite sheet for forming a protective film, or a further configuration is 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.

另外，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，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 addition, in the composite sheet for protective film formation shown in FIG. 2 , FIG. 3 and FIG. 6 , an intermediate layer may be provided between the base material 11 and the adhesive layer 12 . That is, in the protective film-forming composite sheet of the present invention, the support sheet may be formed by sequentially laminating a base material, an intermediate layer, and an adhesive layer. Here, the intermediate layer is the same as the intermediate layer that can be provided in the composite sheet for protective film formation shown in FIGS. 4 and 5 .

另外，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 addition, 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.

另外，本發明之保護膜形成用複合片中，亦可於剝離膜和與該剝離膜直接接觸之層之間產生一部分間隙。 Moreover, in the composite sheet for protective film formation of this invention, some gaps may be produced between the release film and the layer which directly contacts this release film.

另外，本發明之保護膜形成用複合片中，各層之大小或形狀可根據目的任意調節。 Moreover, in the composite sheet for protective film formation of this invention, the size and shape of each layer can be adjusted arbitrarily according to the purpose.

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。此種保護膜形成用複合片可使背面具備保護膜之半導體晶片更容易地拾取。 In the composite sheet for forming a protective film of the present invention, as described later, it is preferable that the layer in the support sheet such as the adhesive layer that is in direct contact with the film for forming a protective film is non-energy ray curable. Such a composite sheet for forming a protective film can more easily pick up a semiconductor wafer provided with a protective film on the back surface.

支持片可為透明亦可為不透明，還可根據目的而著色。 The support sheet may be transparent or opaque, and may be 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, in the present invention in which the film for forming a protective film has energy ray curability, the support sheet is preferably a support sheet that transmits energy rays.

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 at least 30%, more preferably at least 50%, and most preferably at least 70%. When the transmittance of the said light is such a range, when the film for protective film formation is irradiated with an energy ray (ultraviolet ray) via a support sheet, the degree of hardening of the film for protective film formation improves further.

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 of the transmittance of light having a wavelength of 375 nm is not particularly limited, and may be 95%, for example.

亦即，支持片中，波長375nm之光之透過率較佳為30%至95%，更佳為50%至95%，尤佳為70%至95%。 That is, in the support sheet, the transmittance of light with a wavelength of 375nm is preferably 30% to 95%, more preferably 50% to 95%, and most preferably 70% to 95%.

另外，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 addition, in the support sheet, the transmittance of light with a wavelength of 532 nm is preferably at least 30%, more preferably at least 50%, and most preferably at least 70%.

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 said light transmittance is such a range, when irradiating laser light to the film for protective film formation or a protective film via a support sheet, and these are printed, 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 of the transmittance of light having a wavelength of 532 nm is not particularly limited, and may be 95%, for example.

亦即，支持片中，波長532nm之光之透過率較佳為30%至95%，更佳為50%至95%，尤佳為70%至95%。 That is, in the support sheet, the transmittance of light with a wavelength of 532nm is preferably 30% to 95%, more preferably 50% to 95%, and most preferably 70% to 95%.

另外，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 addition, in the support sheet, the transmittance of light with a wavelength of 1064 nm is preferably at least 30%, more preferably at least 50%, and most preferably at least 70%. When the transmittance of the said light is such a range, when printing is performed on these by irradiating laser light to the film for protective film formation or a protective film via a support sheet, it can print 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, and may be 95%, for example.

亦即，支持片中，波長1064nm之光之透過率較佳為30%至95%，更佳為50%至95%，尤佳為70%至95%。其次，對構成支持片之各層進行更詳細的說明。 That is, in the support sheet, the transmittance of light with a wavelength of 1064 nm is preferably 30% to 95%, more preferably 50% to 95%, and most preferably 70% to 95%. 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 aforementioned substrate is in the form of a sheet or a film, and as a constituent material of the aforementioned substrate, For example, various resins are mentioned.

作為前述樹脂，例如可列舉：低密度聚乙烯(簡稱LDPE；low density polyethylene)、直鏈低密度聚乙烯(簡稱LLDPE；linear low density polyethylene)、高密度聚乙烯(簡稱HDPE；high density polyethylene)等聚乙烯；聚丙烯、聚丁烯、聚丁二烯、聚甲基戊烯、冰片烯樹脂等聚乙烯以外的聚烯烴；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-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、聚對苯二甲酸丁二酯、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。 Examples of the aforementioned resin include low-density polyethylene (abbreviated as LDPE; low density polyethylene), linear low-density polyethylene (abbreviated as LLDPE; linear low density polyethylene), high-density polyethylene (abbreviated as HDPE; high density polyethylene), etc. Polyethylene; polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, and bornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, Ethylene-based copolymers such as ethylene-(meth)acrylate copolymers and ethylene-bornene copolymers (copolymers obtained using ethylene as a monomer); vinyl chloride-based resins such as polyvinyl chloride and vinyl chloride copolymers (using vinyl chloride as a monomer); polystyrene; polycycloolefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyisophthalic acid Polyesters such as ethylene glycol, polyethylene 2,6-naphthalene dicarboxylate, and wholly aromatic polyesters with aromatic ring groups in all structural units; copolymers of two or more of the aforementioned polyesters; poly(formaldehyde) base) acrylate; polyurethane; polyacrylate urethane; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene ether; polyphenylene sulfide ; Polymer; Polyether ketone, etc.

另外，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。 Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and resin other than the said polyester, are also mentioned, for example. In the polymer alloy of the aforementioned polyester and a resin other than the aforementioned polyester, it is preferable that the amount of the resin other than the polyester is relatively small.

另外，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。 In addition, examples of the above-mentioned resins include: cross-linked resins obtained by cross-linking one or more of the above-mentioned resins exemplified above; Modified resins such as ionic polymers of one or more of the aforementioned resins as examples.

再者，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)丙烯酸類似的用語亦相同。 In addition, 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 selected arbitrarily.

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 substrate may be composed of one layer (single layer), or may be composed of multiple layers of two or more layers; when composed of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple 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 substrate is preferably from 50 μm to 300 μm, more preferably from 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 adhesiveness to a semiconductor wafer or a semiconductor wafer 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, the "thickness of the substrate" means the thickness of the entire substrate, for example, the thickness of a substrate composed of multiple layers means the total thickness of all the layers constituting the substrate.

再者，本說明書中，所謂「厚度」意指於任意的5個部位利用接觸式厚度計測定厚度所得之以平均顯示之值。 In addition, in this specification, "thickness" means the value displayed by the average which measured the thickness at arbitrary 5 places with the contact type thickness gauge.

基材較佳為厚度精度高，亦即任何部位均可抑制厚度不均。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 can be suppressed in any part. 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, ethylene-vinyl acetate copolymer things etc.

基材中，除了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, and softeners (plasticizers) in addition to the main constituent materials such as the above-mentioned 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，基材可為透明亦可為不透明，還可根據目的而著色，也可蒸鍍其他層。 It is sufficient that the optical properties of the substrate satisfy the optical properties of the support sheet described above. That is, the base material may be transparent or opaque, may be colored according to the purpose, and may be deposited with other layers.

並且，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。 Furthermore, in the present invention in which the film for forming a protective film has energy ray curability, the substrate is preferably a substrate 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 base material can also be subjected to the following treatment to improve the adhesion with other layers such as the adhesive layer disposed on the base material: roughening treatment by sand blasting treatment, solvent treatment, etc.; or corona discharge treatment, electron beam treatment, etc. Irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments, etc.

另外，基材的表面亦可經實施底塗(primer)處理。 In addition, the surface of the substrate may also be treated with a primer.

另外，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。 In addition, the substrate may also have an antistatic coating or a layer for preventing the substrate from adhering to other layers when the composite sheet for forming a protective film is stacked for storage. The sheet or substrate is then attached to the 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 substrate is subjected to an electron beam irradiation treatment from the viewpoint of suppressing fragmentation of the substrate 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 substrate can be produced by a known method. For example, a base material containing a resin can be produced by molding a resin composition containing the aforementioned resin.

○黏著劑層 ○Adhesive layer

前述黏著劑層為片狀或膜狀，並含有黏著劑。 The aforementioned adhesive layer is sheet-like or film-like and contains 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 adhesive include: acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, ester resins, etc. Resin, preferably acrylic resin.

再者，本說明書中，「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。 Furthermore, in this specification, the concept of "adhesive resin" includes both adhesive resin and adhesive resin. A resin that exhibits adhesiveness when used in combination, or a resin that exhibits adhesiveness by the presence of a trigger such as heat or water, 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 multiple layers of two or more layers; when composed of multiple layers, these multiple layers may be mutually compatible The same may be different, and the combination of these plural layers is not specifically 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 from 1 μm to 100 μm, more preferably from 1 μm to 60 μm, especially preferably from 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，黏著劑層可為透明亦可為不透明，還可根據目的而著色。 It is sufficient that the optical properties of the adhesive layer satisfy the optical properties of the support sheet described above. That is, the adhesive layer may be transparent or opaque, and may be colored according to the purpose.

並且，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。 Furthermore, in the present invention in which the film for protective film formation has energy ray curability, the adhesive layer is preferably an adhesive layer that allows energy rays to pass through.

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 may be formed using a non-energy ray-curable adhesive. The adhesive layer formed by using the energy ray curable adhesive can easily adjust the physical properties before and after curing.

<<黏著劑組成物>> <<Adhesive composition>>

黏著劑層可由含有黏著劑之黏著劑組成物形成。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。再者，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 of an adhesive composition containing an adhesive. For example, an adhesive composition can be applied to the surface to be formed of the adhesive layer, and the adhesive composition can be dried as necessary to form the adhesive layer on the target site. Regarding the more specific formation method of the adhesive layer, it is the same as the formation method of other layers. , followed by a detailed description. The content ratio of the components that do not vaporize at normal temperature in the adhesive composition is usually the same as the content ratio of the aforementioned components in the adhesive layer. Furthermore, in this specification, "normal temperature" means a temperature that is neither particularly cold nor particularly hot, that is, an ordinary temperature, for example, a temperature of 15° C. to 25° C. can be mentioned.

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、接觸式塗佈機等。 What is necessary is to apply the adhesive composition by a known method, for example, the method of using the following various coating machines: air knife coater, knife coater, rod coater, gravure coater, roll coater, etc. Cloth machine, roller knife coater, curtain coater, die coater, knife coater, screen coater, wire wound bar (Meyer bar) coater, contact coater Wait.

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, and when the adhesive composition contains the solvent described later, it is preferable to perform heat 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，有時簡稱為「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，有時簡稱為「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, the adhesive composition containing the energy ray curable adhesive, that is, the energy ray curable adhesive composition includes, for example, the following adhesive compositions, etc.: Adhesive The agent composition (I-1) contains a non-energy ray-curable adhesive resin (I-1a) (hereinafter, sometimes simply referred to as "adhesive resin (I-1a)"), and an energy ray-curable compound; The adhesive composition (I-2) contains an energy ray-curable adhesive resin (I-2a) (hereinafter, sometimes simply referred to 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) contains 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 described above, the adhesive composition (I-1) contains a 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 the structural unit derived from an alkyl (meth)acrylate 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 arbitrarily selected.

本說明書中，所謂「源自」意指化學結構發生變化以進行聚合。 In the present specification, "derived from" means that the chemical structure is changed so as to be polymerized.

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 aforementioned alkyl (meth)acrylates include: alkyl (meth)acrylates in which the alkyl group constituting the alkyl ester has 1 to 20 carbon atoms, and the aforementioned alkyl group is preferably linear or branched. chain.

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, isopropyl (meth)acrylate ester, n-butyl (meth)acrylate, (meth) Isobutyl acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, ( 2-ethylhexyl methacrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, (meth) ) decyl acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate (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, stearyl (meth)acrylate (also known as stearyl (meth)acrylate), nineteen (meth)acrylate Alkyl esters, eicosyl (meth)acrylate, etc.

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。並且，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。另外，前述烷基的碳數為4以上之(甲基)丙烯酸烷基酯較佳為丙烯酸烷基酯。 It is preferable that the said acrylic polymer has the structural unit derived from the said alkyl group and C4 or more alkyl (meth)acrylate from the point which the adhesive force of an adhesive agent layer improves. In addition, the carbon number of the alkyl group is preferably 4-12, more preferably 4-8, from the point of view of further improving the adhesive force of the adhesive layer. In addition, the alkyl (meth)acrylate having 4 or more carbon atoms in the alkyl group is preferably an alkyl acrylate.

前述丙烯酸系聚合物中，較佳為除了源自(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。 In the above-mentioned acrylic polymer, it is preferable to further have a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate.

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。 As the aforementioned functional group-containing monomers, for example, the following monomers can be listed: The starting point of crosslinking can be formed by the reaction of the above-mentioned functional group with the cross-linking agent described later, or the reaction of the above-mentioned functional group with the unsaturated group in the unsaturated group-containing compound described later, and on the side of the acrylic polymer Chains introduce unsaturated groups.

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 amino 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 amino 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(亦即，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, 3-hydroxy (meth)acrylate Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyalkyl (meth)acrylates; vinyl alcohol, Non-(meth)acrylic unsaturated alcohols (that is, unsaturated alcohols not having a (meth)acryl skeleton) such as allyl alcohol, 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(亦即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(亦即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。 As the aforementioned carboxyl group-containing monomers, for example, ethylenically unsaturated monocarboxylic acids (that is, monocarboxylic acids having ethylenically unsaturated bonds) such as (meth)acrylic acid and crotonic acid; fumaric acid, Itaconic acid, maleic acid, citraconic acid and other ethylenically unsaturated dicarboxylic acids (that is, dicarboxylic acids having ethylenically unsaturated bonds); anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; methacrylic acid 2-carboxy Carboxyalkyl (meth)acrylate, etc.

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-containing monomer or a carboxyl-containing monomer, more preferably a hydroxyl-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 aforementioned 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 selected arbitrarily.

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構成丙烯酸系聚合物之結構單元的總質量，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 structural units derived from functional group-containing monomers is preferably 1% by mass to 35% by mass, more preferably 2% by mass, relative to the total mass of structural units constituting the acrylic polymer. % to 32% by mass, preferably 3% to 30% by mass.

前述丙烯酸系聚合物中，亦可除了源自(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，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 alkyl (meth)acrylate and the structural unit derived from the functional group containing monomer, the said acrylic polymer may further have the structural unit derived from another monomer.

前述其他單體只要為可與(甲基)丙烯酸烷基酯等進行共聚合之單體，則並無特別限定。 The aforementioned other monomers are not particularly limited as long as they are copolymerizable monomers with alkyl (meth)acrylates 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。 Examples of the other monomers include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide, and the like.

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 aforementioned other monomers constituting the aforementioned acrylic polymer may be only one type , can also be two or more; in the case of two or more, 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(亦稱為能量線聚合性基)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 (also referred to as an energy ray polymerizable group) can be used as the above-mentioned compound. Energy ray curable adhesive resin (I-2a).

再者，本說明書中，所謂「能量線聚合性」意指藉由照射能量線而聚合之性質。 In addition, in this specification, "energy ray polymerizability" means the property of polymerizing by irradiating an energy ray.

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 may be two or more types; in the case of two or more types, these combinations and ratios can be selected arbitrarily.

黏著劑組成物(I-1)中，黏著性樹脂(I-1a)的含量相對於黏著劑組成物(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) relative to the total mass of the adhesive composition (I-1) is preferably 5 mass % to 99 mass %, more preferably 10% by mass to 95% by mass, preferably 15% by mass to 90% by mass.

[能量線硬化性化合物] [Energy Beam Curing 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 energy ray-polymerizable unsaturated groups that can be cured by irradiation. Monomers or oligomers hardened by energy lines.

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, and dipentaerythritol hexa(meth)acrylate. base) acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate and other poly(meth)acrylates; (meth)acrylic acid aminomethyl Ester; 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 oligomer include oligomers obtained by polymerizing the monomers exemplified above, and the like.

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 (meth)urethane acrylate, (meth)urethane 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 may be two or more types; in the case of two or more types, these combinations and ratios can be selected arbitrarily.

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 adhesive composition (I-1), the content of the energy ray-curable compound is preferably 1% by mass to 95% by mass, more preferably 5% by mass to 90% by mass, preferably 10% by mass to 85% by mass.

[交聯劑] [Crosslinking agent]

於使用除了源自(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 further 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), It is preferable that the adhesive composition (I-1) further contains a crosslinking agent.

前述交聯劑例如與前述官能基反應而使黏著性樹脂(I-1a)彼此進行交聯。 The said crosslinking agent reacts with the said functional group, for example, and crosslinks adhesive resin (I-1a) mutually.

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(亦即，具有異氰酸酯基之交聯劑)；乙二醇縮水甘油醚等環氧系交聯劑(亦即，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(亦即具有氮丙啶基之交聯劑)；鋁螯合物等金屬螯合物系交聯劑(亦即具有金屬螯合物結構之交聯劑)；異氰脲酸酯系交聯劑(亦即具有異氰脲酸骨架之交聯劑)等。 Examples of the crosslinking agent include isocyanate crosslinking agents (that is, crosslinking agents having isocyanate groups) such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates. agent); epoxy-based crosslinking agents such as ethylene glycol glycidyl ether (that is, crosslinking agents with glycidyl groups); hexa[1-(2-methyl)-aziridinyl]triphosphine triazine Equal aziridine-based cross-linking agents (that is, cross-linking agents with aziridine groups); metal chelate-based cross-linking agents such as aluminum chelates (that is, cross-linking agents with metal chelate structures); An isocyanurate-based crosslinking agent (that is, a crosslinking agent having an 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 cross-linking agent is preferably an isocyanate-based cross-linking agent in terms of increasing the cohesive force of the adhesive to increase the adhesion of the adhesive layer, and in terms of ease of acquisition.

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 may be two or more types; in the case of two or more types, these combinations and ratios can be selected arbitrarily.

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 preferably 0.01 to 50 parts by mass, more preferably 0.1 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-1a). to 20 parts by mass, 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. Even if the adhesive composition (I-1) containing a photopolymerization initiator is irradiated with relatively low-energy energy rays such as ultraviolet rays, the curing reaction proceeds sufficiently.

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, etc. Ketone compounds; acyl phosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; benzyl Sulfide compounds such as phenyl sulfide and tetramethylthiuram monosulfide; α-ketol 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; benzoyl; dibenzoyl; benzophenone; 2,4-diethylthioxanthone ; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] acetone; 2-chloroanthraquinone, etc.

另外，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。 In addition, as the aforementioned photopolymerization initiator, for example, 1-chloroanthracene can also be used Quinone compounds such as quinones; photosensitizers such as amines, etc.

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 may be two or more types; in the case of two or more types, these combinations and ratios can be selected arbitrarily.

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 to 20 parts by mass, more preferably 0.03 to 20 parts by mass relative to 100 parts by mass of the content of the aforementioned energy ray-curable compound. 10 parts by mass, preferably 0.05 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 range that does not impair the effects 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 aforementioned other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, adhesion imparting agents, Known additives such as a reaction delayer and a crosslinking accelerator (catalyst).

再者，所謂反應延遲劑，例如抑制因混入至黏著劑組成物(I-1)中之觸媒之作用而導致保存中之黏著劑組成物(I-1)中進行目的外的交聯反應。作為反應延遲劑，例如可列舉藉由針對觸媒之螯合物而形成螯合物錯合物之化合物，更具體而言，可列舉：於1分子中具有2個以上之羰基(-C(=O)-)之化合物。 Furthermore, the so-called reaction delaying agent, for example, inhibits the unintended crosslinking reaction in the adhesive composition (I-1) under storage due to the action of the catalyst mixed in the adhesive composition (I-1). . As a reaction retarder, for example, a compound that forms a chelate complex by a chelate against a catalyst, and more specifically, a compound having two or more carbonyl groups (-C( =O)-) 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 may be two or more types; in the case of two or more types, these combinations and ratios can be selected arbitrarily.

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 also contain a solvent. When the adhesive composition (I-1) contains a solvent, the applicability to the surface to be coated improves.

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(例如，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 above-mentioned solvent is preferably an organic solvent, and examples of the above-mentioned organic solvent include: ketones such as methyl ethyl ketone and acetone; esters such as ethyl acetate (for example, carboxylate); ethers such as tetrahydrofuran and dioxane (dioxane) ; Aliphatic hydrocarbons such as cyclohexane and n-hexane; Aromatic hydrocarbons such as toluene and xylene; Alcohols such as 1-propanol and 2-propanol, etc.

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 producing the adhesive composition (I-1), a solvent of the same type or a different type from the solvent used for producing the adhesive resin (I-1a) is additionally added.

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 may be two or more types; in the case of two or more types, these combinations and ratios can be selected arbitrarily.

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 adjusted appropriately.

<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 adhesive composition (I-2) contains the energy ray-curable adhesive resin (I-2a), and the adhesive resin (I-2a) is added to the non-energy ray-curable adhesive resin (I-2a). -1a) has an unsaturated group 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，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 group that can react with a functional group in the adhesive resin (I-1a) to react with the adhesive resin (I-1a). - 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 aforementioned energy ray polymerizable unsaturated group include (meth)acryl, vinyl (also called ethylene), allyl (also called 2-propenyl), and the like, preferably (meth)acryl.

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 the group that can be bonded to the functional group in the adhesive resin (I-1a), for example For example, an isocyanate group and a glycidyl group which can be bonded to a hydroxyl group or an amino group, a hydroxyl group and an amino group which can be bonded to a carboxyl group or an epoxy group, and the like can be mentioned.

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。 Examples of the unsaturated group-containing compound include (meth)acryloxyethyl isocyanate, (meth)acryl isocyanate, and glycidyl (meth)acrylate.

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 may be two or more types; in the case of two or more types, these combinations and ratios can be selected arbitrarily.

黏著劑組成物(I-2)中，黏著性樹脂(I-2a)的含量相對於黏著劑組成物(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) relative to the total mass of the adhesive composition (I-2) is preferably 5 mass % to 99 mass %, more preferably 10% by mass to 95% by mass, more preferably 10% by mass to 90% by 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 the same 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。 Examples of the crosslinking agent in the adhesive composition (I-2) include the same compounds as the crosslinking agent in the adhesive composition (I-1).

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 may be two or more types; in the case of two or more types, these combinations and ratios can be selected arbitrarily.

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 preferably 0.01 to 50 parts by mass, more preferably 0.1 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-2a). to 20 parts by mass, 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. Even if the adhesive composition (I-2) containing a photopolymerization initiator is irradiated with relatively low-energy energy rays such as ultraviolet rays, the hardening reaction proceeds sufficiently.

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。 Examples of the photopolymerization initiator in the adhesive composition (I-2) include the same compounds as the photopolymerization initiator in the adhesive composition (I-1).

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 may be two or more types; in the case of two or more types, these combinations and ratios can be selected arbitrarily.

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 preferably 0.01 to 20 parts by mass, more preferably 0.03 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-2a). Parts to 10 parts by mass, 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-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 range that does not impair the effects 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。 Examples of the other additives in the adhesive composition (I-2) include the same compounds as the other additives in the adhesive composition (I-1).

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 1 type, or 2 or more types; in the case of 2 or more types, these combinations and ratios can be selected arbitrarily.

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 also 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。 Examples of the solvent in the adhesive composition (I-2) include the same solvents as those in the adhesive composition (I-1).

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 may be two or more types; in the case of two or more types, these combinations and ratios can be selected arbitrarily.

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 adjusted appropriately.

<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 adhesive composition (I-3) contains the adhesive resin (I-2a) and an energy ray-curable compound.

黏著劑組成物(I-3)中，黏著性樹脂(I-2a)的含量相對於黏著劑組成物(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) relative to the total mass of the adhesive composition (I-3) is preferably 5 mass % to 99 mass %, more preferably 10% by mass to 95% by mass, preferably 15% by mass to 90% by mass.

[能量線硬化性化合物] [Energy Beam Curing 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，亦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 aforementioned energy ray-curable compound contained in the adhesive composition (I-3) include monomers and oligomers that have an energy ray polymerizable unsaturated group and are curable by irradiation with energy ray, and include The same compound as the energy ray-curing 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 aforementioned energy ray-curable compound contained in the adhesive composition (I-3) may be only one type, or may be two or more types; in the case of two or more types, these combinations and ratios can be selected arbitrarily.

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 preferably 0.01 to 300 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-2a), more preferably 0.03 to 200 parts by mass, 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. Even if the adhesive composition (I-3) containing a photopolymerization initiator is irradiated with relatively low-energy energy rays such as ultraviolet rays, the hardening reaction proceeds sufficiently.

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。 Examples of the photopolymerization initiator in the adhesive composition (I-3) include the same compounds as the photopolymerization initiator in the adhesive composition (I-1).

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 may be two or more types; in the case of two or more types, these combinations and ratios can be selected arbitrarily.

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合計含量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. Parts by mass, more preferably 0.03 parts by mass to 10 parts by mass, especially 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-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 range that does not impair the effects 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。 Examples of the above-mentioned other additives include the same compounds as the other additives in the adhesive composition (I-1).

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 may be two or more types; in the case of two or more types, these combinations and ratios can be selected arbitrarily.

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 also 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。 Examples of the solvent in the adhesive composition (I-3) include the same solvents as those in the adhesive composition (I-1).

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 may be two or more types; in the case of two or more types, these combinations and ratios can be selected arbitrarily.

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 adjusted appropriately.

<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 other than adhesive composition (I-1) to 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的含有成分所說明之成分。 Adhesive composition (I-1), adhesive composition (I-2) and adhesive composition (I-3) have been described above, but all adhesives other than these three adhesive compositions Compositions (in this specification, referred to as "adhesive compositions other than adhesive composition (I-1) to adhesive composition (I-3)") can also be used in the same way as described as these components. ingredients.

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，除了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。 Adhesive compositions other than adhesive composition (I-1) to adhesive composition (I-3), in addition to energy ray curable adhesive compositions, Adhesive compositions that are not curable by energy rays can also be mentioned.

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: acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonate The adhesive composition (I-4) of the non-energy ray-curable adhesive resin (I-1a) such as ester or ester resin 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)等情形相同。 Adhesive compositions other than adhesive composition (I-1) to adhesive composition (I-3) preferably contain one or more cross-linking agents, and the content of the cross-linking agent can be set to be the same as The above-mentioned adhesive composition (I-1) and the like are the same.

<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.

[黏著劑組成物(I-4)中的黏著性樹脂(I-1a)] [Adhesive resin (I-1a) in adhesive composition (I-4)]

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)相同的黏著性樹脂。 Examples of the adhesive resin (I-1a) in the adhesive composition (I-4) include the same adhesive resins as the adhesive resin (I-1a) in the adhesive composition (I-1).

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 may be two or more types; in the case of two or more types, these combinations and ratios can be selected arbitrarily.

黏著劑組成物(I-4)中，黏著性樹脂(I-1a)的含量相對 於黏著劑組成物(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 relatively The total mass of the adhesive composition (I-4) is preferably 5% by mass to 99% by mass, more preferably 10% by mass to 95% by mass, most preferably 15% by mass to 90% by mass.

[交聯劑] [Crosslinking agent]

於使用除了源自(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前述黏著性樹脂(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 further 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 aforementioned adhesive resin (I-1a) , It is preferable that the adhesive composition (I-4) 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。 Examples of the crosslinking agent in the adhesive composition (I-4) include the same compounds as the crosslinking agent in the adhesive composition (I-1).

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 may be two or more types; in the case of two or more types, these combinations and ratios can be selected arbitrarily.

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 preferably 0.01 to 50 parts by mass, more preferably 0.1 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-1a). to 20 parts by mass, 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 range that does not impair the effects 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。 Examples of the above-mentioned other additives include the same compounds as the other additives in the adhesive composition (I-1).

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 1 type, or 2 or more types; in the case of 2 or more types, these combinations and ratios can be selected arbitrarily.

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 also 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。 Examples of the solvent in the adhesive composition (I-4) include the same solvents as those in the adhesive composition (I-1).

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 may be two or more types; in the case of two or more types, these combinations and ratios can be selected arbitrarily.

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 adjusted appropriately.

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，而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之黏著劑層，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, if the adhesive layer is energy ray curable, it may not be possible to suppress the simultaneous hardening of the adhesive layer when the film for forming a protective film is cured by irradiation of energy rays. If the adhesive layer and protective film When the forming film is cured at the same time, the cured protective film forming film and the adhesive layer may adhere to these interfaces to such an extent that they cannot be peeled off. In this case, it is difficult to separate a semiconductor wafer (in this specification, sometimes referred to as a "semiconductor wafer with a protective film") having a cured protective film-forming film, that is, a protective film, from a cured adhesive layer. The support sheet is peeled off, and the semiconductor wafer with the protective film cannot be picked up normally. By setting the adhesive layer in the support sheet of the present invention as a non-energy ray curable adhesive layer, such a problem 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。 This article explained the effect of the adhesive layer being non-energy ray curable, but even if the layer in the support sheet that is in direct contact with the film for forming a protective film is a layer other than the adhesive layer, as long as the layer is non-energy ray Hardening 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可藉由將用以構成前述黏著劑組成物之各成分，亦即前述黏著劑與視需要之前述黏著劑以外之成分加以調配而獲得。 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) Other adhesive compositions can be obtained by mixing the components constituting the aforementioned adhesive composition, that is, the aforementioned adhesive and, if necessary, components other than the aforementioned adhesive.

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 of 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 in the following way: the solvent It is mixed with any formulation component other than the solvent and diluted in advance; it can also be used by mixing the solvent with these formulation components without pre-diluting any formulation component other than the solvent.

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。 There are no particular limitations on the method of mixing the ingredients during preparation, and it may be appropriately selected from the following known methods: a method of mixing by rotating a stirring bar or a stirring blade; a method of mixing by using a mixer; The method 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 for adding and mixing the components are not particularly limited as long as the components are not degraded, and may be appropriately adjusted. The temperature is preferably 15°C to 30°C.

◎保護膜形成用膜 ◎Film for protective film formation

本發明之保護膜形成用複合片中，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，可高選擇性地拾取目標之附有保護膜的半導體晶片。另外，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 composite sheet for forming a protective film of the present invention, the adhesive force between the protective film obtained by curing the film for forming a protective film and the support sheet is preferably 50 mN/25mm to 1500 mN/25mm, more preferably 52 mN/25mm to 1450 mN/ 25mm, preferably 53mN/25mm to 1430mN/25mm. When the aforementioned adhesive force is above the aforementioned lower limit value, when picking up the semiconductor wafer with the protective film, the pickup of the semiconductor wafer with the protective film outside the target is suppressed, and the target semiconductor wafer with the protective film can be picked up with high selectivity. semiconductor wafer. Moreover, when the said adhesive force is below the said upper limit, when picking up the semiconductor wafer with a protective film, cracking and chipping of a semiconductor wafer are suppressed. Thus, the composite sheet for protective film formation has favorable pick-up property by the said adhesive force being in a specific range.

再者，本說明書中，即便為保護膜形成用膜硬化後，亦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，則將該積層結構體稱為「保護膜形成用複合片」。 In addition, in this specification, even after the film for forming a protective film is cured, as long as the laminated structure of the hardened product of the support sheet and the film for forming a protective film (in other words, the support sheet and the protective film) is maintained, the laminated structure is It is called "composite sheet for protective film formation".

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, the composite sheet for protective film formation with a width of 25 mm and arbitrary length was attached to the adherend through the film for protective film formation of this composite sheet for protective film formation.

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 energy rays to harden the film for protective film formation to form a protective film, the support sheet was peeled from the protective film attached to the adherend at a peeling speed of 300 mm/min. The peeling at this time is the following so-called 180° peeling: the support sheet is placed in the longitudinal direction of the support sheet (composite sheet for protective film formation) in such a manner that the surfaces of the protective film and the support sheet in contact with each other form an angle of 180°. length direction) peeling off. Then, the load (peeling force) at the time of this 180° peeling was measured, and the measured value of this load (peeling force) was made into the said adhesive force (mN/25mm).

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。另外，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 protective film-forming composite sheet used for the measurement is not particularly limited as long as it is within the range in which the adhesive force can be stably detected, but is preferably 100 mm to 300 mm. In addition, at the time of measurement, it is preferable to stabilize the attached state of the composite sheet for protective film formation by bringing the composite sheet for protective film formation into the state attached 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 adhesive force between the film for forming a protective film and the aforementioned support sheet is not particularly limited, and 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, especially preferably 150 mN/25 mm or more. It is more than 200mN/25mm. When the adhesive force is 100 mN/25 mm or more, peeling between the film for forming a protective film and the support sheet during dicing is suppressed, for example, scattering of a semiconductor wafer having a 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 of the adhesive force between the film for protective film formation and the said support sheet is not specifically limited, For example, it can set it as any of 4000mN/25mm, 3500mN/25mm, 3000mN/25mm etc. However, these are examples.

亦即，作為一態樣，保護膜形成用膜與前述支持片之間的黏著力可為80mN/25mm至4000mN/25mm，較佳為100mN/25mm至3500mN/25mm，進而更佳為150mN/25mm至3500mN/25mm，尤佳為200mN/25mm至3000mN/25mm。 That is, as an aspect, the adhesive force between the protective film forming film and the aforementioned support sheet can be 80mN/25mm to 4000mN/25mm, preferably 100mN/25mm to 3500mN/25mm, and more preferably 150mN/25mm to 3500mN/25mm, preferably 200mN/25mm to 3000mN/25mm.

關於保護膜形成用膜與支持片之間的黏著力，除了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 to be measured is not hardened by irradiation of energy rays, the adhesion between the above-mentioned protective film and the support 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 above-mentioned adhesive force between the protective film and the support sheet, and the adhesive force between the protective film forming film and the support sheet can be adjusted, for example, by adjusting the protective film formation The type and amount of the component contained in the film, the constituent material of the layer on which the protective film-forming film is provided in the support sheet, the surface state of the layer, and the like are appropriately adjusted.

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 types and amounts of components contained in the film for forming a protective film can be adjusted by the types and amounts of components contained in the composition for forming a protective film described later. Furthermore, by adjusting the type and content of the polymer (b) that does not have an energy ray curable group, the content of the filler (d), or the crosslinking agent (f) among the components contained in the protective film forming composition, content, the adhesive force between the protective film or the film for protective film formation and the support sheet can be adjusted more easily.

另外，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進行調節。 Moreover, for example, when the layer provided with the film for protective film formation in a support sheet is an adhesive layer, the constituent material of this layer can be adjusted suitably by adjusting the kind and quantity of the component contained in an adhesive layer. In addition, the types and amounts of the components contained in the adhesive layer can be adjusted by the types 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，除了藉由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, when the layer on which the protective film-forming film is provided in the support sheet is the substrate, the protective film or the adhesive force between the protective film-forming film and the support sheet depends not only on the constituent materials of the substrate but also on the substrate. , can also be adjusted by the surface state of the substrate. In addition, the surface state of the base material can be adjusted, for example, by performing the surface treatment listed above as the treatment for improving the adhesion between the base material and other layers: embossing 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。 Examples of the film for forming a protective film include energy ray curable films containing, for example, an energy ray curable component (a).

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 adhesive, more preferably uncured and adhesive.

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 protective film formation may be only one layer (single layer), or may be multiple layers of two or more layers; in the case of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers does not matter. special 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。另外，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 protective film formation is preferably from 1 μm to 100 μm, more preferably from 5 μm to 75 μm, especially preferably from 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. Moreover, when the thickness of the film for protective film formation is below the said upper limit, it can suppress that thickness is 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 a film for forming a protective film consisting of multiple layers means the thickness of all the 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 for forming a protective film by curing the film for forming a protective film are not particularly limited as long as the protective film has a degree of hardening sufficient to exhibit the function of the protective film, and are appropriately selected according to the type of 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。並且，前述硬化時，能量線之光量較佳為3mJ/cm2至1000mJ/cm2。 For example, when curing the film for forming a protective film, the illuminance of energy rays is preferably 4 mW/cm 2 to 280 mW/cm 2 . In addition, during the aforementioned hardening, the light quantity of the energy ray is preferably 3 mJ/cm 2 to 1000 mJ/cm 2 .

<<保護膜形成用組成物>> <<Protective film forming composition>>

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 this film for protective film formation. For example, a protective film-forming film can be formed on a target site by applying a protective film-forming composition to the surface to be formed of the protective film-forming film, and drying the protective film-forming composition if necessary. The content ratio of the components that do not vaporize at normal 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 explained 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、接觸式塗佈機等。 What is necessary is just to apply the composition for protective film formation by a well-known method, for example, the method using the following various coaters: an air knife coater, a knife coater, a rod coater, a gravure coater, a roll coater, etc. Coater, Roller Knife Coater, Curtain Coater, Die Coater, Knife Coater, Screen Coater, Wire Rod 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, and when the composition for forming a protective film contains a solvent described later, it is preferable to perform heat drying; Dry under the condition of 10 seconds to 5 minutes.

<保護膜形成用組成物(IV-1)> <Protective 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) are mentioned, for example.

[能量線硬化性成分(a)] [energy ray hardening ingredient (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 cured by irradiation of energy ray, and this component is used to impart film forming property, flexibility, etc. to the film for protective film formation.

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 polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000, and compounds having an energy ray-curable group and having a molecular weight of 100 to 80,000 (a2). The aforementioned polymer (a1) may be at least partially crosslinked by a crosslinking agent (f) described later, or may not be crosslinked.

再者，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 addition, in this specification, unless otherwise specified, "weight average molecular weight" means the polystyrene conversion value measured by the gel permeation chromatography (GPC; Gel Permeation Chromatography) method.

(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 curable 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 the energy ray-curing compound (a12) are polymerized, and the aforementioned acrylic polymer (a11) It has a functional group reactive with a group of another compound, and the energy ray-curable compound (a12) has a group reactive with the functional group and an energy ray-curable group such as an energy ray-curable double bond.

作為可與丙烯酸系聚合物(a11)中的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(胺基中的1個或2個氫原子由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 capable of reacting with groups of other compounds in the acrylic polymer (a11) include: hydroxyl group, carboxyl group, amine group, substituted amine group (one or two hydrogen atoms in the amine group) A group substituted by a group other than a hydrogen atom), an epoxy group, etc. However, the aforementioned 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 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 groups (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，亦可為除了這些單體以外，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。 The aforementioned acrylic polymer (a11) having a functional group includes, for example, a polymer obtained by copolymerizing the aforementioned acrylic monomer having a functional group and the aforementioned acrylic monomer having no functional group. In addition to these monomers, a polymer obtained by further copolymerizing a monomer other than an acrylic monomer (non-acrylic monomer).

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.

作為具有前述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 acrylic monomers having the aforementioned functional groups include: hydroxyl-containing monomers, carboxyl-containing monomers, amine-containing monomers, substituted amino-containing monomers, epoxy-containing monomers, etc. .

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(亦即不具有(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, 3-hydroxy (meth)acrylate Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyalkyl (meth)acrylates; vinyl alcohol, Non-(meth)acrylic unsaturated alcohols (that is, unsaturated alcohols not having a (meth)acryl skeleton) such as allyl alcohol, 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(亦即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(亦即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。 As the aforementioned carboxyl group-containing monomers, for example, ethylenically unsaturated monocarboxylic acids (that is, monocarboxylic acids having ethylenically unsaturated bonds) such as (meth)acrylic acid and crotonic acid; fumaric acid, Itaconic acid, maleic acid, citraconic acid and other ethylenically unsaturated dicarboxylic acids (that is, dicarboxylic acids having ethylenically unsaturated bonds); anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; methacrylic acid 2-carboxyethyl ester, etc., carboxyalkyl (meth)acrylate, etc.

具有前述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 acrylic monomers having the aforementioned functional groups are preferably hydroxyl-containing monomers and carboxyl-containing monomers, more preferably hydroxyl-containing monomers.

構成前述丙烯酸系聚合物(a11)之具有前述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 monomers having the functional groups 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 can be selected arbitrarily.

作為不具有前述官能基之丙烯酸系單體，較佳為構成 烷基酯之烷基為碳數為1至18之鏈狀結構之(甲基)丙烯酸烷基酯等，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。 As an acrylic monomer that does not have the aforementioned functional group, it is preferable to constitute The alkyl group of the alkyl ester is an alkyl (meth)acrylate with a chain structure of 1 to 18 carbon atoms, such as: methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylate, etc. base) n-propyl acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second-butyl (meth)acrylate, second-butyl (meth)acrylate Tributyl, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, ( n-octyl methacrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, (meth)acrylic acid Lauryl (also known as lauryl (meth)acrylate), tridecyl (meth)acrylate, myristyl (meth)acrylate (also known as myristyl (meth)acrylate ester), pentadecyl (meth)acrylate, cetyl (meth)acrylate (also known as palmityl (meth)acrylate), heptadecyl (meth)acrylate, (meth)acrylate base) stearyl acrylate (also known as stearyl (meth)acrylate) and the like.

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。 In addition, examples of the above-mentioned acrylic monomer having no functional group include methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, etc. (meth)acrylic acid esters containing alkoxyalkyl groups such as ethoxyethyl (meth)acrylate; (meth)acrylate; non-cross-linked (meth)acrylamide and its derivatives; (meth)acrylate N,N-dimethylaminoethyl ester, (meth)acrylate N,N- Non-crosslinked (meth)acrylates with tertiary amino groups such as dimethylaminopropyl ester, etc.

構成前述丙烯酸系聚合物(a11)之不具有前述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 the said functional group which comprises the said acrylic polymer (a11) may be only 1 type, and may be 2 or more types. When it is 2 or more types, these combinations and ratios can be chosen arbitrarily.

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; and styrene.

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 monomer which comprises the said acrylic polymer (a11) may be only 1 type, and may be 2 or more types, and when it is 2 or more types, these combinations and ratios can be arbitrarily selected.

前述丙烯酸系聚合物(a11)中，相對於構成前述丙烯酸系聚合物(a11)之結構單元的總質量，由具有前述官能基之丙烯酸系單體衍生之結構單元之比例(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，藉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)中的能量線硬化性基的含量，可將第1保護膜的硬化程度容易地調節為較佳範圍。 In the aforementioned acrylic polymer (a11), the ratio (content) of the structural unit derived from the acrylic monomer having the aforementioned functional group relative to the total mass of the structural units constituting the aforementioned acrylic polymer (a11) is preferably 0.1% by mass to 50% by mass, more preferably 1% by mass to 40% by mass, most preferably 3% by mass to 30% by mass. When the aforementioned ratio is in such a range, the energy ray curability in the aforementioned acrylic resin (a1-1) obtained by copolymerization of the aforementioned acrylic polymer (a11) and the aforementioned energy ray curable compound (a12) The content of the radical can easily adjust the degree of hardening of the first protective film to a preferable range.

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, and when it is 2 or more types, these combinations and ratios can be chosen arbitrarily.

‧能量線硬化性化合物(a12) ‧Energy ray hardening 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 energy ray-curable compound (a12) preferably has one or more kinds selected from the group consisting of an isocyanate group, an epoxy group, and a carboxyl group as a compound that can be combined with the acrylic polymer (a11) The functional group-reactive group preferably has an isocyanate group as the aforementioned group. For example, when the energy ray-curable compound (a12) has an isocyanate group as the group, the isocyanate group reacts easily 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個前述能量線硬化性基。 The aforementioned energy ray curable compound (a12) preferably has 1 to 5 aforementioned energy ray curable groups in 1 molecule, more preferably has 1 to 3 aforementioned energy ray curable groups.

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-curing compound (a12) include 2-methacryloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryl isocyanate, allyl isocyanate, 1,1-(bisacryloxymethyl)ethyl isocyanate; by reaction of diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth)acrylate Acryl 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, the aforementioned energy ray-curable compound (a12) is preferably 2-methacryloxyethyl 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。 The aforementioned energy ray-curable compound (a12) constituting the aforementioned acrylic resin (a1-1) may be only one type, or may be two or more types; in the case of two or more types, these combinations and ratios can be selected arbitrarily.

丙烯酸系樹脂(a1-1)的含量相對於保護膜形成用組成物(IV-1)中的溶劑以外的總質量，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%。 The content of the acrylic resin (a1-1) is preferably from 1% by mass to 40% by mass, more preferably from 2% by mass to 30% by mass, based on the total mass of the protective film forming composition (IV-1) excluding the solvent. % by mass, preferably 3% by mass to 20% by mass.

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。 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) in the acrylic resin (a1-1) It is preferably 20 mol% to 120 mol%, more preferably 35 mol% to 100 mol%, and most preferably 50 mol% to 100 mol%. When the content ratio is in such a range, the adhesive force of the protective film formed by curing becomes greater. Furthermore, in the case where the aforementioned energy ray-curable compound (a12) is a functional compound (having one of the aforementioned groups in 1 molecule), the upper limit of the ratio of the aforementioned content is 100 mol%. When the line-curing 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)可使不符合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，在與前述交聯劑(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 aforementioned polymer (a1) is cross-linked by the cross-linking agent (f), the aforementioned polymer (a1) can make any one of the aforementioned acrylic polymer (a11) that does not meet the above description A monomer having a group reactive with the crosslinking agent (f) is polymerized to perform crosslinking in the group reactive with the aforementioned crosslinking agent (f). ) to carry out cross-linking in the group reacting 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 protective film-forming composition (IV-1) and the protective film-forming film may be only one type, or may be two or more types; in the case of two or more types, these combinations And the ratio can be chosen arbitrarily.

(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 curable group and having a molecular weight of 100 to 80000)

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。 As the energy ray curable group possessed by the compound (a2) having an energy ray curable group and having a molecular weight of 100 to 80,000, a group containing an energy ray curable double bond is exemplified: (a base) acryl, vinyl, etc.

作為前述化合物(a2)，只要滿足上述條件，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 aforementioned compound (a2) is not particularly limited as long as it satisfies the above conditions, and examples thereof include low-molecular-weight compounds having energy ray-curable groups, epoxy resins having energy ray-curable groups, and Phenolic resin etc.

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。 Among the aforementioned compounds (a2), examples of low-molecular-weight compounds having energy-ray-curable groups include polyfunctional monomers or oligomers, and acrylate compounds having (meth)acryl groups are preferred.

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(亦稱為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。 Examples of the aforementioned acrylate-based compounds include: 2-hydroxy-3-(meth)acryloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxy bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A bis(methyl) ) acrylate, 2,2-bis[4-((meth)acryloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloxy Ethoxy)phenyl] fennel, 2,2-bis[4-((meth)acryloxypolypropoxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylate (also known as tricyclodecane 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, polytetramethylene glycol di( Meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-( (meth)acryloxyethoxy)phenyl]propane, neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3 -Bifunctional (meth)acrylates such as di(meth)acryloxypropane; tris(2-(meth)acryloxyethyl)isocyanurate, ε-caprolactone modified isocyanurate Tris-(2-(meth)acryloxyethyl)cyanurate, Ethoxylated Glyceryl Tri(meth)acrylate, Pentaerythritol Tri(meth)acrylate, Trimethylolpropane Tri( Meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, ethyl Oxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, dipentaerythritol hexa(meth)acrylate and other multifunctional (meth)acrylates; Polyfunctional (meth)acrylate oligomers such as (meth)acrylate urethane 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 aforementioned 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 "JP-A-2013-194102" can be used. of resin. Such a 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 aforementioned compound (a2) contained in the composition for forming a protective film (IV-1) and the film for forming a protective film may be only one kind, or may be 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) not having an energy ray curable group]

於保護膜形成用組成物(IV-1)及保護膜形成用膜係含有前述化合物(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 aforementioned compound (a2) as the aforementioned energy ray curable component (a), it is preferable to further contain The 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。 The aforementioned polymer (b) may be at least partially crosslinked by a crosslinking agent (f) , and may not be cross-linked.

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) not having an energy ray curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber-based resins, and acrylic urethane resins. , polyvinyl alcohol (PVA), butyral resin, polyester urethane 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, may be simply referred to as "acrylic polymer (b-1)").

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種以上除了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, or a copolymer of two or more acrylic monomers, or one or more A copolymer of two or more acrylic monomers and one or more monomers other than acrylic monomers (non-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 acrylic monomers constituting the acrylic polymer (b-1) include alkyl (meth)acrylates, (meth)acrylates having a cyclic skeleton, glycidyl group-containing (meth)acrylates, base) acrylates, hydroxyl-containing (meth)acrylates, substituted amino-containing (meth)acrylates, etc. Here, the "substituted amino group" is as described above.

作為前述(甲基)丙烯酸烷基酯，較佳為構成烷基酯之烷基為碳數為1至18之鏈狀結構之(甲基)丙烯酸烷基酯等，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。 As the above-mentioned alkyl (meth)acrylate, preferred are alkyl (meth)acrylates in which the alkyl constituting the alkyl ester is a chain structure having 1 to 18 carbon atoms, for example, (methyl) ) methyl acrylate, (meth) ethyl acrylate, ( n-propyl methacrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, (meth)acrylic acid Tertiary butyl ester, pentyl (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) Lauryl (meth)acrylate (also known as lauryl (meth)acrylate), tridecyl (meth)acrylate, myristyl (meth)acrylate (also known as meth)acrylate myristyl), pentadecyl (meth)acrylate, cetyl (meth)acrylate (also known as palmityl (meth)acrylate), heptadecyl (meth)acrylate, ( Octadecyl methacrylate (also known 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 a cyclic skeleton include cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate; Aralkyl (meth)acrylate such as benzyl acrylate; cycloalkenyl (meth)acrylate such as dicyclopentenyl (meth)acrylate; dicyclopentenyloxyethyl (meth)acrylate, etc. Cycloalkenyloxyalkyl (meth)acrylate, etc.

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, (meth) 2-Hydroxypropyl Acrylate, 3-Hydroxypropyl (Meth)acrylate, 2-Hydroxybutyl (Meth)acrylate, 3-Hydroxybutyl (Meth)acrylate, 4-Hydroxybutyl (Meth)acrylate Wait.

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, N-methylamino ethyl (meth)acrylate 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、冰片烯等烯烴；乙酸乙烯酯；苯乙烯等。 Examples of the non-acrylic monomer constituting the acrylic polymer (b-1) include olefins such as ethylene and norbornene; vinyl acetate; and styrene.

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) that is at least partly crosslinked by the crosslinking agent (f) and does not have the aforementioned energy ray-curable group include: the reactive functional group and the crosslinking agent in the aforementioned polymer (b) (f) Reactive polymers.

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。另外，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 said reactive functional group should just be suitably selected according to the kind of crosslinking agent (f), etc., and it does not specifically limit. For example, when the crosslinking agent (f) is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxyl group, an amino group, and the like; among these, a hydroxyl group having high reactivity with an isocyanate group is preferred. . In addition, when the crosslinking agent (f) is an epoxy-based compound, examples of the reactive functional groups include carboxyl groups, amine groups, and amido groups. Among them, reaction with epoxy groups is preferred. High carboxyl group. However, the aforementioned 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 having the aforementioned reactive functional group and not having energy ray hardening The polymer (b) of the group includes, for example, a polymer obtained by polymerizing at least a monomer having the aforementioned reactive functional group. In the case of the acrylic polymer (b-1), any one or both of the aforementioned acrylic monomers and non-acrylic monomers listed as monomers constituting the acrylic polymer (b-1) , the monomers having the aforementioned reactive functional groups can be used. For example, as the aforementioned polymer (b) having a hydroxyl group as a reactive functional group, for example, a polymer obtained by polymerizing a hydroxyl-containing (meth)acrylate; A polymer obtained by polymerizing a monomer in which one or more hydrogen atoms of the aforementioned acrylic monomers or non-acrylic monomers are replaced by the aforementioned reactive functional groups.

具有反應性官能基之前述聚合物(b)中，相對於構成前述聚合物(b)之結構單元的總質量，由具有反應性官能基之單體衍生之結構單元之比例(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 structural unit derived from a monomer having a reactive functional group relative to the total mass of the structural units constituting the aforementioned polymer (b) is preferable 1% by mass to 25% by mass, more preferably 2% by mass to 20% by mass. When the aforementioned ratio is in such a range, the degree of crosslinking in the aforementioned polymer (b) 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 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 protective film forming composition (IV-1) and the polymer (b) not having an energy ray curable group contained in the protective film forming film may be only one kind or may be Two or more; in the case of two or more, these combinations and ratios can be selected arbitrarily.

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。並且，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)。另外，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)。 Examples of the composition (IV-1) for forming a protective film include a composition containing either or both of the aforementioned polymer (a1) and the aforementioned compound (a2). Furthermore, when the protective film forming composition (IV-1) contains the aforementioned compound (a2), it is preferable to further contain a polymer (b) not having an energy ray curable group; It is preferable to further contain the aforementioned (a1). In addition, the protective film forming composition (IV-1) may not contain the aforementioned compound (a2), and may also contain the aforementioned polymer (a1) and the polymer (b) not having an energy ray curable group.

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，將前述聚合物(a1)及不具有能量線硬化性基之聚合物(b)的合計含量設為100質量份時，保護膜形成用組成物(IV-1)中的前述化合物(a2)的含量較佳為10質量份至400質量份，更佳為30質量份至350質量份。 When the protective film forming composition (IV-1) contains the aforementioned polymer (a1), the aforementioned compound (a2) and the polymer (b) having no energy ray curable group, the aforementioned polymer (a1) The content of the aforementioned compound (a2) in the protective film forming composition (IV-1) is preferably 10 parts by mass when the total content of the polymer (b) having no energy ray curable group is 100 parts by mass to 400 parts by mass, more preferably 30 to 350 parts by mass.

保護膜形成用組成物(IV-1)中，相對於溶劑以外的成分的總質量之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(亦即相對於保護膜形成用膜的總質量之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(質量))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 protective film forming composition (IV-1), the total content of the energy ray curable component (a) and the polymer (b) not having an energy ray curable group relative to the total mass of components other than the solvent ( That is, the total content (mass) of the energy ray curable component (a) and the polymer (b) not having an energy ray curable group relative to the total mass of the protective film forming film is preferably 5% by mass. to 90% by mass, more preferably 10% to 80% by mass, especially preferably 15% to 70% by mass. When 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.

保護膜形成用組成物(IV-1)中，相對於溶劑以外的成分的總含量(總質量)之前述能量線硬化性成分(a)的含量(亦即相對於保護膜形成用膜的總質量之前述能量線硬化性成分(a)的含量)較佳為6質量%至50質量%，更佳為10質量%至40質量%，進而更佳為15質量%至30質量%，尤佳為19.5質量%至27質量%。藉由前述合計含量之比例為此種範圍，適度硬化而造膜性更良好，可防止硬化時過度收縮而可靠性降低。 In the composition for forming a protective film (IV-1), the content of the aforementioned energy ray-curable component (a) relative to the total content (total mass) of components other than the solvent (that is, the total amount of the film for forming a protective film) The content of the aforementioned energy ray-curing component (a) by mass) is preferably 6% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, still more preferably 15% by mass to 30% by mass, and most preferably 19.5% by mass to 27% by mass. When the ratio of the above-mentioned total content is in such a range, the film-forming property is better when moderately cured, and it is possible to prevent excessive shrinkage during curing and decrease in reliability.

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 protective film-forming composition (IV-1) contains the aforementioned energy ray-curable component (a) and the polymer (b) having no energy-ray-curable group, the protective film-forming composition (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, based on 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 ray curability of the film for protective film formation becomes more favorable.

保護膜形成用組成物(IV-1)中，除了能量線硬化性成分(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。 The protective film forming composition (IV-1) may contain, in addition to the energy ray curable component (a) and the polymer (b) not having an energy ray curable group, a photopolymerization initiator selected from (c), filler (d), coupling agent (e), crosslinking agent (f), colorant (g), thermosetting component (h), and general One or more of the group consisting of additives (z). For example, by using the protective film-forming composition (IV-1) containing the aforementioned energy ray-curable component (a) and thermosetting component (h), the formed protective film-forming film is heated against the The adhesive strength of the adhesive body is improved, and the strength of the protective film formed from the film for protective film formation 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 compounds; acyl phosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide ; sulfide compounds such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene Titanocene compounds such as thioxanthone; thioxanthone compounds such as thioxanthone; benzophenone, 2-(dimethylamino)-1-(4-morpholine (morpholine) phenyl)-2-benzyl- 1-butanone, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) Benzophenone compounds; peroxide compounds; diketone compounds such as diacetyl; benzoyl; dibenzoyl; 2,4-diethylthioxanthone; 1,2-diphenylmethane; -Hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; 2-chloroanthraquinone, etc.

另外，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。 In addition, as the photopolymerization initiator (c), for example, 1-chloroanthraquinone can also be used Other quinone compounds; photosensitizers such as amines, etc.

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 protective film forming composition (IV-1) may be only one type, or may be two or more types; in the case of two or more types, these combinations and ratios may be 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2.0質量份至12.0質量份，尤佳為2質量份至10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) relative to the content of the energy ray-curable compound (a) is 100 Parts by mass, preferably 0.01 to 20 parts by mass, more preferably 2.0 to 12.0 parts by mass, especially preferably 2 to 10 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。另外，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 be easily adjusted in thermal expansion coefficient, and the coefficient of thermal expansion can be optimized for the object to be formed in the protective film, thereby using The reliability of the package obtained by the composite sheet for protective film formation improves further. Moreover, when the film for protective film formation contains a filler (d), the moisture absorption rate of a protective film can be reduced, and 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 (d), what 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, and is 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 filler materials, for example, powders of silicon dioxide, alumina, talc, calcium carbonate, titanium dioxide, iron oxide, silicon carbide, boron nitride, etc. can be listed; these inorganic filler materials are spheroidized. Beads; surface-modified 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，更佳為經環氧修飾之二氧化矽。 Among these, the inorganic filler is preferably silicon dioxide or aluminum oxide, more preferably epoxy-modified silicon dioxide.

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0.08μm至15μm，更佳為0.1μm至15μm，更佳為0.1μm至10μm，更佳為0.3μm至10μm，尤佳為0.5μm至8μm。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 size of the filler (d) is not particularly limited, preferably 0.01 μm to 20 μm, more preferably 0.08 μm to 15 μm, more preferably 0.1 μm to 15 μm, more preferably 0.1 μm to 10 μm, more preferably 0.3 μm to 10 μm, more preferably 0.5 μm to 8 μm. When the average particle diameter of the filler (d) is in such a range, the adhesiveness to the formation object of a protective film can be maintained, and the fall of the light transmittance of the protective film can be suppressed.

再者，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 addition, in this specification, unless otherwise specified, the "average particle diameter" means the value of the particle diameter (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 protective film-forming composition (IV-1) and the filler (d) contained in the protective film-forming 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，相對於溶劑以外的全部成分的總含量(總質量) 之填充材料(d)的含量(亦即相對於保護膜形成用膜的總質量之填充材料(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，更容易調整上述熱膨脹係數。 When the filler (d) is used, the total content (gross mass) of all components other than the solvent in the protective film forming composition (IV-1) The content of the filler (d) (that is, the content of the filler (d) relative to the total mass of the film for forming a protective film) is preferably from 5 mass % to 83 mass %, more preferably from 7 mass % to 78 mass % %. When the content of the filler (d) falls within such a range, it becomes easier to adjust the coefficient of thermal expansion.

作為本發明之一態樣，填充材料(d)的含量相對於保護膜形成用膜的總質量，較佳為5質量%至83質量%，更佳為5質量%至70質量%。 As an aspect of the present invention, the content of the filler (d) is preferably 5% by mass to 83% by mass, more preferably 5% by mass to 70% by mass, based on the total mass of the protective film forming film.

作為本發明之另一態樣，填充材料(d)的平均粒徑為0.08μm至0.15μm時，填充材料(d)的含量相對於保護膜形成用膜的總質量，較佳為5質量%至83質量%，更佳為5質量%至70質量%。 As another aspect of the present invention, when the average particle size of the filler (d) is 0.08 μm to 0.15 μm, the content of the filler (d) is preferably 5% by mass relative to the total mass of the protective film forming film to 83% by mass, more preferably 5% to 70% by mass.

作為本發明之又一態樣，填充材料(d)的平均粒徑為0.5μm至8μm時，填充材料(d)的含量相對於保護膜形成用膜的總質量，較佳為5質量%至8質量%。 As another aspect of the present invention, when the average particle size of the filler (d) is 0.5 μm to 8 μm, the content of the filler (d) is preferably 5% by mass to 5% by mass relative to the total mass of the protective film forming film. 8% by mass.

藉由填充材料(d)的含量為此種範圍，更容易將保護膜形成用膜中的至少一方的表面(β)的表面粗糙度(Ra)調整為0.04μm以上，更佳為0.049μm以上，更容易將前述表面(β)的表面粗糙度(Ra)調整為0.15μm以下，更佳為0.129μm以下。 When the content of the filler (d) is in such a range, it is easier to adjust the surface roughness (Ra) of at least one surface (β) of the film for forming a protective film to 0.04 μm or more, more preferably 0.049 μm or more , it is easier to adjust the surface roughness (Ra) of the aforementioned surface (β) to be 0.15 μm or less, more preferably 0.129 μm or less.

亦即，於將填充材料(d)的含量設為上述範圍之情形時，容易將保護膜形成用膜中的至少一方的表面(β)的表面粗糙度(Ra)調整為較佳為0.04μm至0.15μm，更佳為0.049μm至0.129μm。 That is, when the content of the filler (d) is within the above-mentioned range, it is easy to adjust the surface roughness (Ra) of at least one surface (β) of the film for protective film formation to preferably 0.04 μm to 0.15 μm, more preferably 0.049 μm to 0.129 μm.

[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。另外，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 a coupling agent having a functional group reactive with an inorganic compound or an organic compound as the coupling agent (e), the adhesiveness and adhesion of the film for protective film formation to an adherend can be improved. Moreover, by using a coupling agent (e), the protective film obtained by hardening the film for protective film formation improves water resistance, without impairing heat 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) is preferably a compound having a functional group capable of reacting with a functional group possessed by the energy ray curable component (a) or the polymer (b) having no energy ray curable group, more preferably silane Coupler.

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。 As preferred aforementioned silane coupling agents, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl Triethoxysilane, 3-glycidyloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane 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, imidazole silane, 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。 Contained in the composition for forming a protective film (IV-1) and the film for forming a protective film The coupling agent (e) may be only one type, or two or more types; in the case of two or more types, these combinations and ratios can be selected 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，將能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)的合計含量設為100質量份時，偶合劑(e)的含量較佳為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)於樹脂中之分散性提高，或保護膜形成用膜與被接著體之接著性提高等。另外，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。 When the coupling agent (e) is used, the energy ray-curable component (a) and the polymer having no energy ray-curable group are added to the protective film-forming composition (IV-1) and the protective film-forming film When the total content of (b) is set to 100 parts by mass, the content of coupling agent (e) is preferably 0.03 parts by mass to 20 parts by mass, more preferably 0.05 parts by mass to 10 parts by mass, especially preferably 0.1 parts by mass to 5 parts by mass parts by mass. When the aforementioned content of the coupling agent (e) is above the aforementioned lower limit value, the following effect brought by the use of the coupling agent (e) can be obtained more significantly: the dispersibility of the filler (d) in the resin is improved, or Improvement of the adhesion between the film for protective film formation and the adherend, etc. Moreover, when the said content of a coupling agent (e) is below the said upper limit, generation|occurrence|production of outgassing 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。 The initial adhesive force of the film for protective film formation can be adjusted by crosslinking the above-mentioned energy ray curable component (a) or the polymer (b) not having an energy ray curable group by using a crosslinking agent (F). 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 crosslinking agents (crosslinking agents having a metal chelate structure), aziridine crosslinking agents, etc. 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。另外，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 aforementioned organic polyvalent isocyanate compounds include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, and alicyclic polyvalent isocyanate compounds (hereinafter, these compounds may be collectively referred to simply as "aromatic polyvalent isocyanate compounds, etc."); Tripolymers, isocyanurate bodies, and adducts of the aforementioned aromatic polyvalent isocyanate compounds, etc.; terminal isocyanate urethane prepolymers obtained by reacting the aforementioned aromatic polyvalent isocyanate compounds, etc., with polyol compounds, etc. . The aforementioned "adduct" means that the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound is mixed with ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil, etc. Examples of the reactant of the low-molecular-weight active hydrogen compound include xylylene diisocyanate adduct of trimethylolpropane, which will be described later, as examples of the aforementioned adduct. In addition, the "isocyanate-terminated urethane prepolymer" means a prepolymer having a urethane bond and 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 the aforementioned organic polyvalent isocyanate compound, more specifically, for example, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; Isocyanate; Diphenylmethane-4,4'-diisocyanate; Diphenylmethane-2,4'-diisocyanate; 3-Methyldiphenylmethane diisocyanate; Hexamethylene diisocyanate; Isophorone Diisocyanate; Dicyclohexylmethane-4,4'-diisocyanate; Dicyclohexylmethane-2,4'-diisocyanate; Toluene diisocyanate, Hexamethylene di Any one or two or more compounds of isocyanate 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。 Examples of the aforementioned organic polyimine compound include N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-nitrogen Pyridylpropionate, tetramethylolmethane-tris-β-aziridinylpropionate, N,N'-toluene-2,4-bis(1-aziridinecarboxamide) triethylene base 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。 In the case of using an organic polyvalent isocyanate compound 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) having no energy ray curable group . When the crosslinking agent (f) has an isocyanate group and the energy ray-curable component (a) or the polymer (b) without energy ray-curable groups has a hydroxyl group, the crosslinking agent (f) and the energy ray The reaction of the curable component (a) or the polymer (b) not having an 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 crosslinking agent (f) contained in the protective film-forming composition (IV-1) and the protective film-forming film may be only one type, or two or more types; in the case of two or more types, the combination of these And the ratio can be chosen arbitrarily.

於使用交聯劑(f)之情形時，保護膜形成用組成物(IV-1)中，將能量線硬化性成分(a)及不具有能量線硬化性 基之聚合物(b)的合計含量設為100質量份時，交聯劑(f)的含量較佳為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。另外，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。 In the case of using the crosslinking agent (f), the composition for forming a protective film (IV-1) contains an energy ray curable component (a) and a non-energy ray curable component. When the total content of the base polymer (b) is set to 100 parts by mass, the content of the crosslinking agent (f) is preferably from 0.01 parts by mass to 20 parts by mass, more preferably from 0.1 parts by mass to 10 parts by mass, especially preferably 0.5 parts by mass to 5 parts by mass. When the said content of a crosslinking agent (f) is more than the said lower limit, the more remarkable effect by using a crosslinking agent (f) can be acquired. Moreover, the excessive use of a crosslinking agent (f) can be suppressed by the said content of a crosslinking agent (f) being below the said upper limit.

[著色劑(g)] [coloring agent (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 a coloring agent (g), well-known coloring agents, such as an inorganic pigment, an organic pigment, and an organic dye, are mentioned, for example.

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 aforementioned organic pigments and organic dyes include ammonium-based dyes, cyanine-based dyes, merocyanine-based dyes, croconium-based dyes, squalilium-based dyes, azulenium-based Pigments, polymethine dyes, naphthoquinone dyes, pyrylium dyes, phthalocyanine dyes, naphthalocyanine dyes, naphtholactamide dyes, azo dyes, condensed azo dyes, indigo pigments, perinone pigments, perylene pigments, dioxane pigments, quinacridone pigments, isoindolinone pigments, quinophthalone pigments, pyrrole pigments, Thioindigo dyes, metal complex dyes (metal complex dyes), dithiol metal complex dyes, indoxyl dyes, triallyl methane dyes, anthraquinone dyes, naphthol pigments, methine azo pigments, benzimidazolone pigments, pyranthrone pigments, threne pigments, etc.

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(亦即氧化銦錫(Indium Tin Oxide))系色素、ATO(亦即氧化銻錫(Antimony Tin Oxide))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, ITO (that is, indium tin oxide (Indium Tin Oxide)) based pigments, ATO (that is, antimony tin oxide (Antimony Tin Oxide)) based pigments, etc.

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 protective film formation and the film for protective film formation may be only 1 type, and may be 2 or more types; In the case of 2 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，相對於溶劑以外的全部成分的合計含量之著色劑(g)的含量(亦即相對於保護膜形成用膜的總質量之著色劑(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。另外，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), what is necessary is just to adjust content of the coloring agent (g) in the film for protective film formation suitably according to the objective. For example, a protective film may be printed by laser irradiation. By adjusting the content of the coloring agent (g) in the protective film-forming film and adjusting the light transmittance of the protective film, the visibility of the printed characters can be adjusted. In this case, in the composition for forming a protective film (IV-1), the content of the coloring agent (g) relative to the total content of all components other than the solvent (that is, the coloring amount relative to the total mass of the film for forming a protective film) The content of the agent (g)) is preferably 0.1% by mass to 10% by mass, more preferably 0.4% by mass to 7.5% by mass, especially preferably 0.8% by mass to 5% by mass. When the said content of a coloring agent (g) is more than the said lower limit, the more remarkable effect by using a coloring agent (g) can be acquired. Moreover, the excessive use of a coloring agent (g) can be suppressed by the said content of a coloring agent (g) being 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 thermosetting component (h) contained in the composition for forming a protective film (IV-1) and the film for forming a protective film may be only one kind, or may be two or more kinds; in the case of two or more kinds, these Combinations and ratios can be chosen arbitrarily.

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。 Examples of the thermosetting component (h) include: epoxy-based thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, silicone resins, etc., preferably Epoxy based 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 for forming a protective film (IV-1) and the film for forming a protective film 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 chosen arbitrarily.

‧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, such as polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, o-cresol novolac epoxy resins, and polyfunctional 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), epoxy resins with unsaturated hydrocarbon groups can also be used. resin. Epoxy resins with unsaturated hydrocarbon groups are more compatible with acrylic resins than epoxy resins without unsaturated hydrocarbon groups. 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 adding (meth)acrylic acid or a derivative thereof to an epoxy group.

另外，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。 Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which have the group which has an unsaturated hydrocarbon group directly bonded to 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，作為前述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 an unsaturated group with polymerizability. Specific examples of the above-mentioned unsaturated hydrocarbon group include: ethylidene group (also called vinyl group), 2-propenyl group (also called allyl group), (methylidene group) base) acryl group, (meth)acrylamide group, etc., preferably 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 from 300 to 30,000, more preferably from 400 to 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 the present specification, the "number average molecular weight" means the number average molecular weight measured by gel permeation chromatography (GPC) and shown in terms of standard polystyrene unless otherwise specified.

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 from 100 g/eq to 1000 g/eq, more preferably from 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, the term "epoxy equivalent" means the number of grams (g/eq) of an epoxy compound containing 1 gram equivalent of an epoxy group, and can be measured in accordance with 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。 Epoxy resin (h1) may be used individually by 1 type, and may use 2 or more types together; When using 2 or more types together, these combination and ratio can be chosen arbitrarily.

‧熱硬化劑(h2) ‧Heat curing 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 2 or more functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. Examples of the aforementioned functional groups include: phenolic hydroxyl groups, alcoholic hydroxyl groups, amino groups, carboxyl groups, groups formed by anhydrided acid groups, etc., preferably phenolic hydroxyl groups, amino groups, or groups formed by anhydrided acid groups. The base is more preferably a phenolic hydroxyl group or an amino 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 phenolic curing agents having phenolic hydroxyl groups include polyfunctional phenolic resins, biphenols, novolak-type phenolic resins, dicyclopentadiene-based phenolic resins, and aralkylphenolic resins. 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 the amine-based curing agent having an amino group, dicyandiamide (hereinafter, may be abbreviated as "DICY" in some cases) etc. are mentioned, for example.

熱硬化劑(h2)亦可具有不飽和烴基。 The thermosetting agent (h2) may 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 by a group having an unsaturated hydrocarbon group; 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)的軟化點或玻璃轉移溫度以高為佳。 In the case of using a phenolic curing agent as the thermosetting agent (h2), the softening point or glass transition temperature of the thermosetting agent (h2) is preferably high in terms of improving the peelability of the protective film from the support sheet.

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), the number-average molecular weight of resin components such as polyfunctional phenol resins, novolak-type phenol resins, dicyclopentadiene-based phenol resins, and aralkylphenol resins is preferably from 300 to 30,000, more preferably 400 to 10000, preferably 500 to 3000.

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), the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, and 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。 The 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 combination and ratio can be chosen 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) in the composition for forming a protective film (IV-1) and the film for forming a protective film is comparable to that of the thermosetting agent (h2). With respect to 100 parts by mass of the content of the epoxy resin (h1), it is preferably 0.01 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)的合計含量)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 a 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, epoxy resin (h1) and the total content of the thermosetting agent (h2)) is preferably 1 to 500 parts by mass relative to 100 parts by mass of the polymer (b) having no energy ray curable group.

[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, which can be arbitrarily selected according to the purpose, and is not particularly limited. Preferred general-purpose additives include, for example, plasticizers, antistatic agents, antioxidants, getters, etc. .

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 general-purpose additive (z) contained in the protective film-forming composition (IV-1) and the protective film-forming 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 using the general additive (z), the content of the general additive (z) in the protective film forming composition (IV-1) and the protective film forming 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 composition for forming a protective film (IV-1) preferably further contains a solvent. The composition (IV-1) for forming a protective film containing a solvent 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(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 aforementioned solvents are not particularly limited, and examples of preferred aforementioned solvents include: hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropan-1-ol), 1 - Alcohols such as butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (compounds with amide bonds) )Wait.

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 protective film formation 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 chosen arbitrarily.

就可更均勻地混合保護膜形成用組成物(IV-1)中的含有成分之方面而言，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 protective film-forming composition (IV-1) is preferably methyl ethyl ketone, Toluene or ethyl acetate, etc.

<<保護膜形成用組成物的製造方法>> <<Manufacturing Method of Protective Film Forming Composition>>

保護膜形成用組成物(IV-1)等保護膜形成用組成物係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 protective film formation, such as the composition for protective film formation (IV-1), is obtained by preparing each component which comprises this composition for protective film formation.

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 of 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 one of the ingredients other than the solvent and diluting the ingredients in advance; it can also be used by not mixing any of the ingredients other than the solvent. The formulation ingredients are pre-diluted and the solvent is mixed with these formulation 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；使用混合機進行混合之方法；施加超音波進行混合之方法等。 There is no particular limitation on the method of mixing the ingredients during preparation, and it is known from the following Appropriate selection may be made from the following methods: a method of mixing by rotating a stirring bar or a stirring blade; a method of mixing by using a mixer; a method of mixing by applying ultrasonic waves, 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 for adding and mixing the components are not particularly limited as long as the components are not degraded, and may be appropriately adjusted. The temperature is preferably 15°C to 30°C.

與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係有切割晶粒接合片(dicing die bonding sheet)。 Similar to the composite sheet for forming a protective film of the present invention, as a composite sheet attached to a semiconductor wafer or the back surface of the semiconductor wafer opposite to the circuit surface and provided with a layer showing adhesiveness on the support sheet, there is a diced wafer. Dicing die bonding sheet.

但是，關於切割晶粒接合片所具備之接著劑層，於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，發揮作為接著劑之功能。另一方面，關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，具有保護被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，所要求之性能當然亦不同。並且，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。具備能 量線硬化性之保護膜形成用膜之本發明之保護膜形成用複合片，關於附有保護膜的半導體晶片的拾取適性，空前般極其優異。 However, the adhesive layer included in the dicing die-bonding sheet functions as an adhesive when the semiconductor chip is picked up from the support sheet together with the semiconductor chip, and the semiconductor chip is mounted on a substrate, a lead frame, or another semiconductor chip, etc. . On the other hand, the protective film forming film in the protective film forming composite sheet of the present invention is the same as the above-mentioned adhesive layer in terms of picking up from the support sheet together with the semiconductor wafer, but finally becomes The protective film has the function of protecting the back side of the attached semiconductor chip. Thus, the use of the film for protective film formation in this invention is different from the adhesive layer in a dicing die-bonding sheet, and required performance differs naturally. And, reflecting the difference in the use, generally, the film for protective film formation tends to be hard and difficult to pick up when compared with the adhesive layer in the dicing die-bonding sheet. Therefore, it is generally difficult to use the adhesive layer in a dicing die-bonding sheet as it is as the film for protective film formation in the composite sheet for protective film formation. capable The protective film-forming composite sheet of the present invention, which is a radiation curable protective film-forming film, is extremely excellent in pick-up property of a semiconductor wafer with a protective film as never before.

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

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 of this invention can be manufactured by laminating|stacking each said 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，於基材上塗敷上述之黏著劑組成物，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 substrate when manufacturing a support sheet, the above-mentioned adhesive composition may be applied on the substrate, and the adhesive composition may be dried if 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 already laminated on a base material, the composition for forming a protective film can be coated on the adhesive layer to directly form a film for forming a protective film. The layer other than the film for protective film formation can also use the composition for forming this layer, and this layer is laminated|stacked on an adhesive agent layer by the same method. In this way, when forming a continuous two-layer laminated structure using any one of the compositions, the composition can be further coated on the layer formed of the aforementioned composition to form a new layer.

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 laminated structure by using the above-mentioned composition on another release film to form a post-lamination layer of these two layers in advance, and to form the layer of the formed layer with The exposed surface on the opposite side to the side in contact with the peeling film is bonded to the exposed surface of the remaining layer already formed. In this case, the aforementioned composition is preferably applied to the release-treated surface of the release film. . After the laminated structure is formed, the release film may be removed if necessary.

例如於製造於基材上積層黏著劑層並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，並另行於剝離膜上塗敷保護膜形成用組成物，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, the manufacture of a composite sheet for protective film formation in which an adhesive layer is laminated on a base material and a film for forming a protective film is laminated on the adhesive layer (the support sheet is a laminate of the base material and the adhesive layer) In the case of using a composite sheet), apply an adhesive composition on the substrate, dry the adhesive composition if necessary, thereby pre-laminate the adhesive layer on the substrate, and apply a protective film on the release film separately. Composition, if necessary, the adhesive composition is dried to form a film for protective film formation 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 substrate, and the film for forming a protective film is laminated on the adhesive layer to obtain a composite sheet for forming a protective film. .

再者，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。 Furthermore, in the case of laminating an adhesive layer on a substrate, as described above, instead of applying the adhesive composition on the substrate, the adhesive composition can be applied on the release film, and the adhesive composition can be made as necessary. The product is dried to form an adhesive layer on the release film in advance, and the exposed surface of the layer is bonded to one surface of the base material, whereby the adhesive layer is laminated on the base material.

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, it is sufficient to remove the peeling film at any time point after forming the target laminated 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 protective film forming composite sheet can be laminated by the method of forming in advance on the release film and then laminating it on the surface of the target layer. Save A composite sheet may be used for forming the protective film.

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。 Furthermore, the composite sheet for protective film formation is usually stored in a state in which a release film is bonded to the surface of the outermost layer (for example, 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 release film (preferably the release-treated surface of the release film) to form For the composition of the surface layer, dry the composition as needed, thereby preliminarily forming a layer constituting the outermost layer on the release film, and using the above-mentioned Laminate the rest of the layers by either method, without removing the release film and keeping the bonded state unchanged.

◇保護膜形成用複合片的使用方法 ◇How to use the composite sheet for protective film formation

本發明之保護膜形成用複合片例如可利用以下所示之方法使用。 The composite sheet for protective film formation of this invention can be used by the method shown below, for example.

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，對保護膜形成用膜照射能量線，使保護膜形成用膜硬化而成為保護膜。接著，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(亦即以附有保護膜的半導體晶片之形式)自支持片拉離而進行拾取。 That is, the composite sheet for protective film formation is attached to the back surface (surface opposite to the electrode formation surface) of a semiconductor wafer via the film for protective film formation of this composite sheet for protective film formation. Next, energy rays are irradiated to the film for protective film formation, and the film for protective film formation is hardened and becomes a protective film. Next, the semiconductor wafer is divided together with the protective film by dicing to produce semiconductor wafers. Then, the semiconductor wafer is pulled away from the support sheet directly (that is, in the form of the semiconductor wafer with the protective film) while the protective film is still attached, and is picked up.

然後，利用與先前法相同的方法，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。 Then, the obtained semiconductor wafer with protective film was flip-chip connected to the circuit surface of the substrate by the same method as the previous method, and a semiconductor package was produced. Then, it is only necessary to manufacture a target semiconductor device using the semiconductor package.

再者，本文對使保護膜形成用膜硬化而成為保護膜後進行切割之情形進行了說明，但於使用本發明之保護膜形成用複合片之情形時，進行這些步驟之順序亦可相反。亦即，於半導體晶圓的背面貼附保護膜形成用複合片後，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而成為保護膜。隨後，與上述同樣地，將附有保護膜的半導體晶片自支持片拉離而進行拾取，製作目標半導體裝置即可。 In addition, although the case where cutting is performed after hardening the film for protective film formation into a protective film was demonstrated here, when using the composite sheet for protective film formation of this invention, the order of these steps may be reversed. That is, after affixing the composite sheet for protective film formation on the back surface of a semiconductor wafer, the semiconductor wafer is divided together with the film for protective film formation by dicing, and semiconductor wafers are produced. Next, the divided film for forming a protective film is irradiated with energy rays to harden the film for forming a protective film to form a protective film. Then, in the same manner as above, the semiconductor wafer with the protective film is pulled away from the support sheet and picked up to produce a target semiconductor device.

[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 specific examples. However, this invention is not limited at all by the Example shown below.

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

‧能量線硬化性成分 ‧Energy ray hardening ingredients

(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 ‧Polymers without energy ray hardening groups

(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 ( 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-morpholinophenyl)-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-methylbenzoyl)-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 diameter: 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-methacryloxypropyltrimethoxysilane ("KBM-503" manufactured by Shin-Etsu Chemical Co., 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 phthalocyanine-based blue pigment (Pigment Blue 15:3), 18 parts by mass of isoindolinone-based yellow pigment (Pigment Yellow 139), and anthraquinone-based red pigment (Pigment Red 177) A pigment obtained by mixing 50 parts by mass and performing pigmentation such that the total amount of the aforementioned 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 composite sheet for protective film formation>

(保護膜形成用組成物(IV-1)之製造) (Manufacture of protective film forming composition (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 curable 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 their contents (solid content, parts by mass) became the values shown in Table 1. Stirring was carried out at 23°C to prepare a protective film forming composition (IV-1) having a solid content concentration of 50% by mass.

(黏著劑組成物(I-4)之製造) (Manufacture of Adhesive Composition (I-4))

製備固形物成分濃度為30質量%之非能量線硬化性之黏著劑組成物(I-4)，該黏著劑組成物(I-4)含有丙烯酸系聚合物(100質量份，固形物成分)、及3官能苯二甲基二異氰酸酯系交聯劑(三井武田化學公司製造之「Takenate D110N」)(10.7質量份，固形物成分)，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，簡稱為「2EHA」)(36質量份)、BA(59質量份)、及HEA(5質量份)進行共聚合而成，且重量平均分子量為600,000。 Preparation of a non-energy ray-curable adhesive composition (I-4) having a solid content concentration of 30% by mass, the adhesive composition (I-4) containing an acrylic polymer (100 parts by mass, solid content) , and a trifunctional xylylene diisocyanate-based crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (10.7 parts by mass, solid content), and methyl ethyl ketone as a solvent. The aforementioned acrylic polymer is obtained by copolymerizing 2-ethylhexyl acrylate (hereinafter referred to as "2EHA") (36 parts by mass), BA (59 parts by mass), and HEA (5 parts by mass). And the weight average molecular weight was 600,000.

(支持片之製造) (Support the manufacture of the 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，塗敷上述所獲得之黏著劑組成物(I-4)，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。 Polysiloxane treatment on one side of polyethylene terephthalate film Apply the adhesive composition (I-4) obtained above to the peeling-treated surface of the peeling film ("SP-PET381031" manufactured by Lintec, thickness 38 μm), and heat and dry 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(楊氏率400MPa，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)-1。 Next, a polypropylene-based film (Young's modulus 400 MPa, thickness 80 μm) was attached as a base material to the exposed surface of the adhesive layer to obtain a support sheet having the adhesive layer on one surface of the base material. (10)-1.

(保護膜形成用複合片之製造) (Manufacture of composite sheets for protective film formation)

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。 The peeling-treated surface of the peeling film ("SP-PET381031" manufactured by Lintec, thickness 38 μm) that was peeled off by silicone treatment on one side of the polyethylene terephthalate film was coated with a knife coater. The protective film-forming composition (IV-1) obtained above was applied on a loom, and dried at 100° C. for 2 minutes to prepare an energy-ray-curable protective film-forming film (13)-1 with a thickness of 25 μm.

接著，自上述所獲得之支持片(10)-1之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 was removed from the adhesive layer of the support sheet (10)-1 obtained above, and the exposed surface of the protective film forming film (13)-1 obtained above was attached to the exposed surface of the adhesive layer. , producing a composite sheet for protective film formation in which the base material, the adhesive layer, the film (13)-1 for protective film formation, and the release film are sequentially laminated in the thickness direction of these composite sheets. Table 2 shows the composition of the obtained composite sheet for forming a protective film.

<保護膜形成用複合片之評價> <Evaluation of Composite Sheet for Protective Film Formation>

針對所獲得之保護膜形成用複合片，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，自支持片之側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。 The obtained composite sheet for protective film formation was hardened from the side of the support sheet under the conditions of illuminance 195mW/cm 2 and light intensity 170mJ/cm 2 using an ultraviolet irradiation device ("RAD2000m/8" manufactured by Lintec Co., Ltd.) The front test piece was irradiated with ultraviolet rays, thereby curing the film (13)-1 for forming a protective film, and obtaining a hardened test piece.

接著，針對該硬化後試片，移除基材及黏著劑層，針對保護膜形成用膜(13)-1硬化而成之保護膜的露出面，依據JIS Z 0237：2010，測定傾斜角30°下的球黏性值。測定結果示於表2。 Next, for the hardened test piece, the substrate and the adhesive layer were removed, and the exposed surface of the protective film formed by curing the protective film-forming film (13)-1 was measured according to JIS Z 0237:2010, and the inclination angle was measured at 30°. ° ball viscosity value. The measurement results are shown in Table 2.

(蓋帶附著性評價) (Cover Tape Adhesion 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，靜置30分鐘。 Attach the protective film forming composite sheet obtained above to the #2000 polished surface of a 6-inch silicon wafer (thickness 100 μm) through the protective film forming film (13)-1 of the protective film forming composite sheet , and further fix the sheet to a ring frame, and let it 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)-1側對保護膜形成用複合片照射紫外線，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 Co., Ltd.), under the conditions of illuminance 195mW/cm 2 and light intensity 170mJ/cm 2 , the composite sheet for protective film formation was applied from the support sheet (10)-1 side. By irradiating ultraviolet rays, the film (13)-1 for protective film formation is hardened|cured, and it becomes a protective film.

接著，使用切割刀片，將矽晶圓連同保護膜一起切割而單片化，獲得縱3mm×橫3mm、保護層厚度25μm、Si(矽)層厚350μm之矽晶片。 Next, use a dicing blade to cut the silicon wafer together with the protective film into individual pieces to obtain a silicon wafer with a length of 3 mm x width of 3 mm, a thickness of the protective layer of 25 μm, and a thickness of Si (silicon) of 350 μm.

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。 Next, use a die bonder ("BESTEM-D02" manufactured by Canon Machinery Co., Ltd.) to pick up 20 silicon wafers with protective films.

於縱12cm×橫12cm、厚度5mm之鐵板上，以相互間隔均等之方式將前述所獲得之16個附有保護膜之矽晶片以分別縱4個×橫4個載置於正方形之格子狀之位置，於上述矽晶片上被覆縱12cm×橫3.8cm之蓋帶(Sumitomo Bakelite公司製造，CSL-Z7302)，載置於加熱至40℃之熱盤上，於該熱盤上載置金屬板並以施加於附有保護膜之矽晶片之壓力成為350gf之方式進行設置，進行一分鐘過熱。然後，移除金屬板，剝離前述蓋帶，檢測附有保護膜之矽晶片是否附著於蓋帶。結果示於表2。 On an iron plate with a length of 12 cm x a width of 12 cm and a thickness of 5 mm, the 16 silicon wafers with protective films obtained above were placed in a square grid with 4 lengths x 4 widths at equal intervals. The above-mentioned silicon wafer is covered with a cover tape (manufactured by Sumitomo Bakelite, CSL-Z7302) with a length of 12 cm x a width of 3.8 cm, placed on a hot plate heated to 40 ° C, and a metal plate is placed on the hot plate and It was installed so that the pressure applied to the silicon wafer with a protective film became 350gf, and it overheated for 1 minute. Then, remove the metal plate, peel off the cover tape, and detect whether the silicon wafer with the protective film is attached to the cover tape. The results are shown in Table 2.

作為判定方法，於16個附有保護膜之矽晶片中至少一個附著於蓋帶之情形時判定為「A」，於16個附有保護膜之矽晶片中沒有一個附著於蓋帶之情形時判定為「B」。 As a judgment method, it is judged as "A" when at least one of the 16 silicon wafers with a protective film is attached to the cover tape, and when none of the 16 silicon wafers with a protective film is attached to the cover tape The judgment is "B".

[實施例2] [Example 2]

<保護膜形成用複合片之製造及評價> <Manufacture and Evaluation of Composite Sheet for Protective Film Formation>

如表1所示，將能量線硬化性成分(a2)-1的含量(調配量)20質量份替換為30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, except that 20 parts by mass of the energy ray-curable component (a2)-1 content (preparation amount) was replaced by 30 parts by mass, a protective film was prepared by the same method as in Example 1. Composition (IV-1).

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)-25。 An energy ray curable protective film forming film (13)-25 having a thickness of 25 μm was produced in the same manner as in Example 1 except using the protective film forming composition (IV-1) obtained above.

並且，將保護膜形成用膜(13)-1替換為該保護膜形成用膜(13)-25，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。所獲得之保護膜形成用複合片 之構成示於表2。 And the composite sheet for protective film formation was manufactured by the method similar to Example 1 except having replaced the film (13)-1 for protective film formation with this film (13)-25 for protective film formation. The obtained composite sheet for protective film formation The composition is shown in Table 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，進行球黏性值之測定及蓋帶附著性評價。結果示於表2。 Using the composite sheet for forming a protective film obtained above, the measurement of the ball tack value and the evaluation of the cover tape adhesion were performed by the same method as in Example 1. The results are shown in Table 2.

[實施例3] [Example 3]

<保護膜形成用複合片之製造及評價> <Manufacture and Evaluation of Composite Sheet for Protective Film Formation>

如表1所示，將光聚合起始劑(c)-1的含量(調配量)0.3質量份替換為1.0質量份，將光聚合起始劑(c)-2的含量(調配量)0.3質量份替換為1.0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, 0.3 parts by mass of the content (preparation amount) of the photopolymerization initiator (c)-1 is replaced by 1.0 parts by mass, and the content (preparation amount) of the photopolymerization initiator (c)-2 is 0.3 parts by mass. Except having replaced mass parts with 1.0 mass parts, the composition (IV-1) for protective film formation was prepared by the method similar to Example 1.

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)-26。 An energy ray curable protective film forming film (13)-26 having a thickness of 25 μm was produced in the same manner as in Example 1 except using the protective film forming composition (IV-1) obtained above.

並且，將保護膜形成用膜(13)-1替換為該保護膜形成用膜(13)-26，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。所獲得之保護膜形成用複合片之構成示於表2。 And the composite sheet for protective film formation was manufactured by the method similar to Example 1 except having replaced the film (13)-1 for protective film formation with this film (13)-26 for protective film formation. Table 2 shows the composition of the obtained composite sheet for forming a protective film.

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，進行球黏性值之測定及蓋帶附著性評價。結果示於表2。 Using the composite sheet for forming a protective film obtained above, the measurement of the ball tack value and the evaluation of the cover tape adhesion were performed by the same method as in Example 1. 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 Composite Sheet for Protective Film Formation>

如表1所示，將能量線硬化性成分(a2)-1的含量(調配量)20質量份替換為5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, except that 20 parts by mass of the energy ray-curable component (a2)-1 content (preparation amount) was replaced by 5 parts by mass, a protective film was prepared by the same method as in Example 1. Composition (IV-1).

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)-27。 An energy-ray-curable protective film-forming film (13)-27 having a thickness of 25 μm was produced in the same manner as in Example 1 except using the protective film-forming composition (IV-1) obtained above.

並且，將保護膜形成用膜(13)-1替換為該保護膜形成用膜(13)-27，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。所獲得之保護膜形成用複合片之構成示於表2。 And the composite sheet for protective film formation was manufactured by the method similar to Example 1 except having replaced the film (13)-1 for protective film formation with this film (13)-27 for protective film formation. Table 2 shows the composition of the obtained composite sheet for forming a protective film.

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，進行球黏性值之測定及蓋帶附著性評價。結果示於表2。 Using the composite sheet for forming a protective film obtained above, the measurement of the ball tack value and the evaluation of the cover tape adhesion were performed by the same method as in Example 1. The results are shown in Table 2.

[比較例2] [Comparative example 2]

<保護膜形成用複合片之製造及評價> <Manufacture and Evaluation of Composite Sheet for Protective Film Formation>

如表1所示，將光聚合起始劑(c)-1的含量(調配量)0.3質量份替換為0.1質量份，將光聚合起始劑(c)-2的含量(調配量)0.3質量份替換為0.1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, 0.3 parts by mass of the content (preparation amount) of the photopolymerization initiator (c)-1 is replaced by 0.1 parts by mass, and the content (preparation amount) of the photopolymerization initiator (c)-2 is 0.3 parts by mass. Except having replaced mass parts with 0.1 mass parts, the composition (IV-1) for protective film formation was prepared by the method similar to Example 1.

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)-28。 An energy ray curable protective film forming film (13)-28 having a thickness of 25 μm was produced in the same manner as in Example 1 except using the protective film forming composition (IV-1) obtained above.

並且，將保護膜形成用膜(13)-1替換為該保護膜形成 用膜(13)-28，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。所獲得之保護膜形成用複合片之構成示於表2。 And, replace the protective film forming film (13)-1 with this protective film forming The composite sheet for protective film formation was produced by the method similar to Example 1 except the film (13)-28. Table 2 shows the composition of the obtained composite sheet for forming a protective film.

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，進行球黏性值之測定及蓋帶附著性評價。結果示於表2。 Using the composite sheet for forming a protective film obtained above, the measurement of the ball tack value and the evaluation of the cover tape adhesion were performed by the same method as in Example 1. The results are shown in Table 2.

Figure 106113974-A0305-02-0101-1
Figure 106113974-A0305-02-0101-1
Figure 106113974-A0305-02-0102-2
Figure 106113974-A0305-02-0102-2

Figure 106113974-A0305-02-0102-3
Figure 106113974-A0305-02-0102-3

根據上述結果可明確，於使用實施例1至實施例3之保護膜形成用複合片之情形時，保護膜依據JIS Z0237：2010於傾斜角30°下所測定之球黏性值為2以下，附有保護膜的半導體晶片附著於蓋帶之情形得到抑制。 From the above results, it is clear that when the protective film-forming composite sheets of Examples 1 to 3 are used, the ball viscosity value of the protective film measured at an inclination angle of 30° in accordance with JIS Z0237:2010 is 2 or less. The adhesion of the semiconductor wafer with the protective film to the cover tape is suppressed.

[0284] [0284]

相對於此，於使用比較例1至比較例2之保護膜形成用複合片之情形時，推測若保護膜依據JIS Z0237：2010於傾斜角30°下所測定之球黏性值為3至4，則容易附著於蓋帶。 On the other hand, in the case of using the protective film-forming composite sheet of Comparative Example 1 to Comparative Example 2, it is estimated that if the protective film has a ball viscosity value of 3 to 4 measured at an inclination angle of 30° in accordance with JIS Z0237:2010 , it is easy to attach to the cover tape.

另外，於使用比較例1之保護膜形成用複合片之情形時，推測由於保護膜形成用組成物(IV-1)中，前述能量線硬化性成分(a)的含量相對於溶劑以外的成分的總含量之 比例少，為5.8質量%，故而能量線硬化不充分，前述球黏性值變大。另一方面，於使用比較例2之保護膜形成用複合片之情形時，推測保護膜形成用膜中的光聚合起始劑(c)的含量相對於能量線硬化性成分(a)之100質量份少，為1質量份，故而保護膜形成用複合片之硬化不充分，前述球黏性值變大。 In addition, in the case of using the protective film-forming composite sheet of Comparative Example 1, it is presumed that the content of the energy ray-curable component (a) in the protective film-forming composition (IV-1) is higher than that of components other than the solvent. of the total content of The proportion is as small as 5.8% by mass, so the energy ray hardening is not sufficient, and the aforementioned ball viscosity value becomes large. On the other hand, in the case of using the protective film forming composite sheet of Comparative Example 2, it is estimated that the content of the photopolymerization initiator (c) in the protective film forming film is 100% of the energy ray curable component (a). Since there were as few parts by mass as 1 part by mass, the hardening of the composite sheet for protective film formation was insufficient, and the said ball tack value became large.

(產業可利用性) (industry availability)

本發明可用於製造半導體裝置，故而於產業上有用。 Since the present invention can be used in the manufacture of semiconductor devices, it is industrially useful.

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

13:保護膜形成用膜 13: Film for protective film formation

13a:(保護膜形成用膜的)表面 13a: Surface (of film for protective film formation)

13b:(保護膜形成用膜中的與表面為相反側的另一方的)表面 13b: (the other side opposite to the surface in the film for forming a protective film) surface

15':第1剝離膜 15': 1st release film

15":第2剝離膜 15": 2nd release film

Claims (8)

一種保護膜形成用膜，為能量線硬化性之半導體晶圓或半導體晶片的背面保護膜形成用膜；前述保護膜形成用膜具有以下特性：照射能量線而成為保護膜時，依據JIS Z0237：2010於傾斜角30°下所測定之前述保護膜的球黏性值為2以下；相對於前述保護膜形成用膜的總質量，含有5質量%至83質量%的填充材料(d)。 A film for forming a protective film, which is an energy ray curable semiconductor wafer or a film for forming a protective film on the back surface of a semiconductor wafer; the film for forming a protective film has the following characteristics: when it is irradiated with energy rays to form a protective film, according to JIS Z0237: The ball viscosity value of the protective film measured at an inclination angle of 30° in 2010 is 2 or less; with respect to the total mass of the protective film forming film, the filler (d) is contained in an amount of 5 mass % to 83 mass %. 如請求項1所記載之保護膜形成用膜，其中前述保護膜形成用膜係含有能量線硬化性成分(a)。 The film for forming a protective film according to Claim 1, wherein the film for forming a protective film contains an energy ray curable component (a). 如請求項2所記載之保護膜形成用膜，其中前述保護膜形成用膜進一步含有光聚合起始劑(c)。 The film for forming a protective film according to claim 2, wherein the film for forming a protective film further contains a photopolymerization initiator (c). 如請求項3所記載之保護膜形成用膜，其中相對於能量線硬化性成分(a)100質量份，前述光聚合起始劑(c)的含量為2.0質量份至12.0質量份。 The film for forming a protective film according to claim 3, wherein the content of the photopolymerization initiator (c) is 2.0 to 12.0 parts by mass relative to 100 parts by mass of the energy ray curable component (a). 如請求項1所記載之保護膜形成用膜，其中前述填充材料(d)的平均粒徑為0.01μm至20μm。 The film for forming a protective film according to claim 1, wherein the filler (d) has an average particle diameter of 0.01 μm to 20 μm. 一種保護膜形成用複合片，係於支持片上具備如請求項1至5中任一項所記載之保護膜形成用膜。 A composite sheet for forming a protective film comprising the film for forming a protective film according to any one of Claims 1 to 5 on a support sheet. 一種能量線硬化性膜的用途，係用以製造半導體晶圓或半導體晶片的背面保護膜形成用膜；前述能量線硬化性膜具有以下特性：對前述能量線硬化性膜照射能量線而成為保護膜時，依據JIS Z0237：2010於傾斜角30°下所測定之前述保護膜的球 黏性值為2以下；且相對於前述能量線硬化性膜的總質量，含有5質量%至83質量%的填充材料(d)。 An application of an energy ray curable film for manufacturing a semiconductor wafer or a film for forming a backside protective film of a semiconductor wafer; the energy ray curable film has the following characteristics: the energy ray curable film is irradiated with energy rays to form a protective film. When filming, according to JIS Z0237:2010, the ball of the above-mentioned protective film is measured at an inclination angle of 30° The viscosity value is 2 or less; and the filler (d) is contained in an amount of 5 mass % to 83 mass % with respect to the total mass of the energy ray curable film. 一種能量線硬化性膜以及支持片的用途，係用以製造半導體晶圓或半導體晶片的背面保護膜形成用複合片；於前述支持片上具備前述能量線硬化性膜；前述能量線硬化性膜具有以下特性：對前述能量線硬化性膜照射能量線而成為保護膜時，依據JIS Z0237：2010於傾斜角30°下所測定之前述保護膜的球黏性值為2以下；且相對於前述能量線硬化性膜的總質量，含有5質量%至83質量%的填充材料(d)。 A use of an energy ray curable film and a support sheet for manufacturing a semiconductor wafer or a composite sheet for forming a backside protective film of a semiconductor wafer; the aforementioned support sheet is provided with the aforementioned energy ray curable film; the aforementioned energy ray curable film has The following characteristics: when the above-mentioned energy ray curable film is irradiated with energy rays to form a protective film, the spherical viscosity value of the above-mentioned protective film measured at an inclination angle of 30° in accordance with JIS Z0237:2010 is 2 or less; and relative to the above-mentioned energy The total mass of the line curable film contains 5% by mass to 83% by mass of the filler (d).
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